description stringlengths 2.98k 3.35M | abstract stringlengths 94 10.6k | cpc int64 0 8 |
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FIELD OF THE INVENTION
This invention relates generally to chain saws, and more particularly to a saw chain cutter design which permits cutting a wide variety of materials while reducing dulling and breakage.
BACKGROUND OF THE INVENTION
Chain saws have been available for several decades. The chains used in chain saws commonly include drive links which engage into a power sprocket, connecting links and cutter elements. Such saw chains have been primarily intended for cutting wood. It has been found, however, that chain saws can be used to cut many different substances in addition to wood. Materials which can be cut by chain saw means include pumice stone, brick, tile, asbestos cement board, stucco, pipe and frame house and roof structures, which include shingles of a variety of materials including nails, joists, hangers and gravel and stone on top of built-up roofs. Firefighters have to use chain saws for cutting house structures on an emergency basis.
An extensive amount of prior art describes various chains developed for many cutting purposes. The known prior art traces attempts to develop a cutter more resistant to blunting and shock destruction than the conventional stamped-out steel cutter commonly used by the wood industry. A number of inventions relate to the shape of the cutting element and also to the use of hard metal alloy inserts, such as carbide compositions attached to steel supports. The prior art generally shows permanent attachments, that is, connecting of a hard metal insert to a body element by braising or soldering, for example. This type of structure is shown in U.S. Pat. Nos. 3,292,675, 2,976,900, 2,862,533, 2,798,517 and 4,606,253. U.S. Pat. Nos. 2,746,494 and 2,994,350 describe hard metal cutting inserts which are removable from the cutter body. The known prior art is primarily concerned with cutters having cutting edges which are rectangular or L-shaped, and which, due to the rapid movement of the chain, act as chisels, chipping away the material.
No prior art teaches the concept of effectively protecting the entire scope of the cutting edges from the effects of sudden impacts of hard material. Only U.S. Pat. Nos. 3,292,675 and 4,606,253 acknowledge or describe an attempt to remedy the impact problem. The '253 patent concerns a chain using a carbide composition insert supported by a steel element having two parallel flanks and made from a single piece of bent steel of relatively low hardness, intended to withstand the impact shock without detaching the cutting insert. This design, however, does not protect the carbide insert from frontal impact. The softness of the steel from which the chain links are manufactured causes rapid lengthening of the chain during cutting, which in turn may cause the chain to disengage itself from the leading groove of the saw bar or the sprocket or both.
The '675 patent claims a chain adequate for cutting through the mixed materials. It concerns an L-shaped cutter element of carbide with the cutting edge only partially mating with a notch in an L-shaped body of the cutting link.
SUMMARY OF THE INVENTION
Broadly speaking, this invention involves a new cutter element for chains which move rapidly and unidirectionally for the purpose of cutting through various materials. Such chains are predominantly, but not exclusively, used as cutting devices in power chain saws and the like.
A primary objective of this invention is a novel cutter link and cutter element to be incorporated with a chain which cuts rapidly through various materials of different hardness, is resistant to dulling and, more importantly, is able to withstand shock when, in a relatively soft material such as wood, a hard substance such as metal or mineral is encountered during cutting. This need is especially evident in applications such as cutting rapidly through various inhomogenous debris, such as encountered in natural catastrophe containment, for example, home fire, military use and in cutting through timber containing rock or sand. This objective is accomplished by the novel shape and design of the cutter element, providing long lasting sharpness and resistance to impact. One advantage resulting from this novel structure is that the cutting elements in the chain act more as files than as chisels.
The cutter of this invention can readily be incorporated as a component into the construction of existing conventional saw chains. The cutter is provided with a cutting edge being the circumference of a round or a semilunar plate which can be an integral part of the cutter, or be made from a hard metal firmly attached to the support body. The cutting face is effectively protected against frontal impact by a conical raker placed in front of the face's entire operative circumference. Unlike the prior art which generally describes cutter faces with cutting edges of rectangular shapes, this invention provides for a round face with its cutting edge being approximately the entire operative circumference of the face's frontal aspect.
The cutting element may be an integral portion of the body of the cutter chain link. Alternatively, the cutting element may be an insert secured to the body by appropriate means.
BRIEF DESCRIPTION OF THE DRAWING
The objects, advantages and features of the invention will be more clearly perceived from the following detailed description, when read in conjunction with the accompanying drawing, in which:
FIG. 1 shows a section of saw chain of the prior art;
FIG. 2 is an enlarged top view of the cutting link of the prior art device;
FIG. 3 is an enlarged perspective view of a saw chain cutting link constructed in accordance with the invention;
FIG. 4 is a side view of the link of FIG. 3;
FIG. 5 is a top view of the link of FIG. 3;
FIG. 6 is an end view of the link of FIG. 3;
FIG. 7 is a side view similar to FIG. 4 of an alternative embodiment cutting link;
FIG. 8 is a top view of the cutting link of FIG. 7;
FIG. 9 is an end view of the cutting link of FIG. 7;
FIG. 10 is a perspective view similar to FIG. 3 of another embodiment of the cutting link of the invention;
FIG. 11 is a side view of the cutting link of FIG. 10; and
FIG. 12 is a top view of the cutting link of FIG. 10.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
With reference now to the drawing, and more particularly to FIGS. 1 and 2, there is shown a segment of saw chain of the prior art. This cutting chain is intended to be used for cutting hard type materials such as brick, tile, and asbestos cement board, and mixed material items such as frame house structures and roof structures, without requiring the cutting elements to be touched up or sharpened on a very frequent basis. It is intended to withstand severe impacts without separating the cutting element from the body or cutting link.
The chain of FIG. 1 is comprised of three different elements, a multiplicity of which are connected together to form the continuous chain. Each of these elements is connected together by specific types of rivets, sometimes referred to as pintles, which allow one element to pivot with respect to the element to which it is coupled. Connecting side links 11 interconnect sprocket drive lugs 12 by means of pintles 13. Normally two connecting links are required for each connection of two drive lugs, one on each side. Alternating positions of the connecting links on the chain include cutter links 14 and 15 replacing one of connecting links 11. These cutter links are positioned on alternating sides of the chain as shown in FIG. 1. For example, cutter link 14 is shown on the upward side of the chain in the plane of the paper and cutter link 15 is shown on the lower side of the chain. This alternating arrangement is normal in saw chains, much like a typical saw of any type which has alternating teeth set in opposite directions with respect to the center line of the movement direction of the teeth. Pintles 13 are also used for connecting cutter links 14 and 15 to drive lugs 12 in conjunction with one of the connecting links.
Cutter link 15 is shown in FIG. 2 having cutting element or tip 16 having face 17 offset from a perpendicular to the line of travel 18 by an angle indicated by reference normal 21. This results in a sharp leading point 22. Preceding the cutting element as it passes through the material being cut is depth gauge 23 spaced forwardly of the cutting edge. The purpose of the depth gage is to limit the depth of bite for the cutting tips as they engage the material being cut. Note that the cutting tip of the prior art acts as a chisel, removing chunks of material as it passes through the kerf which the saw creates.
One embodiment of the cutting tip of the invention is shown in FIGS. 3-6. Base 36 of cutter link 31 is formed substantially the same as the equivalent prior art devices. Lobes 32 and 33 are made to accommodate openings 34 and 35 through which the pintles pass to connect the cutter link to the drive lugs of the chain, in conjunction with connecting links. The cutter link is provided with a hard steel body comprised of base 36 on top of which is cutting element 37 having cutting face 41 of circular or semilunar shape. On the forward top part of the cutter link, aligned with the longitudinal axis of cutting element 37, is conical raker 42 having a crest 43 at its superior aspect and a circular profile 44 at its posterior aspect.
Cutting face 41 has a cutting angle θ (FIG. 4) typically ranging between 3° and 20°, and a rake angle α (FIG. 5), typically ranging between 10° and 45°. For cutting hard materials such as would be expected on a gravel covered asphalt roof, and when expecting sudden impact in the cut material such as nails, the cutting angle will preferably be in the range of 8° to 15° and the rake angle will be in the range of 15° to 25°. When cutting predominantly homogenous and softer materials, such as wood, the preferred cutting angle will be in the range of 10° to 20° and the rake angle would preferably be about 30° to 4520 . The cutting angle θ is the angle between face 41 and the vertical plane (FIG. 4). The rake angle α is the angle between face angle 41 and the transverse plane (FIG. 5).
None of the prior art devices provides for effective protection of the entire cutting face and cutting edge against impact. This is understandable, since the previously described cutting elements generally are either L-shaped, rectangular, or nearly rectangular. The prior art only describes "depth gauges", that is, teeth-shaped promontories protruding upwardly from the frontal part of the cutter base, generally having the same thickness as the base, and mating with the cutting face, although minimally (see FIG. 2).
The cutting element of this invention is distinctly different from the prior art. It is especially designed to be a round face. The face's cutting edge can be either a full circle or a substantial part of a circle. The diameter of the cutter face is generally in the range of 0.12 to 0.38 inch. Nearly the entire face 41 is solidly protected by the anteriorly placed raker. The shape of raker face 44 roughly matches cutter face 41 except the average diameter of face 44 is somewhat smaller to allow for exposure of cutting edge 45 as shown in FIG. 6. Typically, the difference in the average diameter will vary from 0.0005 to 0.050 inch and will most typically be about 0.015 inch for cutting hard material and for use in situations when sudden impact is expected. The diametrical difference will typically be about 0.040 inch when homogenous, soft materials such as wood is being cut. Different cutter link configurations are provided for the expected use of the saw chain. When viewed in the lateral plane, the raker has a bullet-shape with crest 43 allowing for the pre-scoring of the cut material. The gradual increase of the raker in its anterior/posterior aspect serves to deflect any suddenly encountered inhomogenous substances. The difference in diameter with respect to the cutter face enables the saw chain to function as a file rather than as a group of chisels.
The embodiment of FIGS. 3-6 is a hard steel body 37 which has an integral cutting face 41, which is protected by solid, bullet-shaped raker 42. An alternative embodiment is shown in FIGS. 7-14 9, having an identical raker 51 on an identical base 52 but with a two-piece cutter portion, body 53 and cutter element 54. The cutter element is secured by welding or brazing or other suitable means to body 53. Notch 55 in the body receives tab 56 on the cutter element for proper mating alignment. Cutter element 54 is preferably made of a carbide composition which holds a cutting edge very well. Otherwise this embodiment has the same shape and functions in the same way as the embodiment of FIGS. 3-6.
Another embodiment of the cutter link is shown in FIGS. 10-12. Body 61 is formed from a stamped plate formed through a series of dies into a cylinder. This cylinder receives cutter element 62 on the forward end. The cutter element is preferably formed with a rearward projection 63 which provides mating alignment. That projection may be cylindrical or have any desired shape with at least three side points which engage or lie closely adjacent the inside surface of cylindrical body 61. These components may be secured together by soldering, brazing, welding, or by other suitable means.
Raker 64 is similarly formed into a cone from a flat stamped plate by a series of dies. Both the body or the raker, or both, are spot welded, laser welded, or otherwise suitably secured to base 65. Note that the body and raker of this embodiment may not be completely rounded but may be formed with a gap the width of base 65 with the elongated edges welded to the base.
The body and raker of the other embodiments could be made integral with their respective bases, or they could be separate elements welded to the base.
Actual testing has been conducted to determine how the cutter of this invention performs compared with other cutters in identical chains. The other cutters advertise the ability to effectively cut through the various materials discussed above.
This cutter was incorporated into a 3/8" chain base and tested in a double blind experiment against commercially available carbide-tip chains sold under the names Repco 404 and Stihl Duro, all mounted on identically performing motor saws of the same type and origin. The test consisted of four consequential cuts to a total of a 60 linear feet, through a prop simulating a wood/tar/felt paper with gravel and/or corrugated metal roof construction of the type prevalent in the United States. This was immediately followed by perpendicular cuts through standard construction nails ("16 penny") of about 3 millimeters diameter and inserted longitudinally in wooden beams. The results are shown in Table 1.
TABLE 1__________________________________________________________________________ Elements of Damage Elements of Damage Saw Speed Cutter Average Duration of After 60 Feet and 4 Nails After Additional 14 Nails RPM Max % Temperature °C. 60 Feet Cut Cut- Dull- Carbide Cut- CarbideChain Start Decrease After 60 Feet Cut (min/sec) ter ing Chip Loss ter Dulling Chip Loss__________________________________________________________________________STIHL DURO 12,500 39.02 153 1.54 / yes / / 11 yes 7 19*REPCO 404 12,500 40.08 162.5 1.50 5 no / 17 not applicable due to previous damageINVENTION 12,500 41.06 167.5 1.52 / no / / 1 yes 1 4__________________________________________________________________________ *Could not be tested further due to the extensive damage
In conclusion, while there were no significant differences in the saw speed, cutter temperature or speed of cutting, only the chain with cutters made in accordance with this invention remained operational at the conclusion of the test.
In view of the above description, it is likely that modifications and improvements will occur to those skilled in the art which are within the scope of the accompanying claims. | A cutter link for a chain saw chain containing a conical raker spaced forward of a round cutter face. The raker protects most of the cutter face from sudden impact and, together with the cutting and rake angles of the cutter face, provides for a filing rather than a chiseling action by the cutter link. Saw chains incorporating the novel cutter link are impact and wear resistant. | 1 |
FIELD OF THE INVENTION
This invention relates to water reducible or dispersible polyester resin compositions useful as textile sizes. It also relates to a method of preparing such polyester resin compositions by increasing the molecular weight of the polyester resin after it is dispersed in water.
BACKGROUND OF THE INVENTION
It is known that water dispersible polyester resins may be prepared by partially reacting trimellitic anhydride (TMA) with hydroxy terminated polyesters to produce polyesters containing sufficient carboxyl groups to make the polyester resin water soluble. This reaction is shown schematically below: ##STR1## The resulting polyester composition is poured into water which contains an amine dispersing agent, e.g. triethyl amine. However, in order to avoid rapid boiling and foaming of the water/amine solution, the temperature of the molten polyester must be less than about 200°-220° C. Since the temperature at which the polyester remains molten is a function of the resin's Tg and molecular weight, an effective upper limit is thus placed on them. Also, if the Tg and molecular weight of the polyester is too high, the polyester will solidify or become too viscous in the water/amine mixture (even if the water/amine mixture is kept close to boiling) before the polyester can be dispersed. The addition of solvent to the polyester before dispersing it, in an effort to obviate these problems, is undesirable since the flash point would be lowered and organic pollutants to the atmosphere increased when the product is ultimately dried.
Known water dispersible polyesters include those sold by Eastman Chemical Products, Inc. under the designations WD 3652, WD 9519, WJL 6342, FPY 6762 and MPS 7762. These polyesters are described as having molecular chains whose end groups are mostly primary hydroxyl groups, and which have sodium sulfonate groups positioned along the molecular chain at random intervals. These sodium sulfonate groups contribute to water dispersibility. Also available from Eastman is an air-drying water-reducible alkyd enamel prepared from a resin designated as WA-17-2T. This resin is prepared from 10.56 eq. of TMPD glycol (2,2,4-trimethyl-1,3-pentanediol), 8.12 eq. of pentaerythritol, 9.00 eq. of isophthalic acid, and 4.43 eq. of linoleic fatty acid. The resulting polymer is then reacted with 4.72 eq. of trimellitic anhydride. Other Eastman products containing water-reducible polyesters are WS-3-1C, WA-17-6C and WS-3-2C enamels. WS-3-1C enamel is prepared from a polyester made from 17.16 eq. of 1,4-cyclohexanedimethanol; 8.59 eq. of trimethylolpropane; 14.85 eq. of phthalic anhydride and 10.90 eq. of adipic acid. WA-17-6C enamel is prepared using a polyester made from 5.94 eq. of 1,4-cyclohexanedimethanol; 15.10 eq. pentaerythritol; 8.67 eq. isophthalic acid; 3.18 eq. benzoic acid and 3.65 eq. linoleic fatty acid. The resulting polymer is further reacted with 3.93 eq. of trimellitic anhydride. WS-3-2C enamel employs a polyester prepared from 7.12 eq. 1,4-cyclohexanedimethanol; 1.40 eq. trimethylolpropane; 4.17 eq. phthalic anhydride and 2.78 eq. adipic acid.
High molecular weight (i.e., over 4500 molecular weight) water reducible polyester resins have also been developed by Amoco Chemicals Corporation. One such resin is a polyester diol of isophthalic acid and glycol which is coupled with trimellitic anhydride. The prepolymer mole ratio of isophthalic acid to glycol must be at least 4:5 and near stoichiometric amounts of trimellitic anhydrides are used. A typical such resin is prepared from 120 moles of isophthalic acid (or an 85/15 isomer blend of isophthalic and terephthalic acids) and 140 moles of diethylene glycol. Twenty moles of the resulting prepolymer diol is then reacted with 21 mole of trimellitic anhydride. Similar Amoco polyesters are prepared by reacting the same ingredients described above, except that the glycol component contains 91 moles of diethylene glycol and 49 moles of 1,4-cyclohexanedimethanol.
U.S. Pat. No. 3,546,008, issued Dec. 8, 1970 to Shields, et al. discloses sizing compositions containing linear, water-dissipatable polyesters derived from at least one dicarboxylic acid component, at least one diol component (at least 20 mole percent of the diol component being a poly (ethylene glycol)), and a difunctional monomer containing a --SO 2 M group attached to an aromatic nucleus, where M is hydrogen or a metal ion.
U.S. Pat. No. 3,563,942, issued on Feb. 16, 1971 to Helberger, discloses linear copolyester compositions which can be dispersed in aqueous mediums. Water dispersibility is gained by the addition to the copolyesters of the metal salt of a sulfonated aromatic compound.
U.S. Pat. No. 3,734,874, issued May 22, 1973 to Kibler, et al., discloses water-dissipatable, meltable polyesters and polyesteramides. A polyester said to be typical is composed of 80 mole parts of isophthalic acid, 10 mole parts of adipic acid, 10 mole parts of 5-sodiosulfoisophthalate, 20 mole parts of ethylene glycol and 80 mole parts diethylene glycol.
U.S. Pat. No. 4,148,779, issued Apr. 10, 1979 to Blockwell, et al., discloses water-dispersible dye/resin compositions which are solutions of disperse dyes in, for example, copolyesters of 5-sodiosulfoisophthalic acid optionally blended with aliphatic or cycloaliphatic dicarboxylic acids.
U.S. Pat. No. 4,391,934, issued July 5, 1983 to Lesley, et al., discloses dry textile warp size compositions containing a polyester in particulate form, a film former and, optionally, a lubricant. The preferred polyester resin is produced by reacting a glycol such as diethylene glycol with a dicarboxylic acid, e.g., isophthalic acid, and trimellitic anhydride.
U.S. Pat. No. 4,401,787, issued Aug. 30, 1983 to Chen, discloses polyester latex compositions which contain a polyester having from 0.5 to 5.0 mole percent dicarboxylic acid derived repeating units having a component selected from salts of alkali metal or ammonium iminodisulfonyl and alkali metal or ammonium sulfonate.
U.S. Pat. No. 4,493,872, issued Jan. 15, 1985 to Funderburk, et al., discloses a water dispersible copolyester made from 65 to 90 mole percent of isophthalic acid, 0 to 30 mole percent of at least one aliphatic dicarboxylic acid, 5 to 15 mole percent of at least one sulfomonomer containing an alkali metal sulfonate group attached to a dicarboxylic aromatic nucleus, and stoichiometric quantities of about 100 mole percent of at least one copolyerizable aliphatic or cycloaliphatic alkaline glycol having 2 to 11 carbon atoms.
U.S. Pat. No. 4,525,419, issued June 25, 1985 to Posey, et al., discloses a water dispersible copolyester which is the condensation product of 60 to 70 mole percent of terephthalic acid, 15 to 25 mole percent of at least one dicarboxylic acid, greater than 6 up to 15 mole percent of at least one sulfomonomer containing an alkali metal sulfonate group attached to a dicarboxylic aromatic nucleus, and stoichiometric quantities of at least one aliphatic or cycloaliphatic alkylene glycol having 2 to 11 atoms.
SUMMARY OF THE INVENTION
In accordance with the present invention there is provided a process for preparing a dispersion of a polyester resin in water comprising:
(A) dispersing a molten carboxyl containing polyester in water which contains a neutralizing agent in an amount effective to disperse the polyester in the water;
(B) adding to the mixture produced in Step A an epoxide containing at least two epoxy groups per molecule capable of reacting with the carboxyl groups of the polyester in an amount less than that required stoichiometrically to react with all of the carboxyl groups while the mixture produced in step A is held at a temperature which will effect reaction of the carboxyl containing polyester and epoxide, but which is below the boiling point of the mixture; and
(C) mixing the product of step B until a dispersion is formed.
There is also provided in accordance with the present invention a process for preparing an aqueous dispersion of a polyester resin comprising:
(A) forming a carboxyl containing polyester resin which has a molecular weight and Tg which allows it to be dispersed in water by reacting a hydroxy terminated polyester and a stoichiometric excess of trimellitic anhydride;
(B) melting the product of step A and adding the molten product to water containing an effective amount of a dispersing agent;
(C) dispersing the product of step A in the water; and
(D) adding to the resulting dispersion an epoxide having at least two epoxy groups per molecule capable of reacting with the carboxyl group of the polyester resin, said epoxide being added in an amount less than that required stoichiometrically to react with all of the carboxyl groups and while the dispersion is held at a temperature which will effect reaction of the carboxyl containing polyester and epoxide, but which is below the boiling point of the dispersion.
In accordance with this invention there is further provided a chain extended, carboxyl containing polyester resin comprising a hydroxy terminated polyester condensation product of the following monomers or their polyester forming equivalents:
(A) about 49 to about 30 mole percent of a discarboxylic acid or mixture of dicarboxylic acids; and
(B) about 51 to about 70 mole percent of an aliphatic or cycloaliphatic glycol or mixture of aliphatic or cycloaliphatic glycols;
wherein about 20 to about 96 percent of the residual hydroxyl groups on the polyester have been reacted with trimellitic anhydride to form carboxyl groups on the polyester to yield an acid number of about 25 to about 90, and the polyester has been chain extended with an epoxide having at least two epoxy groups per molecule capable of reacting with the carboxyl groups in an amount sufficient to react with about 10 to about 90 percent of the carboxyl groups.
There is also provided in accordance with the present invention a chain extended, carboxyl containing polyester resin comprising the product produced by:
(A) forming a carboxyl containing polyester resin by reacting a hydroxyl terminated polyester resin and a stoichiometric excess of trimellitic anhydride; and
(B) chain extending the product by step A by reacting said product and an epoxide having at least two epoxy groups per molecule capable of reacting with carboxyl groups of said product in an amount less than that required stoichiometrically to react with all of the carboxyl groups of said product.
Further provided in accordance with this invention are aqueous dispersions comprising an aqueous continuous phase having dispersed therein a chain extended, carboxyl containing polyester resin comprising the product produced by:
(A) forming a carboxyl containing polyester resin by reacting a hydroxyl terminated polyester resin and a stoichiometric excess of trimellitic anhydride; and
(B) chain extending the product of step A by reacting said product and an epoxide having at least two epoxy groups capable of reacting with the carboxyl groups of said product in an amount less than that required stoichiometrically to react with all of the carboxyl groups of said product.
The present invention also provides a method of sizing a yarn or textile comprising applying to the yarn or textile a coating of an aqueous dispersion comprising an aqueous continuous phase having dispersed therein a chain extended, carboxyl containing polyester resin comprising the product produced by:
(A) forming a carboxyl containing polyester resin by reacting a hydroxyl terminated polyester resin and a stoichiometric excess of trimellitic anhydride; and
(B) chain extending the product of step A by reacting said product and an epoxide having at least two epoxy groups per molecule capable of reacting with the carboxyl groups of said product in an amount less than that required stoichiometrically to react with all of the carboxyl groups of said product; and
drying or curing said coating.
This invention also includes the yarn or textile product produced by the above process.
There is further provided in accordance with this invention a coated substrate wherein the coating comprises the product produced by drying or curing an aqueous dispersion which has been applied to the surface of the substrate and wherein said dispersion comprises an aqueous continuous phase having dispersed therein a chain extended, carboxyl containing polyester resin comprising the product produced by:
(A) forming a carboxyl-containing polyester resin by reacting a hydroxyl terminated polyester resin and a stoichiometric excess of trimellitic anhydride; and
(B) chain extending the product of step A by reacting said product and an epoxide having at least two epoxy groups capable of reacting with the carboxyl groups of said product in an amount less than that required stoichiometrically to react with all of the carboxyl groups of said product.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention relates to the concept that reacting multifunctional epoxy resins with water dispersed polyester resins that contain residual unreacted carboxyl groups gives higher molecular weight polyesters with enhanced physical properties. This reaction also allows the polymers to be crosslinked more readily due to increased hydroyl groups that are generated along the polyester backbone as the epoxy groups react with carboxyl groups.
The polyester resin dispersions and the method for making them may be outlined schematically as follows:
A. Produce Hydroxy Terminated Polyester
A hydroxy terminated polyester prepolymer is produced by reacting a slight excess (e.g. 14 moles) of a glycol with a dicarboxylic acid (e.g. 12 moles). The reaction can be depicted as: ##STR2##
B. Produce Carboxyl Containing Polyester
Excess trimellitic anhydride (TMA) is reacted with part of the hydroxyl groups on the hydroxy terminated polyester to produce of polyester of acid no. of about 45-50. This reaction may be depicted as: ##STR3##
C. Disperse Carboxyl Containing Polyester
The carboxyl-containing polyester is poured molten (at 180°-220° C.) into a solution of hot triethyl amine and water. The triethyl amine neutralizes (or salts) the carboxyl groups on the polyester, as depicted below, and aids in dispersing it in the water. ##STR4##
D. Extension of Polyester with Epoxide
A portion of the carboxyl groups on the dispersed polyester is reacted with a multifunctional epoxide to increase the molecular weight of the resin and increase the number of hydroxyl groups along the polyester backbone to provide cure sites for later reaction with a curing agent, e.g. melamine resins. The chain extension is depicted as follows: ##STR5##
It is emphasized that the foregoing reaction scheme is intended to depict the reactions and products of the present invention only in a general manner so as to teach those skilled in the art how to make and use the present invention. It should be understood by those skilled in the art that many products and by-products other than the idealized structures indicated above will be produced when the present invention is practiced. Therefore, the above-depicted reaction scheme is intended for illustrative purposes only and is not intended to limit the present invention in any way.
The hydroxyl terminated polyester resins used to prepare the resins of the present invention may be made in a conventional manner from a dicarboxylic acid and a glycol. Suitable dicarboxylic acids include, but are not limited to isophthalic acid, terephthalic acid and adipic and other aliphatic acids. A mixture of isophthalic acid and terephthalic acid is preferred in order to prevent crystallization of the polyester. Suitable glycols include aliphatic glycols (such as ethylene glycol, butane diol, hexane diol), diethylene glycol and dimethylol propionic acid. A slight amount of trimethylol propane may also be advantageously added to the glycol to increase branching of the polymer. In preparing the hydroxyl terminated polyester a stoichiometric excess of the glycol is used in order to ensure that the polyester is hydroxyl terminated.
The compound used to provide carboxyl groups on the polyester is preferrably trimellitic anhydride (TMA) because of its high carboxyl content and functionality, but other compounds, such as phthalic anhydride or hexahydrophthalic anhydride may be used. These latter compounds, while not forming products identical to products made from TMA, do provide dispersions with the same characteristics and benefits of those made from TMA. Accordingly, for the purpose of this invention, these other anhydrides (and their products) are considered to be equivalent to TMA. Normally, about 10 to about 96 percent of the residual hydroxyl groups on the polyester are reacted with TMA to form carboxyl groups on the polyester. The resulting carboxyl-containing polyester has an acid number from about 25 to about 90.
Any base which will neutralize or salt the carboxyl groups on the polyester and render the resin water soluble may be employed as the neutralizing agent. Use of such neutralizing agents assists in dispersing the carboxyl containing polyester in the water. Examples of such bases include, but are not limited to, ammonia, alkyl amines (such as triethyl amine and tributyl amine), alkali metal hydroxides (such as NaOH and KOH), and alkanol amines (such as triethanol amine). A sufficient amount of base should be employed to salt substantially all of the carboxyl groups.
The epoxy compounds used to chain extend the polyester can be any of many readily available epoxy-containing compounds. Materials such as EPON 828 resin, Ciba GY-9482 resin and EPI-REZ resin 510 (epoxy resins which are all glycidyl ethers of bisphenol A) are typical examples. Epoxies such as EX-614 (tetrafunctional epoxy sorbitan), Dow DEN-438 resin (epoxy novalac), EPI-REZ 5048 resin (trifunctional aliphatic epoxy) and XU-238 resin (difunctional epoxy hydantoin) may also be used. Of these, the glycidyl ethers of bisphenol A are preferred. Normally, an amount of epoxy compound is employed such that about 10 to about 90 percent of the carboxyl groups on the polyester are chain extended with the epoxy compound.
The dispersions of the present invention comprise about 30-50 weight percent (on a solids basis) of the chain extended polyesters of this invention, the neutralizing base and the balance water. A surfactant may optionally be employed to increase the stability of the dispersion.
The dispersions of this invention are useful as sizes for textile yarns, such as nylon acetate or filament polyester yarn. The size is coated onto the yarn to protect the yarn from abrasion during the weaving process whereby the yarn is woven into fabric. In a typical such process, the polyester yarn is unwound from a creel frame and passed through a size box which contains the textile size at about 8-10% solids in water. The excess size is squeezed off through nip rolls and dried over steam heated dry cans (at about 200°-250° F.) until the yarn is dried to a moisture regain of 0.4 to 1.0%. The dried yarns are then separated from one another by a series of split rods and wound side by side onto a loom beam under controlled tension. The loom beam is then ready for weaving.
The continuous yarns with the applied size on the loom are known as the warp yarn. The unsized yarn that is attached to the shuttle and travels back and forth through the warp yarn is known as the fill yarn. It is the primary purpose of the resin size to act as a protective agent for the warp yarn against the abrasive forces that are encountered during weaving. (A break in one warp yarn requires the shutdown of the loom for retieing). The size coats each individual filament of the warp yarn and bonds all of the filaments together.
After the fabric is woven, the polyester size may be removed by subjecting the fabric to a mild alkaline scour (typically 0.2% sold ash and 0.2% surfactant with a bath temperature of 180°-200° F.). The scoured textile is then passed over dry cans and approximately 0.5% of the dried yarn weight would be retained size.
For some applications it is desirable to make the resin size permanent on the fabric. For instance, it may be used as a binder to hold pigment or dyestuff to the yarn. This process is known as slasher dyeing wherein pigment or dyestuff and a crosslinking or curing agent (such as a melamine) and a catalyst for the crosslinking or curing agent (such as citric acid when a melamine is used) are added to the slasher bath with the polyester resin size dispersion. The crosslinking agent crosslinks residual hydroxyl and carboxyl groups on the polyester to make the polyester size permanently hold the pigment or dyestuff to the yarn.
The dispersions of the present invention are also useful to coat substrates, e.g., polymeric films such as polyester film. The coating may be applied to the substrate to provide a gloss coating or as an adhesive layer between two substrates.
The present invention provides several advantages over the prior art. First, the method of making the polyester resins permits high molecular weight polyesters to be made without causing gellation of the resin and avoiding the aforementioned problem of causing the water/dispersing agent solution to boil upon addition of the molten resin to it. Second, the polyester resin dispersions of this invention provide sizes with excellent toughness, abrasion resistance, water release, resiliency and less water regain compared to the sizes currently available. Also, the reaction with the epoxides provides additional hydroxyl functionality to the polyester resin which aids in curing when the resin is crosslinked with, e.g., melamines.
EXAMPLE 1
This example illustrates the preparation of a hydroxy terminated polyester which may be used to prepare the polyester resins of the present invention.
The following starting materials were charged to a suitable reaction vessel at room temperature:
______________________________________Starting Material Moles Wt. %______________________________________Ethylene glycol 3.5 6.42Diethylene glycol 8.5 26.661,4-Butane diol 3.0 7.99Terephthalic acid 1.8 8.84Isophthalic acid 10.2 50.09______________________________________
The resulting reaction mixture was then heated to about 135° C. with a nitrogen sparge and about 0.1 wt% of a catalyst (Fascat 4100) was added to the reaction mixture. The reaction was continued for about 3.5 hours, with the temperature of the reaction mixture rising steadily to about 230° C. and approximately 435 g. of by-product water being produced fro a 3383 g. charge. The reaction was stopped and the product, a hydroxy terminated polyester resin, was stored under nitrogen overnite.
EXAMPLE 2
This example illustrates the preparation of a carboxyl-containing polyester resin which may be used to prepare the polyester resins of the present invention.
The hydroxy terminated polyester of Example 1 was heated in a suitable reaction vessel to about 160° C., and the esterification allowed to continue until the acid no. dropped from about 11.8 to about 2.9 during which time the temperature of the reaction mixture rose to about 243° C. and additional by-product water was given off.
The reaction mixture was then cooled to about 190° C. and 2.1 moles of trimellitic anhydride were added. The reaction mixture was heated to about 220° C. until an acid no. of about 45-47 was achieved.
The resulting carboxyl-containing polyester resin was maintained in a molten state at about 190° C. About 2550 g of the molten polyester was then poured into a hot (about 65°-70° C.) aqueous solution containing about 5750 g. deionized water and 202 g. triethyl amine, and the resin dispersed therein. The resulting dispersion contained about 30% solids.
EXAMPLE 3
This example illustrates the chain extension of a carboxyl-containing polyester with a multifunctional epoxide to produce an aqueous dispersion of a polyester resin of this invention.
About 8500 g of the dispersion produced in Example 2 was charged to a suitable reaction vessel and heated to about 55° C. About 141 g of a multifunctional epoxy resin (a liquid epoxy resin having an epoxide equivalent of 195 and a viscosity at 25° C. of about 16,000 cps, sold by Ciba-Geigy Corp. under the designation ARALDITE GY-9482 resin) was added to the vessel along with about 330 g of water.
The reaction was allowed to proceed for about 1.5 hours at 60°-65° C. and then the reaction mixture was cooled to room temperature. The resulting product had a pH of 7.04, a viscosity of about 38 cps (#2 spindle at 100 rpm), was semi-transparent in appearance and contained 30% solids.
EXAMPLE 4
The procedure of Example 3 was repeated using the following multifunctional epoxies:
EX-614--tetrafunctional epoxy sorbitan sold by Nagase Chemicals Ltd.
EPI-REZ 5048--trifunctional aliphatic epoxy resin sold by Interez Inc.
Dow DEN-438--3.6 functional epoxy novolak sold by The Dow Chemical Co.
XU-238--Hydantoin difunctional epoxy resin sold by Ciba-Geigy Corp.
The resulting polyester resins had the following properties:
______________________________________Epoxy UsedEX-614 Epi-Rez 5048 Dow DEN-438 XU-238______________________________________Viscosity Thick Moderately Thick Moderately Thick ThickSolids 30% 30% 30% 30%______________________________________
EXAMPLE 5
The molecular weight distribution was determined for the products of Examples 1 and 3 by preparing 2% solutions of each resin in tetrahydrofuron(THF). The samples were filtered and then injected into a liquid chromatograph utilizing a set of non-aqueous gel permeation columns with THF as the mobile phase. The column effluent was monitored with a U.V. diode array detector and a refractive index (R.I.) detector maintained at 40° C. The columns were calibrated with a series of polystyrene standards ranging in molecular weight from 890 Daltons to 1,260,000 Daltons. The R.I. detector signal was used for the calculation of the molecular weight distribution parameters listed below:
______________________________________Free Monomer Analysis Resin From Resin From Meth-Monomer Example 1 Example 3 od______________________________________Ethylene glycol 0.04% 0.02% GC1,4-Butanediol Less than 0.01% Less than 0.01% GCDiethylene glycol 0.06% 0.05% GCIsophthalic acid Less than 1.5% Less than 1.0% LCTerephthalic acid Less than 1.5% Less than 1.0% LCTrimellitic anhydride Less than 1.5% Less than 1.0% LCEpoxy -- Less than 1.0% LC______________________________________Molecular Weight DistributionBy Gel Permeation Chromatography Resin From Resin FromParameter Example 1 Example 3______________________________________Number avg. M.W. (M.sub.n) 8,000 8,000Weight avg. M.W. (M.sub.W) 30,000 67,000Z-avg. M.W. (M.sub.z) 63,000 165,000M.W. at sample maximum -- --% sample less than 2 21000 M.W.% sample less than Less than 0.5% Less than 0.5%500 M.W.______________________________________
EXAMPLE 6
This example illustrates the use of a polyester resin size of the present invention in a slasher dyeing process.
Slasher dyeing sizes were prepared having the following formulation:
______________________________________Ingredient Parts By Weight______________________________________Water 303.6Ammonium nitrate 2.0Melamine crosslinker 2.4Size from Table A 80.0Pigment or Dyestuff 12.0______________________________________
Formulations were tested using the following polyester resin sizes:
TABLE A______________________________________ResinDesignation Composition______________________________________A Resin made according to Example 2 with 1,4-butanediol substituted for the diethylene glycol.B Resin made according to Example 3 with neopentyl glycol substituted for the diethylene glycol.C Resin from Example 2.D Resin made according to Example 3 with diethylene glycol substituted for the 1,4-butanediol.E Resin from Example 3.F EASTMAN WD ResinG Resin made according to Example 3 with neopentyl glycol substituted for the 1,4-butanediol (1,4-BDO) and a higher ratio of diethylene glycol (DEG) to neopentyl glycol than the ratio of DEG to 1,4-BDO in Example 3.______________________________________
Each in turn of these sizes was padded onto unfinished polyester cloth and dried in an oven at 250° F. for 2.5 minutes. The material was then divided into three parts. One part was cured at 275° F. for 1 minute, the second part was cured at 350° F. for 1 minute and the third part was left uncured.
The samples were rated for color fastness and solvent resistance with the following results:
______________________________________ Size______________________________________ E Best B ↓ G ↓ D ↓ A ↓ C ↓ F Worst______________________________________ | High molecular weight, water reducible or dispersible polyester resin compositions are prepared by dispersing a molten carboxyl-containing polyester in water and chain extending it with an epoxide. The dispersions are useful as sizes for textiles and as coatings. | 3 |
RELATIONSHIP TO PRIOR APPLICATION
[0001] This is a U.S. non-provisional application relating to and claiming the benefit of U.S. Provisional Patent Application Ser. No. 61/252,197, filed Oct. 16, 2009.
BACKGROUND OF THE INVENTION
[0002] Physical contact optical fiber connectors are widely used in the communication industry. These connectors have one or more optical fiber physical contacts which are supported by ferrules which also physically align the contacts. These optical fiber physical contacts are often formed by polishing the end face of the optical fiber to a precise radius of curvature. A connector actually includes two connector halves which are intermatable. However, a connector half is often simply referred to as a connector. Thus, the single or multiple contacts are actually received within a connector half. When a corresponding connector half containing fibers and contacts are mated with the other connector half, the optical fiber contacts are brought together at their respective radii of curvature. If the intermated surfaces of the optical contacts are clean and undamaged, the contacts should have reasonably low insertion loss and small back reflection. In addition, it is important to correctly match these intermated optical contacts; for example, the corresponding intermated contacts must be correctly sized and aligned. Ideally, two fibers should be optically and physically identical and held by a connector that aligns the fibers precisely so that the interconnection does not exhibit any influence on the light propagation there through. This ideal situation is impractical because of many reasons, including fiber properties and tolerances in the connector.
[0003] The ends of the fibers or contacts have been prepared by several methods, including scoring and breaking the fibers, as well as polishing the ends. Optical fiber connector contacts having very low back reflection become more important at higher data rates. The current practice to obtain low back reflection is to angle polish the physical contact. However, because of this angle, the connector must be keyed to have the proper orientation to mate with its corresponding angle-polished contact.
SUMMARY OF THE INVENTION
[0004] In accordance with one form of this invention, there is provided a fiber optic connector for use with a fiber optic network having at least one predetermined operating wavelength. A first housing containing at least one optical fiber is provided. The optical fiber has a free end forming a physical contact. The physical contact is coated with a protective film. The optical thickness of the protective film is at least 0.10 of the operating wavelength of the fiber optic network.
[0005] In accordance with another form of this invention, there is provided a fiber optic connector for use with a fiber optic network having at least one predetermined operating wavelength including a first housing. The first housing contains at least one optical fiber. The optical fiber has a free end forming a physical contact. The physical contact is thermally shaped. The thermally shaped terminus is coated with a thin protective film. The optical thickness of the film is less than twice the operating wavelength of the fiber optic network, but is at least 0.10 of the operating wavelength.
[0006] In accordance with yet another form of this invention, there is provided a method for manufacturing a fiber optic connector including providing a length of at least one optical fiber. The optical fiber has first and second free ends. The first free end forms a physical contact. A quick connect device is attached to the optical fiber wherein the physical contact projects from one end of the quick connect device and a portion of the optical fiber projects from the other end of the quick connect device thereby forming a termini. A vacuum is applied to the termini. The physical contact is coated with a protective film while the vacuum is applied.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] The subject matter which is regarded as the invention is set forth in the independent claims. The invention, however, may be better understood in reference to the accompanying drawings in which:
[0008] FIG. 1 is a simplified partial side elevational view showing two mating optical fiber physical contacts of the subject invention.
[0009] FIG. 2 is a perspective view showing a fiber optic connector and a plurality of the fiber optic contacts of FIG. 1 .
[0010] FIG. 3 is a front view of the fiber optic connector of FIG. 2 .
[0011] FIG. 4 is a sectional view of the fiber optic connector of FIG. 3 taken through section line A-A.
[0012] FIG. 5 is a more detailed sectional view of a portion of fiber optic connector of FIG. 4 .
[0013] FIG. 6 is a perspective view showing a fiber optic termini with a quick connect device which may be used in connection with the apparatus of the subject invention.
[0014] FIG. 7 is a perspective view showing the quick connect device of FIG. 6 having been spliced to fiber optic cable.
[0015] FIG. 8 is a perspective view showing an apparatus used in the manufacture of the optical fiber physical contacts of the subject invention.
[0016] FIG. 9 is a sectional view showing one of the holes in the apparatus of FIG. 8 receiving a termini and a quick connect of FIG. 6 .
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0017] Referring now more particularly to FIG. 1 , there is provided optical fiber 10 , having core 12 and cladding 14 . There is also provided optical fiber 16 , having core 18 and cladding 20 . Fiber 10 is encapsulated by alignment ferrule 21 and fiber 11 is encapsulated by alignment ferrule 23 . As will be discussed below, optical fibers 10 and 16 are mounted in corresponding connector halves which are designed to be intermated.
[0018] Optical fiber 10 includes tip 22 , which forms a physical contact. Optical fiber 16 includes tip 24 , which forms a corresponding physical contact. These contacts 22 and 24 are preferably not angle polished, but preferably have coating thickness adjusted for low reflection and may be thermally shaped for additional reflection reduction.
[0019] This thermal shaping may be done by various methods known to those skilled in the art, including the methods taught in U.S. Pat. Nos. 6,413,450 and 6,738,554, both assigned to Megladon Manufacturing Group. The teachings of these two Megladon Patents are hereby incorporated herein by reference.
[0020] Each physical contact 22 and 24 is coated with thin film 26 , which is made of a hard material, i.e., a material having a Knopp hardness which is greater than the Knopp hardness of optical fibers. The preferred coating material is Al 2 O 3 , also known as corundum. Corundum is a very hard material, and thus resists scoring. Other hard coatings may also be used. Preferably this corundum film is thin enough so that light passing through is substantially unaffected, i.e., insertion losses are low but thick enough to resist scoring, and the optical thickness is adjusted so that reflection is low. For the embodiments in which a single layer of the film is applied, the thickness of film 26 should be at least 0.10 of but less than 1.00 of the operating wavelength of the light within the fibers. For embodiments in which multiple layers of film are applied, the thickness of the film can be as high as 2.00 of the operating wavelength of the light within the fibers.
[0021] FIG. 2 shows a plurality of optical fibers 10 having physical contacts 22 all of which are mounted in connector body 28 . Multi-fiber cable 30 extends from the rear of connector body 28 . Preferably the embodiment of FIG. 2 utilizes quick connect optical fiber device as shown in FIG. 6 which are known to those skilled in the art such as the quick connect devices described in U.S. Patent Publication No. US2009/0060427 invented by Wouters. The teachings of the Wouters Patent Publication are hereby incorporated herein by reference.
[0022] FIG. 6 shows termini 34 including quick connect device 37 , optical fiber 10 and physical contact 22 , physical contact is coated at the tip by corundum film 26 . After coating, which is described below, termini 34 is placed in connector body 28 , and optical fiber 10 is spliced to a corresponding optical fiber located within cable 30 by a splicing technique known to those skilled in the art. A spliced cable 30 /termini 34 is shown in FIG. 7 with the splicing area indicated as item 35 . Preferably, contact 22 has been thermally shaped, although the invention is not limited to a thermally shaped contact.
[0023] It is preferred that corundum thin film coating 26 is applied to the contacts in a vacuum chamber using a coating process known to those skilled in the art. In embodiments in which the connector is terminated to a reel of optical fiber cable, if quick connect optical fiber termini are not used, the reel, which can be very large depending on the length of the cable, must be placed within the vacuum chamber which can be impractical and expensive. Using termini 34 , individual termini may be placed in the vacuum chamber for disposition of the corundum coating application without the cable attached since the termini may be spliced onto the cable after coating of the film has taken place. A single layer vacuum coating run is expensive, and there could be several layers for the embodiment in which the film is used or an anti-reflective coating in addition to providing the hardware discussed above. In addition, each item will need to be rotated inside of the vacuum chamber during the coating process. By using the quick connect optical fiber termini approach, many more contacts can be coated at the same time with a single coating run, and/or a smaller vacuum chamber may be used, resulting in a substantial money savings. If the connector is terminated to a short patch cord(s) the quick-terminated optical fiber termini are not needed since a short patch cord(s) will easily fit into the vacuum chamber.
[0024] During the coating process, it is important that only the tip 22 of the optical fiber be coated since the coating materials are very expensive and it would be wasteful to coat other parts of the termini.
[0025] FIG. 8 illustrates a plate 36 which may be used to segregate the fiber tips 22 from the remainder of the termini during the coating process. Plate 36 includes a plurality of holes 38 which are adapted to receive termini 34 so that the tip 22 projects below the bottom of plate 36 and the remainder of the termini projects above the plate 36 as shown in FIG. 9 . For illustration purposes only, a single termini is shown. In reality, it is preferred that each hole in plate 36 receives a termini for the sake of efficiency. Plate 36 is sized with a protective cover on the top of the plate within the vacuum chamber such that the coating occurs in the bottom of the plate, and only the tips 22 are coated. Plate 36 is also rotatable so that the coating is uniform. Once the tips 22 have been coated, termini 34 are removed from the plate and thus from the vacuum chamber and inserted into connector 28 as illustrated in FIGS. 4 and 5 . Termini 34 is spliced to optical fiber 40 , which is received within cable 30 , at splice region 35 using splicing techniques known to those skilled in the art, including techniques described in the Wouters patent publication.
[0026] The hard corundum coating can be applied onto several layers of anti-reflective coating to also form a thicker hardened anti-reflective coating, which may in some instances eliminate the need for thermally shaping the contact. In some multi-layer embodiments, the outer layer may be hard corundum and the inner layers may be made of other low or high index of refraction materials having hardness closer to the glass fiber. This anti-reflective coating can be used for one or multiple wavelength bands of operation, including, but not limited to, the bands centered around 850 nm and 1,300 nm or 1,310 nm and 1,550 nm for example. The thickness of the anti-reflective coating depends on the number of layers of the film which are used. For example, the thickness might vary between 0.10 and 2.00 times the operating wavelength. However, where thermally shaping is used, the hardened coating further increases the hardness of the thermally shaped contact.
[0027] Multi fiber circular connectors, such as the one shown in FIG. 2 , are often used in harsh environments. Since such connectors must be keyed if the contacts are angle-polished, the contact orientations are hard to maintain. The combination of a hardened surface, scratch resistant contact and low back reflection without the need for keyed contact orientation is a great benefit for harsh environment multi-fiber circular connectors.
[0028] The physical contact fiber end faces described herein are axially symmetric, rugged and have low back reflection and may be used with single or multi-fiber connectors.
[0029] From the foregoing description of various embodiments of the invention, it will be apparent that many modifications may be made therein. It is understood that these embodiments of the invention are exemplifications of the invention only and that the invention is not limited thereto. | A fiber optic connector for use with a fiber optic network having at least one predetermined operating wavelength is provided. First housing contains at least one optical fiber. The optical fiber has a free end forming a physical contact. The physical contact is coated with a protective film. The optical thickness of the protective film is at least 0.10 of the operating wavelength of the fiber optic network. Preferably, the physical contact is thermally shaped. Also preferably, the optical fiber is attached to a quick connect device forming a termini. The physical contact of the optical fiber can be readily coated with the protective film by placing the termini in a vacuum chamber. | 8 |
The invention relates to single use transcervical catheterization cannulas for use in performing various procedures including the catheterization of blocked fallopian tubes.
DESCRIPTION OF THE PRIOR ART
In the performance of many transcervical procedures, the uterine cavity must be filed with a radiopaque dye fluid in order to examine the uterine cavity and associated structures such as the fallopian tubes with a fluoroscope.
In the case of blocked fallopian tubes, the point of blockage can readily be determined as the point beyond which the radiopaque dye fluid does not flow. During the catheterization procedure, the uterine cavity and fallopian tubes are first filled with the radiopaque dye fluid. A catheter wire is then passed, with the aid of a transcervical catheterization cannula, through the patient's vagina, through her cervical canal, into her uterine cavity, and finally into the fallopian tube. It is the action of the catheter wire which actually accomplishes the unblocking function.
In order to ensure that the radiopaque dye fluid remains in the uterine cavity and fallopian tubes during the catheterization procedure, and to help properly guide and support the catheter wire, various types of cannulas have been utilized. With all of the prior art devices, the cannulas are positioned to provide a liquid-tight seal with the cervical canal prior to the insertion of the catheter.
The prior art cervical cannulas achieve the needed liquid-tight cervical canal-cannula positioning by a variety of approaches. One such cannula, the Bard ® Cervical Cannula, has a pair of inflatable balloons located on the shaft of the cannula. The shaft of the cannula is forced through the cervical canal and is positioned so that one balloon lies on the inside opening of the cervical canal (termed the "internal os") and one balloon lies on the outside opening of the cervical canal (termed the "external os"). Once the Bard® Cannula is positioned, the two balloons are inflated, liquid-tightly clamping the cannula in place in the cervical canal. However, due to the sizing requirements of the shaft carrying the balloons, the cannula must have a relatively large shaft diameter. The relatively large shaft is difficult for the operating physician to insert through the cervical canal, and as a result, considerable pain and discomfort is caused to the patient.
Another device, disclosed in U.S. Pat. No. 3,385,300 to Holter, depends on a helically threaded cone to provide the desired liquid-tight cervical canal-cannula seal. The Holter threaded cone is literally "threaded" into the cervical canal. Although the seal thus established is satisfactory, the Holter device is very painful for the patient and causes trauma to the cervix and therefore its use has long been discontinued.
A third type of cannula, the Thurmond-Rosch Movable Cup Hysterocath T.M., manufactured by Cook Incorporated, sealably engages a cone (called an "acorn") positioned on the distal end of its shaft with the os externum by means of a sliding vacuum cup connected to a vacuum port. Once the vacuum cup is evacuated, it seals with the cervix, pushing the acorn into the os externum. One major problem with this type of device is that due to a not infrequent mismatch between the size of the cup and the size of the os externum, it is often difficult to achieve the desired liquid-tight cervical-canal-cannula seal. Another drawback to this device is that it must be used with a leading catheter passed through the cannula. It is the leading catheter which is used to aim the catheter wire towards the blocked fallopian tube. This results in a larger sized cannula shaft being required, which is in turn sometimes difficult to insert through the cervical canal.
A fourth type of device is disclosed in U.S. Pat. No. 4,775,362, to Kronner establishes the liquid-tight cervical canal-cannula seal by combining a balloon to be inflated on the interior os with a slidable cup to seat on the os externum. The Kronner device suffers from problems similar to the Thurmond-Rosch Movable Cup Hyterocath T.M.
Lastly, the Cohen self-retaining cannula in somewhat similar in appearance to the invention of this application, although it is only used to flood the uterine cavity with a radiopaque dye fluid, and is not used to guide a catheter wire. The liquid tight seal is established by seating an acorn located on the cannula's shaft firmly into the os externum. The Cohen device has a spring-loaded forceps holding handle on its shaft. A pair of tenaculum forceps is clamped onto the exterior of the cervix and the locking flats of the forceps are engaged with the forceps holding handle. The spring force provided by the spring-loaded handle forces the acorn tightly into the cervical canal.
SUMMARY OF THE INVENTION
There is a need for a disposable, single use transcervical catheterization cannula which is relatively painless for the patient, yet which provides a liquid-tight cervical canal-cannula seal and which is easy to insert into the cervical canal and easily manipulated once it is placed therein. It is also preferably for such a device to be relatively inexpensive to manufacture.
From the foregoing, it can be seen that an object of the present invention is to provide a transcervical catheterization cannula retained by forceps and for use with a catheter wire and radiopaque dye fluid, comprising:
an elongate shaft member having a proximal end and a distal end and having at least one lumen passing therethrough through which the catheter wire and the fluid can pass;
a tip means provided at said distal end of said shaft member, said tip member being in communication with said at least one lumen and being open at its distal end;
a cervical canal seating member positioned on said shaft rearward of said tip means; and
a handle member which is rotatable and axially movable on said shaft, said handle member being located rearward of said abutting member and having a locking means allowing said handle to be axially and rotatably locked on said shaft, said handle member being adjustable to positively engage with the forceps clamped to the patient's cervix to thereby cause said cervical canal member to liquid-tightly engage with the patient's cervical canal, yet allow said shaft member, said sealing member and said tip means to rotate relative to the cervical canal.
Another object of the invention is to provide a transcervical catheterization cannula retained by forceps and for use with a catheter wire and radiopaque dye fluid, comprising:
an elongate shaft member having a proximal end and a distal end and having a lumen therethrough through which the catheter wire and the fluid can pass;
a curved tip positioned at said distal end of said shaft member, said tip member being in communication with said lumen, said tip means being opened at its distal end;
a cervical canal seating member positioned on said shaft rearward o said curved tip; and
a handle member which is rotatably and axially movable on said shaft, said handle member being located rearward of said abutting member and having a locking means allowing said handle member to be axially and rotatable locked on said shaft, said handle member being adjustable to positively engage with forceps clamped to the patient's cervix to thereby cause said cervical canal seating member to engage with the patient's cervical canal, yet allow said shaft member, said seating member, and said tip means to rotate relative to the cervical canal.
Yet another object of the invention is to provide a transcervical catheterization cannula retained by forceps and for use with a catheter wire and radiopaque dye fluid, comprising:
an elongate shaft member having a proximal end and a distal end and having a lumen therethrough through which the catheter wire and the fluid can pass;
a curved tip positioned at said distal end of said shaft, said tip means being opened at its proximal end;
a cervical canal seating member positioned on said shaft rearward of said curved tip; and
a handle member which is rotatably and axially movable on said shaft member, said handle member being located rearward of said abutting member, said handle member comprising an elongate tubular sleeve member with an inner diameter slightly larger than the outer diameter of said shaft member, said sleeve member being slideably positioned on said shaft member, said tubular sleeve member having an outer diameter which is smaller at its distal end than at its proximal end, said tubular member having at least one elongate slit passing longitudinally through said proximal end of said sleeve, and a collar member having an inner diameter slightly larger than the outer diameter of said sleeve member at its distal end but smaller than the outer diameter of said sleeve member at its proximal end, said collar member having at least one wing member extending outwardly from said collar member, said wing members having a notch means to engage with the forceps to thereby cause said cervical canal sealing member to engage with the patient's cervical canal, whereby said handle member can be locked at its desired axial and radial position relative to the shaft member by sliding said collar member rearwardly onto said sleeve member, thereby causing said collar member to compress said proximal end of said sleeve member to frictionally engage and grip said elongate shaft member, thereby locking said handle member on said shaft member.
Other objects of the invention and advantages of the invention will be apparent as the description proceeds.
BRIEF SUMMARY OF THE INVENTION
In accordance with the illustrated embodiment of the present invention, a cannula is provided which can be liquid-tightly engaged with the cervical canal, yet which can be rotated while in place to properly position the tip of the cannula so that the catheter inserted therethrough will have proper angle of attack to gain entrance to the fallopian tube which is to be unblocked by the catheterization procedure.
In a preferred embodiment of the invention, a forceps holding handle is provided which relies on a friction sleeve to set the handle's position on the cannula's shaft.
BRIEF DESCRIPTION OF THE DRAWINGS
In describing the invention, reference will be made to the accompanying drawings wherein:
FIG. 1 is a partially exposed view of a human female reproductive system;
FIG. 2 is a perspective view of a first embodiment of the device;
FIG. 3a is a close-up view of the distal end of the device showing the curved tip with the catheter wire partially extending therethrough, the acorn, and the outer and inner tubes of the cannula's shaft;
FIG. 3b is a side view of the handle member of the first embodiment of the invention;
FIG. 3c is a perspective view of the sleeve member of the handle of the first embodiment;
FIG. 4 is a perspective view of a pair of tenaculum forceps gripping the cervix; and
FIG. 5 is a perspective view of a first embodiment in use with tenaculum forceps.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to the drawings, there is illustrated in FIG. 1 a partially exposed view of a human female's internal reproductive system. The vaginal cavity 10 communicates with the cervix 12, through which the cervical canal 14 passes into the uterine cavity 16. The outer opening of the cervical canal 14 is the os externum 18 and the inner opening of the cervical canal 14 is the internal os 20. The uterine cavity 16 although shown in an expanded shaped, is actually normally a virtual cavity wherein the uterus walls 22 are in contact with each other. However, when the uterine cavity is filled with a fluid, the uterine walls 22 move away from each other.
At the upper end of the uterine cavity 16 the fallopian tubes 24 merge with the uterine cavity at a portion called the isthmus 26. Each fallopian tube 24 is approximately four inches in length and connects with the ovaries 28 via the passages 30 through the fallopian tubes 24.
The fallopian tubes 24 are sometimes blocked by scarring, tissue build up, or for some other reason, thereby preventing the ova from being conveyed down the fallopian tubes 24 into the uterine cavity, thereby causing some forms of female sterility. Transcervical catheterization of blocked fallopian tubes is sometimes effective in reversing these forms of sterility.
FIG. 2 is a perspective view of a preferred embodiment of the transcervical catheterization cannula 40. The elongate cannula shaft 42 has at least one passage passing therethrough and has a cervical canal seating member, called an acorn 44, located at its distal end. As best shown in FIG. 3a, the cannula shaft 42 includes an inner tube 58 which passes through and fits inside an outer tube 60. The curved tip member 46 comprises the portion of the inner tube 58 which extends beyond the distal end of the acorn 44. Fixed at the proximal end of the cannula shaft 42 is an access and injection port 48, such as a Tuohy-Borst adapter. The access and injection port 48 can be connected to a supply of radiopaque dye fluid and will also allow a catheter wire 50 to slide therethrough without permitting the fluid to leak out through the cannula. A handle member 52 on the cannula shaft can be positioned at a desired axial and radial position on the cannula shaft 42. The entire cannula is about 14 inches long from end to end.
FIG. 3a is a close-up view of the distal end of the cannula 40. The acorn 44 is made of semi-rigid silicone rubber or other plastics. It is symmetrical about its radial axis and is curved downwards from its proximal end to its distal end to gently meet the proximal end of the tip member 46. The tip member 46 is curved at approximately a 25 to 30 degree angle to the cannula shaft 42, such, a range of curvature being found to be ideal to guide the catheter wire 50 into the fallopian tube 24. The catheter wire 50 extends through the open distal end 52 of the tip member 46. Located near the end 52 of the tip member 46, a radiopaque marker 54, such as a band of platinum wire, may be positioned to aid the operating physician in determining the position of the open tip 52. As an additional aid in properly orienting the tip member 46, visual indication marks 56, such as a number of dash marks, can be put on the cannula shaft 42.
As stated above, and as shown in FIG. 3a, the cannula shaft 42 includes an inner tube 58 which fits inside an outer tube 60. Both the inner and outer tubes 58 and 60 are ideally made of flexible material, such as nylon. The catheter wire 50 slides through the interior of the inner tube 58, as does the fluid which is used fill the uterine cavity and fallopian tubes. The outer tube 60 can partially enter a receiving hole 62 formed in proximal end of the acorn to hold the acorn 44 in place. In addition, cement or glue can be used. The inner tube 58 passes through the axis of the acorn 44 and the part in front of the distal end of the acorn 44 defines the curved tip member 46. The purpose of the outer tube 60 is to increase the rigidity of the cannula shaft 42 while still allowing it to have some flexibility. The tip member 46 is rounded at its open end 52 so as to avoid injury to cervical canal 12, uterine cavity 16 and fallopian tubes 24 during the procedure.
FIG. 3b is a side view of the preferred embodiment of the handle member 52. The handle member 52 has an elongate sleeve member 64 with at least one slit 66 in its wall at a proximal end of the sleeve 64. FIG. 3c is a perspective view of the sleeve member 64. The sleeve member 64 is sized so that its outer diameter at its distal end 68 is smaller than its outer diameter at its proximal end 70. The inner diameter the sleeve 64 is slightly greater than the outer diameter of outer tube 60 so that the sleeve member 64 can normally slide on the outer tube 60. If desired, finger grips 74 can be positioned at the proximal end of the sleeve member 64 in the vicinity of the slits 66 to aid the gripping and positioning the sleeve member 64. A collar member 76 with a pair of wings 78 is slideably engageable around the outside of the sleeve member 64. The inner diameter of the collar member 76 is larger than the outer diameter of the sleeve member at its distal end 68 but smaller than the outer diameter of the sleeve member at its proximal end 70. Thus, as the proximal portion of the collar member 76 and proximal end 70 of the sleeve member 64 are brought closer together, the collar member 76 compresses the proximal end 70 of the sleeve member 64, particularly the region of the sleeve member with slits 66, causing the collar member 76, sleeve member 64 and cannula shaft 42 to frictionally engage with each other, thereby locking the handle member 52 at a desired axial and radial position on the cannula shaft 42. The cannula shaft 42 and its associated acorn 44 and its curved tip member 46, however, can be rotated relative to the handle member 52 by twisting the cannula shaft 42, thereby allowing the curved tip member 46 to be precisely directed by the physician. On the rearwardly facing edges of each of the pair of wings 78, a notch 80 is provided. As will be discussed in further detail below, the notch 80 serves as a catch to engage with the locking flats of tenaculum forceps.
FIGS. 4 and 5 show a pair of tenaculum forceps 81 clamped onto the cervix 12. The tenaculum forceps have a pair of locking flats 82. The physician wishing to perform a transcervical fallopian tube catheterization procedure first inserts the transcervical catheterization cannula through the vagina (not shown) and inserts the tip member 46 through the cervical canal 14 and gently positions the acorn 44 so that it seats with the os externum 18. Due to the flexibility of the cannula shaft 42, the cannula shaft 42 can be flexed to aid in inserting the tip member 46 into the cervical, canal 14. Thereafter, a pair of tenaculum forceps 81 are clamped on the cervix 12 to secure them in place and the locking flats 82 of the forceps 81 are engaged. The handle member 52 is then positioned so that one of the notches 80 on one of the rearwardly facing edges of the wings 78 catch the locking flats 82.
By moving the handle member 52, rearwards and locking it in place, the tenaculum forceps 81 exerts a pulling force on the handle member 52, which is translated via the cannula shaft 42 to the acorn 44, thereby establishing a liquid-tight seal between the acorn 44 and the os externum 18.
Once the transcervical catheterization cannula is positioned, the physician can fill the uterine cavity 16 and the fallopian tubes 2 to the extent possible with the radioscopy fluid or dye via the inner tube 58. The access and injection port 48 allows the fluid to be first injected, the fluid access to be shut off, and then the catheter wire 50 to be slid through the access and injection port 48 through the inner tube 58 and out the opening 52 in the curved tip member 46, all while the fluid remains in the uterine cavity 16. During the transcervical catheterization procedure, the physician monitors the position of the transcervical catheterization cannula 40, the catheter wire 50 and the inner confines of the uterine cavity 16 and fallopian tubes 26 by a fluoroscope or other means. The radiopaque marker 54 located near the opening 52 of the curved tip member 46 shows up on the fluoroscope, which helps to indicate the position of the tip 52 in relationship to the isthmus 26 of the fallopian tubes 24. This, in connection with the visual indication mark 56 on the surface of the cannula shaft 42 greatly aids the physician in determining the optimum angle of attack necessary for the catheter wire 5 to easily enter the blocked fallopian tube 24. During the procedure, the handle member 52 and rear half or so of the cannula shaft 24 remains outside of the patient's body.
Due to the ability of the handle member 52 to be rotated relative to the cannula shaft 42 and its associated acorn 44 and the tip member 46, the physician can easily rotate the cannula shaft 42 and its associated acorn 44 seating on the os externum 18 relative to the handle member 52 and the tenaculum forceps 80 clamped on to the cervix in order to change the angle of attack of the tip member 46, all without having to the tenaculum forceps 81 from the cervix 12 and reclamp clamp them after the desired angle of attack has been attained. Obviously, the ability to easily change the angle of attack without having to repeatedly clamp and unclamp the tenaculum forceps 81 for the cervix 12 makes the transcervical catheter procedure less unpleasant and painful for the patient, and easier and quicker for the operating physician.
It should be borne in mind that the drawings are not rendered in actual scale so that certain features of the invention can be brought out and depicted.
The drawings and the foregoing description are not intended to represent the only form of the invention in regard to the details of its construction and manner of operation. In fact, it will be evident to one skilled in the art that modifications and variations may be made without departing from the spirit and scope of the invention. Changes in form and in the proportion of parts, as well as the substitution of equivalents, are contemplated as circumstances may suggest or render expedient; and although specific terms have been employed, they are intended in a generic and descriptive sense only and not for the purpose of limitation, the scope of the invention being delineated in the following claims: | The invention is a single use transcervical catheterization cannula retained by forceps for use with a catheter wire and radiopaque dye fluid. The cannula has a flexible shaft portion, an acorn to seat with the cervical canal, a fluid/catheter wire access port, and a handle member which is rotatably and axially movable on the shaft of the cannula but which can be locked at a desired position on the shaft of the cannula. A notch on a wing of the handle member engages with forceps to hold the cannula in liquid tight contact with the cervical canal. Extending beyond the end of the acorn is a curved tip, through whose open end the catheter wire is extended. | 0 |
CROSS REFERENCE TO RELATED APPLICATION
This application is a continuation of Ser. No. May 11, 1987 now abandoned.
BACKGROUND OF THE INVENTION
An oscilloscope is an electronic instrument which is used to detect, analyze and display voltage signals. A logic analyzer is an electronic instrument used to detect, analyze and display digital voltage signals. (Generally, digital voltage signals may be regarded as a sub-set of voltage signals. Typically, a digital voltage signal conveys binary information, that is, the signal is either logic "high" or logic "low". For instance, signal voltage is above a according to one convention, if the given threshold voltage value it is "high" whereas if it is below the threshold value it is "low". In conventional binary logic, "high" represents a "1" and "low" represents a "0".) Both instruments acquire input signals and display their representative waveforms. The instruments' display screens are essentially windows through which users can view acquired signal waveforms.
The oscilloscope displays an input voltage signal's waveform as a function of voltage-versus-time, typically with voltage amplitude measured along a vertical axis and time measured along a horizontal axis. Like an oscilloscope, the logic analyzer also displays a digital signal's waveform as a function of voltage-versus-time with voltage amplitude measured along a vertical axis and time displayed along a horizontal axis. Unlike an oscilloscope, however, the logic analyzer does not display high vertical (that is, voltage) resolution. Rather, for a given signal the logic analyzer waveform will resemble a square-wave and therefore be either "high" or "low". Since the signal carries binary information, that is, 1's and 0's, it is the signal's transition above or below the threshold value, rather than its absolute value, that is important. Therefore, the logic analyzer's square-wave waveform display mode is both adequate and ideal for digital signals.
Certainly, the oscilloscope, as opposed to the logic analyzer, is the more general purpose instrument and most engineers, particularly electrical engineers, are familiar with its function and operation. The operational user-interface for the oscilloscope comprises two major controls: seconds-per-division, also known as range, and delay. Typically, the display screen of an oscilloscope is divided into equal size divisions along both the voltage amplitude and the time axes. The seconds-per-division control allows the user to change the amount of time displayed across the time axis of the display screen. The total time across the screen is known as the range. For any given display, decreasing seconds-per-division increases display resolution in a manner analogous to increasing the magnification of a microscope. The delay control positions the display window in time relative to the trigger event. The trigger defines the conditions which the input signal must meet before it is acquired by the instrument. By adjusting the oscilloscope's delay, the user can move the waveform display window forward or back in time relative to the trigger.
The function and operation of the logic analyzer, however, is not as familiar to most engineers. Typically, the logic analyzer displays the digital waveforms of many individual digital signals at once, such as the signals on the multiple lines of a data-bus or an address-bus. The logic analyzer samples an input signal, digitizes the samples, stores the digitized samples in memory and maps the stored digital values into a representative square-wave waveform on the display screen. The typical logic analyzer can show sixteen digital waveforms at once. Thus, on such an analyzer the signals on the sixteen lines of a 16-bit address bus would be shown as sixteen individual square-wave waveforms positioned from the top to the bottom of the display screen. The user of the logic analyzer can then view the sixteen waveforms simultaneously in a single display. Typically, the user is interested in visually comparing the transitions from high to low of numerous waveforms, such as a comparison of the transitions on certain address lines of a microprocessor with the transitions on certain control lines.
The major operational user-interface controls for a logic analyzer are: sample-period, magnification, magnify-about, magnify-about marker-movement, start/center/end, and hardware-delay. The sample-period control allows the user to set the sample period of the sampling circuit which acquires and digitizes samples of the input signal. The magnification control allows the user to select various magnifications of the display window. The magnify-about control allows the user to select one of two markers (usually an "x" and an "o") located in the display window; magnification can only occur about the location of a magnify-about marker. The magnify-about marker-movement control allows the user to position magnify-about markers in the display window. The start/center/end control allows the user to define where, in the digitized samples that are stored in memory, the trigger condition is located. (Similar to an oscilloscope trigger, the logic analyzer trigger defines a condition which the input signal(s) must meet before the instrument begins acquiring samples of input signal(s). The logic analyzer user can define the trigger using so-called edge, pattern and glitch controls.) Finally, the hardware-delay control allows the user to specify a certain delay time from trigger that the sample acquisition hardware will wait before acquiring samples. These typical logic analyzer operational controls are fully explained in the Hewlett-Packard 1984 Operating and Programming Manual for the Model 1630A/D/G Logic Analyzer. These logic analyzer controls give the user much control but they also require a certain degree of understanding of the logic analyzer's sampling hardware function and the schemes for storage of digitized samples in memory. The relatively large number of controls therefore can make the logic analyzer seem confusing to a person who is familiar with the oscilloscope.
SUMMARY OF THE INVENTION
The present invention significantly simplifies user control of the logic analyzer with a new oscilloscope-like user-interface. The oscilloscope-like user-interface substitutes two oscilloscope-like controls (seconds-per-division and delay) for the six logic analyzer controls (sample-period, magnification, magnify-about, magnify-about marker-movement, start/center/end, and hardware-delay). The sample-period and magnification user controls are replaced with one seconds-per-division user control. The magnify-about, magnify-about marker-movement, start/center/end and hardware-delay user controls are replaced with one delay user control. The present invention uses software to automatically adjust sample-period and magnification (in a manner invisible to the user) when the user adjust seconds-per-division. Likewise, start/center/end and hardware-delay are automatically and invisibly adjusted by software when the user adjusts delay. Finally, the magnify-about and magnify-about marker-movement controls are essentially eliminated because magnification is automatically adjusted via seconds-per-division.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a frontal view of a logic analyzer such as would be used with the present invention.
FIG. 2 shows how an input signal is digitized and the digital information converted into a square-wave like waveform.
FIG. 3 shows a functional block diagram of a logic analyzer.
FIG. 4 shows how digitized waveform information for a single waveform is mapped into a single-waveform display.
FIG. 5 shows how digitized waveform information for multiple waveforms is mapped into a multiple-waveform display.
FIG. 6 shows how digitized samples in memory are windowed and magnified using prior art logic analyzer controls. windowed and magnified using the present invention.
FIG. 7 shows the steps in a method for drawing a waveform on the display window of a logic analyzer using the present invention.
FIGS. 9A through 9D show how the present invention's seconds-per-division control/effects the display window of a logic analyzer.
FIG. 10A through 10D show how the present invention's delay control effects the display window of a logic analyzer.
DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 shows a frontal view of a logic analyzer 5, such as would be used with the present invention. Logic analyzer 5 is user-controlled with keyboard 20 and control knob 25. The user may select various control menus with keyboard 20. The user can roll through various options within the menus by turning knob 25. Disc drive 15 is available for loading and storing software. Digital signal square-wave waveforms are displayed on cathode ray tube (CRT) display screen 10.
FIG. 2 shows how a signal 50 is converted into a square-wave like waveform 65. Signal 50 is a voltage signal having a changing voltage amplitude. Given an arbitrary voltage threshold level 55, signal 50 may be regarded as being either above or below threshold level 55 at any given time. Signal 50 may then be sampled at discrete time intervals 60. At each sampling interval, signal 50 will either be above or below threshold level 55. Convention dictates that when the signal 50 sample value is below threshold level 55, that sample is considered to be logic low, that is, 0. Likewise, when the signal 50 sample value is above threshold level 55, that sample is considered to be logic high, that is, 1. Signal 50 sample values may then be converted into binary logic 1's and O's. For instance, at sample interval 60A, signal 50 is below threshold level 55 so that sample 60A is a 0. At sample interval 60B, signal 50 is above threshold level 55 so that sample 60B is a 1. Likewise, at sample interval 60C, signal 50 is again below threshold level 55 so that sample 60C is a 0. Finally, square-wave waveform 65 may be constructed from the time-ordered sequence 60 of 0's and 1's generated from sampling signal 50. As can be seen from FIG. 3, square-wave waveform 65 is high when signal 50 is above threshold level 55, that is, when the sample values 60 are 1's. Likewise, square-wave waveform 65 is low when signal 50 is below threshold level 55, that is, when the sample values 60 are 0's. Digitizing a signal, that is, converting a changing voltage signal to 1's and 0's based upon whether the signal is above or below a given threshold, allows for representing the signal as a square-wave, such as representing signal 50 with square-wave 65. Moreover, the digitized values, that is the 1's and 0's, may be easily stored and manipulated in memory.
FIG. 3 shows a functional block diagram of a logic analyzer, such as logic analyzer 10. A signal, such as signal 50, is input to logic analyzer 10 and applied via bus 90 to trigger circuit 100 and sample 105. (It should be observed that logic analyzer 10 can process multiple input signals in parallel, as suggested by bus 90, but only a single input signal 50 is discussed herein for the sake of explanation of FIG. 3. The functional process which is described herein concerning single signal 50 can occur in parallel if multiple signals are input in parallel.) Sampling circuit 105 digitizes signal 50, that is, it converts signal 50 into 1's and 0's in the manner described in connection with FIG. 2. Sampling circuit 105 samples signal 50 at regular periodic intervals defined by sample clock 110. Clock 110 emits clock signals which activate both sampling circuit 105 and trace memory 135 via lines 112 and 114 respectively. The time length of each interval is known as the sample period. The sample period is user-defined via sample clock 110. The digitized sampling information generated by sampling circuit 105, that is, the 1's and 0's, are stored in trace memory 135 via bus 120. However, trigger circuit 100 defines a trigger condition which input signal 50 must meet before the sampling can begin. Trigger circuit 100 essentially activates logic analyzer 10 in that regard. If the trigger condition is met by input signal 50, trigger circuit 100 emits a signal via line 125 to memory control circuit 130 which allows the sample values that are generated by sampling circuit 105 to be stored in trace memory 135. The digitized sampling information which is stored in trace memory 135 is then read and processed by microprocessor 150 via bus 140, according to predetermined programs. Using the digitized information, microprocessor 150 generates display waveforms which it writes into display memory 160 via bus 155. Display memory 160 is then mapped onto display 15 via bus 165 to produce the square-wave which are visible to the viewer. Collectively, sampling circuit 105, clock 100, trigger circuit 100 and memory control 130 may be referred to as the acquisition hardware of the logic analyzer since these components essentially "acquire" the input signal(s).
FIG. 4 shows how digitized waveform information for a single input signal is mapped into a single square-wave waveform display. On the far left in FIG. 4 is a column 200 of sixteen sample-periods marked t n through t n+15 . To the right of column 200 is a column 205 of digital values, that is, 1'sand 0's, which correspond to the digitized sample values of the input signal for each corresponding sample-period. Thus, for sample period tn the digitized sample value is 1; for sample period t n+5 the digitized sample value is 0; for sample period t n+8 the digitized sample value is 1, and so forth. Moreover, the sample-periods are numbered chronologically in time such that t n designates the first sample value acquired, t n+2 designates the second sample value acquired, and so forth. In practice, the column 200 of sample-periods, that is, t n through t n+15 , is implemented in memory by chronological memory addresses. Thus, FIG. 4 shows a column 200 of sixteen 1-bit memory addresses wherein at each address is the digitized sample value, in column 205, of the input signal for a given sample period. The digitized sample values can be mapped from memory onto a raster display as shown on the left in FIG. 4. Final square-wave waveform 285 represents a direct mapping of the information in memory column 200 onto a raster display screen. The time-units of horizontal time axis 207 of the display screen correspond to the sample periods in memory-address column 200. (In a raster display screen, the time-units 207 would be implemented with pixels such that the number of time-units across the screen equals the number of pixels in a horizontal line across the screen.) The mapping scheme between memory and the display is as follows: given a predetermined correspondence between memory-address column 200 and horizontal time axis 215 of the display, where there are 1's in memory 205, waveform 295 is high in the corresponding time-unit of the display; and where there are 0's in memory 205, waveform 285 is low in the corresponding time-unit of the display. (The predetermined correspondence between the samples in memory and the time-unit on the display in FIG. 4 is one-to-one.) The digitized information in column 205 is mapped onto the display screen in serial order such that the final waveform 285 is drawn onto the display screen, from left to right, in a sequence of segments shown by segmental waveforms 210 through 280.
FIG. 5 shows how digitized waveform information for multiple waveforms is mapped into a multiple-waveform display. Using the mapping scheme described in connection with FIG. 4, we see in FIG. 5 that the digitized information in column A maps into waveform A; the digitized information in column B maps into waveform B; the digitized information in column C maps into waveform C; and the digitized information in column D maps into waveform D. The waveforms A, B, C and D are simply mapped onto the display screen separately from each other, each starting at a different level on the display screen, using the mapping scheme described in connection with FIG. 4.
FIG. 6 shows how digitized samples in memory are windowed and magnified using prior art logic analyzer controls. In FIG. 6, arbitrary input signals A, B, C and D have been sampled and their digitized sample values stored in trace memory 135. Each word of trace memory 135 contains the digitized samples for signals A, B, C and D acquired in a single user-specified sampling period; trace memory 135 as a whole contains a single trace acquisition. A single trace acquisition fills trace memory 135 with digitized sample values of the input signals following user-specification of the trigger, the hardware-delay time and the location of the trigger in trace memory. (FIG. 6 shows trace memory 135 as a 1023 4-bit word memory structure for the sake of explanation.) Therefore, once the trigger condition is detected and the hardware-delay time has elapsed, the acquisition hardware (sampling circuit 105, clock 110, trigger circuit 100, and memory control 130 of FIG. 3) would fill trace memory 135 with digitized sample values of the input signals. Each word of trace memory 135 therefore holds the digitized samples for a single sample period. Using the start/center/end control of the prior art logic analyzer, the user could specify that the trigger be stored at the start (word 0 ), center (word 511 ) or end (word 1023 ) trace memory 135. If the trigger was stored at the start, word 1 through word 1023 would hold post-trigger digitized samples; if the trigger was stored at the center, word 0 through word 510 would hold pre-trigger digitized samples through word 1023 would hold post-trigger digitized samples; if the trigger was stored at the end, word 0 through word 1022 would hold all pre-trigger digitized samples. Suppose the user specified the trigger to ABCD=1010, to be stored at the start of memory and set the hardware-delay equal to one sample-period. In that case, FIG. 6 shows trace memory 135 with the trigger stored in word 0 with word 1 through word 1023 having post-trigger information. Digital waveforms corresponding to the digitized samples in trace memory 135 are shown in the top center of FIG. 6. Trigger line 315 is shown at the start of the waveforms. The digital waveforms can be mapped onto display screen 10 as shown in display window 10A. Display window 10A shows a mapping of word 8 through word 19 onto the display screen 10 at a magnification of 1X. The magnification factor for a given mapping is the ratio of sample-periods-in-memory to time-units across the time axis of the display window. Thus, at 1× magnification, one sample period in memory maps into a single time-unit; at 2× magnification, one sample period maps into a two time-units; at 10× magnification, one sample period map into ten time-units and so on. (As noted in connection with FIG. 4, display window time-units can be implemented with pixels in a raster screen such that the number of time-units across the window equals the number of pixels in a horizontal line across the screen.) For the sake of explanation, display window 10A shows twelve time-units. Thus, at a 1× magnification, twelve sample-periods, that is, twelve words from trace memory 135 map into display window 10A. In FIG. 6, word 8 through word 19 map into window for a 1× magnification of the waveforms. Magnify-about markers 325 and 320 allow the user to indicate which portion of display window 10A is to be magnified. Magnify-about marker 325 and 320 may be moved along the horizontal time axis of display window 10A with user-controlled magnify-about marker-movement user controls. The user may specify the degree of magnification (1×, 2×, . . . , 10×, etc.) and the marker about which magnification is to occur. For instance, display window 10B shows a 2× magnification of display window 10A about marker 320. Note that since window 10B is a 2× magnification of window 10A, only half as many sample periods in memory, that is, words for trace memory 135, map into display window 10B. Thus, one sample period in memory maps into two time-units of display window 10B to create a 2× magnification of window 10A. (Indirectly, magnification may also be accomplished by decreasing the size of the sample period. However, altering the sample period size would require a new acquisition trace. Thus, for a given acquisition trace in trace memory, magnification is accomplished by increasing the mapping the ratio of time-units to sample periods.)
FIG. 7 shows how digitized samples in trace memory can be windowed and magnified using the present invention. Display screen 10 has display window 10C showing an arbitrary digital waveform E whose digitized sample values are in trace memory 400. Window 10C is a raster display implemented with pixels as shown in the blow-up of bubble 10D represents a pixel; each large dot represents an illuminated pixel. In the preferred embodiment of the present invention, digitized sample values in memory column E can be mapped into time-units, that is, pixel columns, of display window 10C using a formula based on user selected values for seconds-per-division and delay. Seconds-per-division is the user-selected amount of time per division along the horizontal time axis of display window 10C. (Display window 10C has ten divisions so that the seconds-per-division value is the range, that is, the total time across the time axis, divided by ten.) Delay is the user-selected time difference between the center of the display window and the trigger. As a reference, the present assigns the trigger condition the time value t 0 such that when delay =0, then the trigger is mapped into the center of the display window. (For instance, in FIG. 7, the delay is zero since the trigger t 0 trace memory 400 is mapped into the center of display window 10C.) Thus, increasing delay moves the display window forward in time into post-trigger information (that is, toward the end of the trace memory); likewise, decreasing delay moves the display window backward in time into pre-trigger information (that is, toward the start of trace memory). Given that the trigger is referenced as t 0 , the trace memory is time scaled such that the digitized samples in trace memory preceding the trigger are referenced as t -1 , t -2 , t -3 , and so on to the start of trace memory; likewise, the digitized samples following the trigger are referenced as t 1 , t 2 , t 3 , and so on to the end of trace memory. The trace memory can then be mapped onto the display window based formula (1) below which assigns each pixel, that is, time-unit, across the display window a time value relative to the time scale of trace memory.
(1) Pixel.sub.--Time=[ (Pixel#.sub.--Ctrpixel)(Sec/Div)+(Delay)(Pix/Div)]/[(Pix/Div)(Sec/Sample)].(1)
The variables in formula (I) are defined as follows:
Pixel# is the number of a given pixel in the horizontal row of pixels across the display window. In the preferred embodiment of the present invention, there are 500 pixels across the display window numbered P 0 through P 499 .
Ctrpixel is P 249 .
Sec/Div is the user-selected value of seconds-per-division.
Sec/Sample is the sample period. In the preferred embodiment of the present invention, the sample period is acquisition to be the current value of the seconds-per-division setting divided by fifty (although the lowest possible sample-period value is at 10 ns, despite the sec/div setting).
Delay is the user-selected value of delay. In the preferred embodiment of the present invention, if the user selects a delay time less than or equal to 20 ns, then it is presumed that the user is interested primarily in pre-trigger information and therefore the trigger will be stored at the end of trace memory on the following acquisition trace. Likewise, if the user selects a delay greater than 5 ms, then it is presumed that the user is primarily interested in post-trigger information and therefore the trigger will be stored at the start of trace memory on the following acquisition trace. Otherwise, the hardware-delay is set to the user-selected value of delay and the trigger will be stored in trace memory such that the difference between the trigger and the center of trace memory, measured in units of sample periods, is equal to the delay. In addition, if the user specifies a delay which exceeds the sum of the maximum hardware delay time (5 ms in the preferred embodiment) plus the width of the trace memory time scale (where the width of the time scale is the number of sample locations times the sample-period) then the sample-period is automatically increased until the width of the trace memory time scale incorporates that delay. Likewise, if the user specifies a delay which is less than the difference between the minimum hardware-delay time (20 ns in the preferred embodiment) and the width of the trace memory time scale then the sample-period is again automatically increased to incorporate the delay. In the first case the increased sample-period yields greater post-trigger reach, and in the second case the increased sample-period yields greater pre-trigger reach, although in both cases such reach is gained at the expense of resolution.
Pix/Div is the number of pixels across the display window divided by the number of divisions. In the preferred embodiment of the present invention, Pix/Div=50 since there are 500 pixels and ten divisions across the display window.
In the preferred embodiment of the present invention, the Pixel 13 Time value for each pixel, that is, P 0 through P 499 , is calculated and stored in a look-up table at the start of each new acquisition trace. (Alternatively, pixel times could be calculated on the fly as the waveform is being drawn, as opposed to being calculated and stored, but such an alternative is likely to slow down the overall waveform update rate for waveforms having frequent transitions from high-to-low or from low-to-high.) Thus, following each acquisition trace, each pixel in the display window (P 0 through P 499 ) will have a Pixel 13 Time which serves to map that pixel into a particular location in the trace memory. (Since formula (1) can generate non-integer number, the present invention uses a rounding rule such that a pixel with a non-integer is mapped into the location in trace memory closest to the non-integer number.) The result is that the logic analyzer user need only manipulate a seconds-per-division and a delay control. The prior art sample-period control is eliminated because sample-period is automatically calculated, at the start of each acquisition trace, to be the user-selected seconds-per-division setting divided by fifty. All of the prior art magnification controls (magnification, magnify-about, and magnify-about marker-movement) are eliminated by the seconds-per-division control: decreasing seconds-per-division increases magnification while increasing seconds-per-division decreases magnification. The prior art start/center/end control for placement of the trigger in trace memory is eliminated because the present invention automatically positions the trigger as described above. Finally, the hardware-delay is essentially replaced with the present invention's delay control.
FIG. 8 shows the steps in a method for drawing a waveform on the display window of a logic analyzer using the present invention. The first step 400 is to execute an acquisition trace and fill trace memory 135 of FIG. 1 with digitized samples. An alternate first step 401 is a user change of the seconds-per-division or delay controls. The next step 405 is to calculate Pixel 13 Time values using formula (1) as discussed above in connection with FIG. 7. In the preferred embodiment of the present invention, there are five hundred pixels across the display window of the logic analyzer such that there are five hundred calculated Pixel-Times indexed P 0 through P 499 . The Pixel 13 Time values for P 0 through P 499 are calculated using the current user-selected values for seconds-per-division and delay and are stored in a look up table. The next step 410 is to find the left edge of the display window of the logic analyzer as that left edge is represented in trace memory. The left edge is identified in trace memory as that digitized sample whose value on the trace memory time scale is less than or equal to the Pixel 13 Time value of P 0 . (The trace memory time scale is defined in reference to the location of the trigger (t 0 ) as discussed in connection with FIG. 6. The time value of each digitized sample's location on the trace memory time scale is that location's distance from trigger (measured in samples) times the value of the sample-period.) The next step 415 is to set a counter variable P base equal to the index value of P n . (For instance, if P base gets P 0 then P base would contain 0; if P base gets P 231 then P base would contain 231; and so on.) Also in step 415, a variable t base is set equal to t sample , where t sample is the trace memory time-scale value of the location of the digitized sample identified in step 410. In addition in step 415, a variable V base is set equal to V t-- sample, where V t-- sample is the logical value (high or low, 13 that is, 1 or 0) of the contents of the location corresponding to t sample . In the next step 420, the next vertical transition edge of the waveform is found by stepping forward in trace memory until the next location having a sample value different from the current location's value is identified. The variable t next is assigned the trace memory time scale value of that next location. The variable V next is assigned the logical value (high or low, that is, 1 or 0) of the sample in that location. The next step 425 is to find the pixel P next whose Pixel 13 Time value in the Pixel -- Time look-up table is closest to t next . Given identification of P next , a horizontal line (corresponding to the logical level of V base ) is drawn on the display window from pixel P base to pixel P next in step 430. A vertical transition edge is also drawn at pixel P next in step 430. In the next step 435, the variables P base , V base and t base are updated to P next , V next and t next , respectively. In the next step 440, a test is made to check for the end of trace memory and/or the right-hand edge of the display window. If either test is true, then the waveform is complete; otherwise the method reiterates beginning at step 420 as indicated by loop 445. Note that a single acquisition trace, as executed in step 400, can load trace memory with information for multiple waveforms. Therefore, additional waveforms from the one acquisition trace executed in step 400 can be drawn by re-executing steps 410 through 445 for each additional waveform. Note also that step 405 only has to be executed once for each acquisition trace of step 400 or change in seconds-per-division or delay controls in step 401.
FIGS. 9A through 9D show how the present invention's seconds-per-division control effects the display window of a logic analyzer. FIG. 9A shows display window 500A showing the acquisition trace waveforms for seven address signals (ADDR 00 through ADDR 06) and one control signal (VMA 00). In FIG. 9A, the seconds-per-division setting is 50 ns as shown in the sec/div window. (The delay setting is 0s as shown in the delay window.) In FIG. 9B, user-controlled seconds-per-division selection window 510 is shown having the current value of sec/div (50 ns). The values in window 510 may be changed by rolling control knob 25 of FIG. 1. (The sec/div values change in the standard 1-2-5 sequence available on most oscilloscopes.) In FIG. 9C, user-controlled numeric entry window 520 is shown whereby the user may enter a new sec/div setting (179ns). (Note in FIG. 9D that the user is able to enter sec/div values outside the 1-2-5 sequence which constrains most oscilloscopes. For instance, the value 179 ns was entered using numeric punch keys.) In FIG. 9D, display window 500D is shown having new sec/div setting 179 ns. A comparison of FIG. 9D with FIG. 9A shows that the smaller sec/div setting in FIG. 9A (50ns) is a magnification of the display in FIG. 9D (179 ns).
FIGS. 10A through 10D show how the present invention's delay control effects the display window of a logic analyzer. FIG. 10A shows display window 600A showing the acquisition trace waveforms for seven address signals (ADDR 00 through ADDR 06) and one control signal (VMA 00). In FIG. 10A, the delay setting is 0s, as shown in the display window. (The seconds-per-division setting is 50 ns as shown in the sec/div window.) In FIG. 10B, user-controlled delay selection window 610 is shown having the current value of the delay setting (0s). The user may enter new values for delay in window 610 by turning control knob 25 of FIG. 1. In FIG. 10C, user-controlled numeric entry window 620 is shown whereby the user may enter a new delay setting (-40 ns) using numeric punch keys. In FIG. 9D, display window 600D is shown is shown having new delay setting -40 ns. A comparison of FIG. 10D with FIG. 10A shows that window 600D is shifted 40 ns to the left of window 600A. | Provided is an oscilloscope-like user-interface for a logic analyzer. The oscilloscope-like user-interface simplifies user control of the logic analyzer. The oscilloscope-like user-interface substitutes two oscilloscope-like controls (seconds-per-division and delay) for six logic analyzer controls (sample-period, magnification, magnify-about, magnify-about marker-movement, start/center/end, and delay-from-trigger). The result of the substitution is a logic analyzer which is operable with oscilloscope-like controls and which does not require user understanding of the logic analyzer's sampling hardware for effective user operation. | 6 |
FIELD OF THE INVENTION
This application relates in general to geofencing management of wireless devices, and more particularly relates to methods and systems for monitoring and supervisory action based on geographic locations of wireless devices.
BACKGROUND
Location-based services for wireless devices are only beginning to become adopted. Such wireless devices may include cell phones and personal digital assistants (PDAs), as well as more application-specific devices intended for use by service persons and other workers. Cell phones and PDAs are typically small in size, so that the individual user can carry such devices on his or her person for example, in a belt holster, a backpack, or a book bag. Purpose-specific wireless devices may be incorporated into vehicle-mounted communications equipment or other apparatus used in connection with the service or field visits of the person, although of course service persons may as well carry individual cell phones or other wireless devices.
Although the service of tracking the geographic locations of wireless devices is known, those services are generally used only to track the location of field service workers, children, or others carrying wireless devices and subscribed to a tracking service. The tracking services may monitor the location of a participating wireless device and periodically prepare reports, based on locations and times of the location information, so that a parent or supervisor may later take action as deemed appropriate. In the case of application-specific wireless devices, such devices may monitor additional inputs, such as vehicle speed and ignition on-off status, and periodically report that information for supervisory attention. However, such prior systems generally do not provide real-time or near-real-time remote management of wireless devices or their features and functions.
SUMMARY
Stated in general terms, systems according to embodiments of the present invention monitor the location of a wireless device and takes one or several supervisory actions if that device is not at an expected location. The expected location may be one or more locations where the wireless device and its user are expected at one or more particular times, such as the user's house or the house of a friend, or a daycare center or other location previously designated or approved by a subscriber of the monitoring service. For the purpose of this disclosure, it should also be understood that an “expected location” can include one or more locations outside of a predetermined geofencing arrangement, namely, locations where the user of the wireless device should not be present. Examples of such excluded locations might include, for example, bars or theatres in the case of service persons in the course of their employment.
Action taken on location information not corresponding to an expected location of a wireless device, e.g., at a particular time, or the location of a wireless device at a location previously determined as unapproved for that wireless device and its user, may take various forms according to embodiments of the present invention. Location information of a wireless device is periodically received and compared with a database or other source containing predetermined location information for that wireless device. If the location information indicates that the wireless device is at other than an expected location, an exception is determined and, in response to the exception, an action is taken. According to embodiments of the present invention, that responsive action may include sending a notification signal to the wireless device, as well as disabling one or more functions of that wireless device. Exception-responsive action may also include sending a message to one or more destinations different from the wireless device whose location is being monitored, for example, to notify a parent or guardian that a child has not arrived at a predetermined location within the time expected for that arrival. Such third-party notification may also operate in several escalating levels, for example, a first level being notification sent to a parent or guardian, followed by a second level of notification sent to a school principle or administrator if the first-level notification is not acknowledged within a certain time. A third level of notification might, for example, provide an alert to local police and/or a local 911 emergency provider.
Location information of the wireless device may be obtained by any suitable technique including techniques known in the art, as discussed below. According to an embodiment of the present invention, location information for a person may also be obtained by sensors or information-reading devices other than cell phones or PDAs. For example, the arrival of a person at a particular location, e.g., a daycare center or a school, may be signaled by swiping or otherwise reading an ID card or other device carried by that person and encoded with readable information identifying the carrier of the card or device. Non-contact sensing devices such as RFID devices may also provide a source of identification information when that device is scanned by a reader as a person carrying the device enters or leaves a particular location. The location information thus derived by scanning or otherwise sensing an information device carried by the person is transmitted, by wire or wirelessly, to the provider of monitoring services. The service provider can compare that location information to a database or other source of information provided for the particular person, to determine whether or not that person has arrived at an expected destination within a predetermined time, for example, within a maximum amount of time after that person departed from a previous location as indicated by location information derived from a wireless device of that person.
Other systems, methods, and/or computer program products according to embodiments will be or become apparent to one with skilled in the art upon review of the following drawings and detailed description. It is intended that all such additional systems, methods, and/or computer program products be included within this description, be within the scope of the present invention, and be protected by the accompanying claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a functional block diagram showing monitoring and supervisory management of a wireless device according to a disclosed embodiment of the invention.
FIG. 2 is a flow chart representing operation of the embodiment according to FIG. 1 .
FIG. 3 is a flow chart illustrating operation of an alternative disclosed embodiment according to the present invention.
DETAILED DESCRIPTION
FIG. 1 shows in functional terms an apparatus according to a disclosed embodiment for monitoring the location of a wireless device, and by extension the location of a person carrying that wireless device. The wireless devices in that embodiment are indicated generally at 10 , and it will be understood that those wireless devices may be cell phones, PDAs equipped for radio communication, or any other wireless device operating for radio communication with a central location or service provider for such wireless devices.
A wireless network 12 is in radio communication with the one or more wireless devices 10 . Where the wireless devices 10 comprise cell phones, it will be understood that the wireless network 12 comprises a number of cell sites for radio communication with the wireless devices. The wireless network 12 is operated by a wireless service provider 14 , which those skilled in the art will understand as including one or more mobile switching centers each of which may serve more than one cell site. The wireless service provider 14 can establish communication between two or more wireless devices 10 through the wireless network 12 , or between a wireless device and one or more landline phones by the interconnection 16 with the public switched telephone network (PSTN) or with other wired or wireless communications networks such as the Internet and Voice Over Internet Protocol (VOIP).
A monitoring service provider 20 according to the disclosed embodiment provides monitoring services for participating wireless devices 10 , and receives information from the wireless service provider 14 concerning the identities and geographic locations of those participating wireless devices 10 . It should be understood that the services and operations of the monitoring service provider 20 may be provided by a wireless service provider 14 or by an entity separate from the wireless service provider 14 , although the two service providers 14 and 20 are shown functionally separated in FIG. 1 . In either case, the monitoring service provider 20 provides monitoring and administrative functions for subscribers to the service, based on the identification of one or more wireless device 10 provided to the monitoring service provider 20 by those subscribers. Typical subscribers to the present monitoring and administrative services could be parents concerned with the locations of one or more children caring cell phones or other wireless devices 10 , and business operators desiring to monitor and administer activities of their service persons carrying wireless devices 10 .
The monitoring service provider 20 includes a processor 22 operatively communicating at 24 with the wireless service provider 14 , and a database storage device 26 operatively connected to the processor 22 for receiving and storing information identifying particular wireless devices 10 being monitored and location information for those wireless devices 10 . Information concerning the geographic location of the wireless devices 10 may be obtained by any technique known in the art. Such geographic location techniques currently include the global positioning system (GPS) relying on satellite information that can be received by GPS-enabled wireless devices 10 . Other current techniques for locating wireless devices 10 include, without limitation, time-difference-of-arrival measurement based on signals transmitted by the wireless device 10 and received at multiple radio towers of the wireless network 12 . Techniques for obtaining and processing geographic location information of cell phones and other wireless devices 10 are known to those skilled in the art. See, for example, U.S. Pat. No. 7,110,749, assigned to the assignee of the present invention and hereby incorporated by reference.
The monitoring service provider 20 may also receive location inputs from one or more sources other than the location information specific to the wireless devices 10 . Those sources appear in FIG. 1 as the one or more fixed location inputs 30 , with the understanding that “fixed” is herein used to denote location-based information derived from one or more sources other than the wireless devices 10 . As previously mentioned, examples of fixed information inputs 30 include information-card scanners or readers associated with a building or room containing, for example, a nursery school or day-care center, and RFID sensors that produce a unique signal when a person carrying an RFID device moves within a certain proximity to the sensor. A keypad entry device, onto which a person entering or leaving a particular location would enter a personal ID code, is another possible source of fixed location input information. Whatever the source, the one or more fixed location inputs 30 are supplied to the processor 22 of the monitoring service provider 20 through any suitable data link include wireless or wireline connections and using Internet Protocol (IP) or any other suitable data-transfer technique.
The monitoring service 20 compares the location information received for a wireless device 10 with the expected geographic location information supplied by a subscriber to the service and stored on the database 26 , as discussed below. If the comparison indicates that the wireless device 10 is not at an approved location, the monitoring service provider 20 notes an exception and initiates one or more supervisory action outputs at 32 . Examples of such supervisory actions are discussed below with reference to FIG. 2 .
FIG. 2 illustrates an example of monitoring and supervising the wireless device 10 according to the embodiment of FIG. 1 . At the start 202 of the process illustrated in FIG. 2 , it is assumed that a subscriber or account holder of the monitoring service has registered, with the monitoring service provider 20 , at least one wireless device 10 whose location and movement is to be monitored. That registration would typically include providing a unique identifier of the wireless device 10 , such as the unique Manufacturer's Identification Number and/or the telephone number associated with a cell phone whose location is to be monitored, or some other unique identifier such as the IP address in the case of a wireless device communicating over the Internet. Registration with the monitoring service provider would also include identifying at least one expected location or other geographic location of interest to the subscriber. Such geographic locations could include, for example, the location of one or more places where the wireless-device user is expected to be present, and/or locations that are not approved for visit by the user of a particular wireless device 10 . Furthermore, the subscriber may provide time- or date-relevant information pertaining to one or more locations, denoting approved times for arriving at or departing from particular locations. Such times may be absolute (“Leave the party at location X by 11 p.m.”) or relative, e.g., arrival at the location of a certain day-care center within 30 minutes after departing a particular school or other certain location. The information furnished to the monitoring service provider 20 by a subscriber is stored on the database 26 by the processor 22 .
Referring again to FIG. 2 , location information is obtained at 204 from a participating wireless device 10 . That location information may be obtained at periodic intervals, as known in the art. The processor 22 of the monitoring service provider 20 compares that location information at 206 with approved location information previously stored in the database 26 , with that comparison continuing unless the comparison of location information shows at 209 that that the wireless device 10 is at an unapproved location. In that latter case, the processor 22 at 208 notes an exception and at 210 initiates one or more predetermined supervisory actions in response to the exception, as shown by the output 32 on FIG. 1 . Exemplary supervisory actions according to the embodiment shown in FIG. 2 are identified at 212 . For example, the monitoring service provider 20 may at 214 contact the wireless device 10 , working through the wireless service provider 14 for that wireless device as shown at 216 . Contacting the wireless device 10 as at 214 may include a short audible and/or visual message appearing on the wireless device 10 , or may produce a characteristic ring tone, buzz, or vibration depending on the alerting capabilities of the particular wireless device 10 .
Supervisory action may also include partial or full disablement of operation of the wireless device 10 , as indicated at 218 . For example, the operation of a participating wireless device 10 would be temporarily restricted to block outgoing calls to anyone other than certain phone numbers identified by the subscriber (e.g., parent or supervisor numbers) and 911 emergency calls. Disabling operation of the wireless device 10 at 218 could occur concurrent with contacting that wireless device 10 as at 214 , so that the user of that wireless device 10 would receive a message alerting the user of arrival at an unapproved location and that operation of the wireless device 10 was thereafter restricted until being reset at the discretion or control of the monitoring-service subscriber.
Supervisory action may also comprise contacting one or more authorized persons as at 220 . Examples of authorized persons include one or both parents, a school administrator, or a supervisor of a service person carrying a wireless device 10 being monitored. Such alerting contacts to other recipients are initiated by the monitoring service provider 20 as indicated at 32 in FIG. 1 , and may include initiating one or more messages to addresses such as wireline or wireless phone numbers or IP addresses previously furnished to the monitoring service provider 20 by the subscriber. That monitoring service provider 20 may establish a hierarchy of authorized contacts, with an initial contact attempted to a first parent, and thereafter a contact to a second parent, followed by a contact to an administrator or other person if no preceding contact attempt is completed or acknowledged within a predetermined amount of time.
It is also within the purview of the present system to take supervisory action by contacting a 911 emergency call center as at 222 . Any such 911 contact could also transfer the last-available location information of the wireless device 10 to the 911 center as at 224 . Such emergency contact action may be appropriate only in certain situations, such as monitoring the location of a child or an elderly person who might be unable to seek emergency assistance.
FIG. 3 shows another embodiment for monitoring and supervisory control of the wireless device 10 according to a modified embodiment of the present invention. The method shown with respect to FIG. 3 starts at 302 and obtains destination information at 303 relating to one or more scheduled destinations for an individual. That destination information may include a time the person is expected to arrive at a particular destination, and each such time may be expressed either as an absolute time of day or as a relative time after received location information indicates that person has left a previous destination. Examples of destination information include the location of a daycare center or other post-school destination for a minor person, as well as a post-daycare destination (e.g., a friend's house) for that person. Intended destinations for service persons might include customer visits scheduled for that person throughout a work period.
The method according to FIG. 3 also obtains location information at 304 of the wireless device 10 , as with the corresponding element 204 described above with respect to FIG. 2 . Obtaining location information of the wireless device 10 at 304 may be accomplished using geographic location information received from the wireless service provider 14 as described above. Alternatively, the present location of the wireless-device 10 user may be obtained from a fixed-location input 30 as described with respect to FIG. 1 . For example, a person may present an identification card or other device when entering a particular location, and that information is transmitted to the monitoring service provider 20 from the sensor at that fixed location. A later departure of that person from the location may likewise be obtained either by geographic-location information derived from the wireless device 10 , or from a fixed-location input as the person scans an identification reader when exiting that location.
The method of FIG. 3 monitors location information of the wireless device 10 at 306 , and at 308 determines whether that wireless device 10 has departed a present location. If the wireless device 10 has departed the present location, then the processor 22 determines at 310 whether or not the person has timely arrived at the next destination previously scheduled at 303 . That destination arrival is determined from the location information either as obtained from the wireless device 10 carried by the person, or by a fixed-location input 30 derived from the next location. Assuming a timely arrival at that next location, the process moves to 312 where the processor 22 sees whether information concerning another destination for that person is in the system. If another destination is present, then at 314 the processor 22 returns to determining whether the person has departed from the current present location as at 308 . However, if at 312 the processor 22 determines that no other destination is scheduled for that person, the process ends.
If the processor 22 determines at decision 310 that the person has not arrived at the predetermined next destination within the time set for that arrival, then at 316 the processor 22 branches to note an exception at 208 on FIG. 2 , and to take appropriate supervisory action on that exception as at 210 and 212 on FIG. 2 . As discussed above, what may constitute appropriate action depends on the circumstances and the person being monitored; an appropriate supervisory action for a service person not timely arriving at the next scheduled customer location would likely be different from the action to be taken when a child has not reached a destination within a certain amount of time after departing a previous location.
It should also be understood that the foregoing relates only to disclosed embodiments of the present invention and that numerous changes and modifications therein may be made without departing from the spirit and scope of the invention as defined in the following claims. | Method and apparatus are for monitoring the location of a wireless device and taking supervisory action in response to that location. Location information obtained from a user's wireless device, or otherwise concerning the present location of the user, is monitored and compared with one or more locations previously approved for that user. An exception is noted if the user reaches a non-approved location, or fails to timely arrive at an approved destination. In response to an exception, supervisory action is taken which may include contacting the wireless device, partially or completely disabling further service of that device, or contacting another person. | 6 |
STATEMENT REGARDING RELATED APPLICATIONS
This application is a continuation of and claims priority to application Ser. No. 11/200,873 filed Aug. 10, 2005, now U.S. Pat. No. 7,340,180 entitled “Countermeasures for Idle Pattern SRS Interference in Ethernet Optical Network Systems,” the entire contents of which are incorporated by reference.
FIELD OF THE INVENTION
The present invention relates to countermeasures that can be used to mitigate the effects of Stimulated Raman Scattering (SRS) that causes data transmission propagated at a first optical wavelength to interfere with broadcast video transmission propagated at a second optical wavelength in optical waveguides used in optical networks. More particularly described, the present invention relates to modifying idle transmission patterns or transmitting random data to a non-existent MAC address to decrease the SRS optical interference and improve the quality of video transmissions.
BACKGROUND OF THE INVENTION
The Institute of Electrical and Electronics Engineers (IEEE) has defined the 802.3ah Ethernet in the First Mile (EFM) Point-to-Multipoint standard for Ethernet-based Passive Optical Networks (EPONs). These networks can act as optical access networks for residential and business subscribers, providing a full range of communications services to those users. Consistent with such deployments, the IEEE 802.3ah standard specifies optical wavelengths that leave room or capacity for communication services other than Ethernet, particularly broadcast video.
Unfortunately, key characteristics of Ethernet data transmission can cause significant optical interference to video signals through a phenomenon known as Stimulated Raman Scattering (SRS). The IEEE 802.3ah standard specifies that Ethernet data is transmitted to the subscriber using the 1490 mn optical wavelength. Wavelength division multiplexing (WDM) permits an optical network using the 1490 nm optical wavelength to propagate data to also deliver broadcast video on the same optical fiber using the 1550 nm optical wavelength. When the network transmits on two optical wavelengths simultaneously, such as the 1490 nm and 1550 nm wavelengths, it can be vulnerable to SRS. In IEEE 802.3ah EPON networks, the Ethernet signal transmitted at 1490 nm amplifies any video signal transmitted at 1550 nm, and therefore interference can result in a noticeable degradation of video quality. A particularly egregious case occurs when an Ethernet idle pattern is transmitted because no data is available to transmit. This causes extreme interference with broadcast video on certain channels.
FIG. 1 illustrates a conventional PON network 100 that is subject to SRS. Signals originate at a data service hub 110 and are transported on a passive optical network (PON) 120 . The PON 120 comprises optical fibers 160 and 150 , and an optical tap, or splitter 130 , which divides the signals between a plurality of Subscriber Optical Interfaces 140 . The Subscriber Optical Interfaces 140 are placed on the premises of each subscriber where they convert optical signals into the electrical domain in order to deliver video, voice, and data services to that subscriber. The PON 120 comprises a trunk fiber 160 , which carries optical signals to a plurality of subscribers, and a drop fiber 150 , which carries optical signals to a single subscriber. In some instances there can be an intermediate fiber which follows a portion of the optical splitting.
SRS between optical signals can develop in the trunk fiber 160 , and is a function of the signal levels and optical wavelengths used. The amount of SRS optical interference introduced is a complex function of the distance 170 to the split. Very short lengths of optical fiber are not susceptible to SRS, but trunk fibers 160 of practical length tend to be quite susceptible to SRS. The IEEE 802.3ah EFM standard specifies distances of 10 and 20 km, which can be all in the Trunk Fiber 160 , or some portion can be after the split, in the drop fiber 150 . The worst case situation is where all the fiber is in the trunk portion 160 . The IEEE 802.3ah standard also specifies the signal levels to be used.
FIG. 2 illustrates the related phenomenon of noise when a random signal is optically transmitted over a fiber, as it would manifest itself in a worst-case IEEE 802.3ah system. FIG. 2 illustrates the frequency spectrum of optical video signals. When an Ethernet idle pattern is transmitted, the signal power becomes concentrated at a few frequencies rather than being spread out evenly across the entire bandwidth as is the case illustrated in FIG. 2 . This means that the idle pattern will affect fewer channels, but the effect will be much greater on those channels.
The curve plots the effect of SRS on an optical system carrying random data and also analog video. Better performance is reflected at higher points on the graph. The effect of random data is to worsen the carrier-to-noise ratio (C/N) of the received optical signal, to well below acceptable levels. The curve plots the C/N on each lower-frequency channel where the problem is the worst for a family of PONs of different practical lengths.
The figure also illustrates C/N limits for cable TV good engineering practice 220 and typical Fiber-to-the-Home (FTTH) typical performance absent SRS 210 . If SRS causes the C/N to get significantly worse than the C/N without it 210 , then the performance of the optical system will be degraded and users will not perceive the benefits that FTTH is supposed to offer. PONs with distances to the split 170 of 2 km 230 , 5 km 240 , 10 km 250 and 20 km 260 are shown. From this curve, one can see that a 2 km distance will not drop the C/N below cable TV good engineering practices 220 , but it will be close at the lowest channel, and the performance will be worse than what a FTTH system should deliver. Longer PONs will cause unacceptable C/N performance on several channels.
One of ordinary skill in the art knows that a different selection of optical wavelengths could reduce or effectively eliminate the problem introduced by SRS. For example, other FTTH systems are known which use 1310 nm for bidirectional transmission of data. These systems are usually not troubled by SRS. However, the IEEE 802.3ah standard requires that downstream data be transmitted at 1490 nm, where the problem exists. It is possible to move the wavelength of the video transmission as high as possible in the 1550 nm window, but this will only result in slight improvement.
One of ordinary skill in the art is familiar with the specification for Gigabit Ethernet, which requires a prescribed bit pattern to be transmitted as an idle pattern when there is no data available to be transmitted. This method used in gigabit Ethernet and in certain other applications, is called 8B/10B encoding. The purpose of the 8B/10B encoding is to remove the low frequency dc component that digital optical systems are not able to transmit and to ensure clock synchronization to prevent the clock from wandering out of phase, which can damage data recovery. In 8B/10B encoding, for every 8 bits (one byte), a 10 bit code is substituted. The substituted 10 bit code is chosen to have very close to an equal number of 1s and 0s and three to eight transitions per symbol. The codes satisfy the requirement of no dc component in the signal, and the large number of transitions ensure clock synchronization. Furthermore, since a limited number of the available codes are used, the encoding provides another way to detect transmission errors.
The downside of 8B/10B encoding is that because 10 bits must be transmitted to represent 8 bits, the bandwidth required is increased by 25%. For instance, in a gigabit Ethernet system, the desired data is transmitted at 1 Gb/s, but because of 8B/10B encoding, the data rate on the fiber (the so-called wire rate) is 1.25 Gb/s. Furthermore, it has been found that when the idle pattern is transmitted and encoded with 8B/10B encoding, the resulting signal has strong power concentration at certain frequencies. These frequencies for Gigabit Ethernet happen to be at 62.5 MHz and all harmonics thereof, with the odd harmonics having virtually all of the power.
The IEEE 802.3ah standard defines two different idle codes. The first idle code, referred to as /I1/, has two versions. One version changes the running disparity on the link from positive (a preponderance of 1s—designated as /I1 + /) to negative (a preponderance of 0s—designated as /I1 − /), while the second version changes the running disparity from negative to positive. As known to one or ordinary skill in the art, the running disparity rules change the transmitted value from one column to the other based on certain rules related to the number of 1s or 0s that have been transmitted in the previous code group. These rules ensure that there is no dc content in the optical signal and that there is not a long string of like binary digits, thus ensuring reliable clock recovery.
The second idle code, referred to as /I2/, maintains the existing running disparity on the link. In a normal procedure for using these two idle codes the systems performs one of the following: (a) If, after the last transmitted frame, the link has a positive running disparity, the system transmits one /I1 + / to reverse the running disparity, and then transmits /I2/ continuously or (b) if, after the last transmitted frame, the link has a negative running disparity, the system transmits /I2/ continuously.
FIG. 3 is illustrates a measured spectrum 300 of a Gigabit Ethernet signal when it is carrying an idle pattern in the conventional art. On the spectrum 300 , frequency in MHz is plotted along the x-axis, and relative amplitude in decibels (dB) along the y-axis. The amplitude scale shows increments of 10 dB. Note the strong presence of odd harmonics of 62.5 MHz. When this pattern is optically transmitted downstream in a network over an optical waveguide such as the one shown in FIG. 1 , the SRS optical interference will cause very severe crosstalk in the video channels at these frequencies. The lowest frequency, 62.5 MHz, is of particular concern, as the worst SRS crosstalk usually occurs at lower frequencies such as this. Television channel 3 occupies this spectrum on the video layer. Its picture carrier is at 61.25 MHz (as prescribed by FCC frequency allocations), so the interference caused by the idle pattern appears 1.25 MHz above the picture carrier. One or ordinary skill in the art knows that this is a frequency at which the signal is particularly sensitive to interference. The interference will show up as a “beat,” or moving (usually) diagonal stripes in the picture.
In view of the foregoing, there is a need in the art to mitigate the effects of SRS optical interference on video transmissions in optical networks that use the IEEE 802.3ah data standard. Particularly, a need exists in the art for reducing or substantially eliminating the optical interference between data transmitted on a first optical wavelength and video information transmitted on a second optical wavelength when the data and video information are propagated along the same optical waveguide.
SUMMARY OF THE INVENTION
The present invention can mitigate the effects of SRS optical interference in optical networks between data transmitted at a first optical wavelength, such as 1490 nm, and video information transmitted at a second optical wavelength, such as 1550 nm. Specifically, the present invention can substantially reduce or eliminate SRS optical interference produced by idle transmission patterns generated in accordance with the IEEE 802.3ah data standard that are propagated at 1490 nm and that can interfere with video information propagated at 1550 nm. The invention can reduce or substantially eliminate SRS optical interference in optical networks by modifying the idle transmission pattern or transmitting random data to a non-existent MAC address.
One exemplary aspect of an optical network system embodying the invention can be described as follows: Data signals can be received by a tap routing device from different data sources including telephone switches or internet routers. These data signals can then eventually be transmitted at a first optical wavelength to a plurality of subscriber optical interfaces which are located on the premises of subscribers. Video information such as broadcast video can be transmitted at a second optical wavelength along the same optical waveguide of the data signals to the plurality of subscriber optical interfaces.
For data sent to subscribers downstream along the optical waveguide according to a standard that requires idle patterns, such as the IEEE 802.3ah data standard, and when no data signals are being transmitted, the tap routing device can transmit ten-bit idle patterns downstream. An idle pattern replacement device can monitor the downstream data of the tap routing device in the electrical domain and can detect when the idle patterns are being transmitted. In response to the transmission of an idle pattern in the electrical domain or the absence of data, the idle pattern replacement device can generate substitute data in the electrical domain to replace the idle pattern that is produced according to the data standard, such as the IEEE 802.3ah standard. The substitute data in the electrical domain may then be converted into the optical domain and then transmitted at the first optical wavelength along with the video information at a second optical wavelength to the plurality of subscriber optical interfaces.
According to one exemplary aspect of the present invention, the idle pattern replacement device can generate substitute data in the electrical domain by generating non-repetitive random data and transmitting it to a non-existent MAC address. First, the idle pattern replacement device can create a predetermined Ethernet header based on a group of non-existent MAC addresses. Next, the idle pattern replacement device can generate forty bytes of random data. Finally, the cyclical redundancy check (CRC) can be calculated from the previously created Ethernet header and random data and the entire Ethernet frame can be transmitted to the optical transmitter. The optical transmitter can then convert data generated in the electrical domain into the optical domain for optical transmission over a waveguide. The generation of substitute data in the electrical domain can reduce any electrical interference between data and video signals in the electrical domain. And when the substitute data is converted to the optical domain, the substitute data can reduce any optical interference between data and video signals in the optical domain.
For another exemplary aspect of the invention, an idle pattern replacement device can reduce the effect of SRS between optical signals by modifying the normal idle transmission pattern. As previously discussed, SRS optical interference is caused by the repetition of the normal idle transmission pattern. In accordance with an exemplary aspect of the present invention, an alternative idle transmission pattern may be transmitted in the electrical domain to break up the normal idle transmission pattern of sending a repetitive pattern. The increased randomness of this pattern after it is converted to the optical domain can reduce the effect of SRS while still conforming to the specifications of the IEEE standard.
For another exemplary aspect of the invention, non-repetitive random data can be generated and then transmitted to a non-existent MAC address using an idle pattern replacement device comprising a CPU, a Layer 2 (L2) switch fabric, and an EPON chip. As is understood by one of ordinary skill in the art, L2 refers to the second layer of the ISO seven layer data transmission model, and specifically is where Ethernet is implemented. Ethernet implementations are usually done using a combination of hardware and software. The term “switch fabric” refers to the combination of hardware and software that allows data packets to be switched from one of a plurality of inputs to one of a plurality of outputs. In this aspect of the invention, the Ethernet frame data can be assigned an associated priority value. A CPU, or other special circuitry, can continuously transfer random data frames in the electrical domain to the L2 switch fabric with the lowest priority value. When the L2 switch fabric receives real data from the logic interface, data in the electrical domain can be immediately transferred to the tap routing device while the random data frames can be dropped. However, when the L2 switch fabric stops receiving real data and no data is being transmitted, the random data frames can be made available and can be transmitted to the tap routing device in place of the normal idle patterns. The optical transmitter that follows the tap routing device and tap multiplexer can convert any data in the electrical domain into the optical domain for optical transmission.
These and other aspects, objects, and features of the present invention will become apparent from the following detailed description of the exemplary embodiments, read in conjunction with, and reference to, the accompanying drawings.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is a block diagram illustrating the operating environment of a conventional PON network that is subject to SRS.
FIG. 2 is a graph illustrating the phenomenon of SRS optical interference for a conventional analog video transmission.
FIG. 3 is a graph illustrating the spectrum of a conventional Gigabit Ethernet optical signal comprising an idle pattern with 8B/10B encoding.
FIG. 4A is a block diagram illustrating the operating environment of a data service hub in accordance with an exemplary embodiment of the present invention.
FIG. 4B is a block diagram illustrating the operating environment of a data service hub in accordance with an alternative exemplary embodiment of the present invention.
FIG. 5 is a block diagram illustrating the operating environment of the tap routing device and subscriber optical interface in accordance with an exemplary embodiment of the present invention.
FIG. 6 is a block diagram illustrating the operating environment of the idle pattern replacement device in accordance with an exemplary embodiment of the present invention.
FIG. 7 is a logic flow diagram illustrating an exemplary method for reducing the effect of SRS by generating substitute data in accordance with an exemplary embodiment of the present invention.
FIG. 8 is a logic flow diagram illustrating an exemplary method for reducing the effect of SRS by generating non-repetitive random data and transmitting it to a non-existent MAC address in accordance with an exemplary embodiment of the present invention.
FIG. 9 is a logic flow diagram illustrating an exemplary method for reducing the effect of SRS by modifying the idle transmission pattern in accordance with an exemplary embodiment of the present invention.
FIG. 10 is a block diagram illustrating the operating environment of a data service hub in accordance with an alternative exemplary embodiment of the present invention.
FIG. 11 is a logic flow diagram illustrating an alternative exemplary method for reducing the effect of SRS by generating non-repetitive random data and transmitting it to a non-existent MAC address in accordance with an exemplary embodiment of the present invention.
FIG. 12 is a graph illustrating the reduction of the power spectrum of an idle Ethernet link using the alternate idle code strategy in accordance with an exemplary embodiment of the present invention.
DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS
The present invention relates to mitigating SRS optical interference between data propagated at a first optical wavelength and video information propagated at a second optical wavelength on the same waveguide. More specifically, the invention relates to improving the quality of video transmissions on a optical network by modifying idle transmission patterns or transmitting random data to a non-existent MAC address when data is transmitted according to a data standard at a first optical wavelength and when the video information is transmitted on a second optical wavelength.
In an exemplary embodiment of the present invention, an idle pattern replacement device can monitor the downstream data stream of a tap routing device in the electrical domain in order to detect the idle patterns that the routing device generates and that cause SRS optical interference between the optical data signals and optical video signals propagated at two different optical wavelengths. To mitigate the SRS optical interference, the idle pattern replacement device generates non-repetitive substitute data in the electrical domain to take the place of the previously generated repeating or constant idle patterns. The idle pattern replacement device accomplishes this goal by modifying the idle transmission patterns or transmitting random data to a non-existent MAC address. The substitute data of the idle pattern replacement device can be converted from the electrical domain to the optical domain and then optically transmitted to subscriber optical interfaces at a first optical wavelength that is different than a second optical wavelength used to carry video information.
Referring now to the drawings, in which like numerals represent like elements, aspects of the exemplary embodiments will be described in connection with the drawing set.
FIG. 4A is a block diagram illustrating the operating environment of a data service hub 400 in accordance with an exemplary embodiment of the present invention. Data is received by a logic interface 415 that is connected to data sources such as a telephone switch 410 and an Internet router 405 . The logic interface 415 can be connected to other data sources/sinks that are not illustrated.
The logic interface 415 is also connected to a tap routing device 433 . The tap routing device 433 can comprise a commercial chip that implements the IEEE 802.3ah standard by using 8B/10B encoding on the incoming data. Therefore, the tap routing device 433 can transmit idle code patterns when no data is received from the logic interface 415 . Alternatively the 8B/10B encoding may be added at the tap multiplexer 430 , as discussed below. The 8B/10B encoding process includes steps in which each 8-bit word of data is replaced with a specified 10-bit symbol. According to one exemplary embodiment, the tap routing device 433 sends the downstream data to a plurality of tap multiplexers 430 . The tap multiplexer 430 , that can comprise a Serializer/Deserializer (SERDES), divides the signal among a plurality of subscriber optical interfaces, and it handles serialization of data. In some exemplary embodiments, the tap multiplexer 430 can produce idle pattern codes. Usually when the tap multiplexer 430 has the capability to produce idle pattern codes, the tap routing device 433 does not.
In order to minimize the speed at which electrical circuits must operate, the data signals through the tap routing device are often handled in parallel. That is, a signal path that is, usually, 8, 16, 32, or 64 bits wide handles the signals, with many bits being handled on different wires at the same time. For example, if a data processing element is 32 bits wide, it handles 32 bits simultaneously on 32 wires, but the data rate on any one wire is only 1/32 of the overall data rate. However, before the signal can be supplied to the fiber optic optical transmitter 435 , it must be converted to a faster serial data on a single wire, since there is only one optical transmitter 435 and one fiber optic cable to handle data to each group of subscriber optical terminals. This is the purpose of the serialization portion of the SERDES, to convert the parallel paths to a single serial path. At the same time, the 8B/10B encoding may be added. The deserialization portion of the SERDES operates on the received signal coming in from Optical Receiver 440 , converting from serial to parallel format. This process is understood by one of ordinary skill in the art.
The tap multiplexer 430 can also add idle code patterns when no input data is available. The plurality of tap multiplexers 430 are connected to a plurality of optical transmitters 435 and optical receivers 440 . The optical transmitters 435 can comprise can comprise one of Fabry-Perot (F-P) Laser Transmitters, distributed feedback lasers (DFBs), or Vertical Cavity Surface Emitting Lasers (VCSELs). However, other types of optical transmitters are possible and are not beyond the scope of the invention. The optical receivers 440 can comprise one or more photoreceptors or photodiodes that convert optical signals into electrical signals. According to one exemplary embodiment, when downstream data to subscribers is transmitted according to a standard, such as the IEEE 802.3ah standard, the optical transmitters 435 transmit downstream data at a wavelength of approximately 1490 nm. Meanwhile, the optical receivers 440 receive upstream data on a wavelength of 1310 nm.
Further describing FIG. 4A , broadcast video signals are modulated on RF carriers with modulators 455 and 460 , whose outputs are combined in combiner 465 . According to one exemplary embodiment, there can be over one hundred modulators 455 , 460 (not illustrated). The combined RF signals can be used to modulate a 1550 nm optical signal in optical transmitter 470 , whose output is amplified if necessary in amplifier 475 . Splitter 480 divides the optical signal among all outputs, supplying a portion of the signal to respective three wavelength optical multiplexers 445 .
Each optical multiplexer 445 combines the downstream data of a first optical wavelength, such as 1490 nm, with the downstream video broadcast signals of a second optical wavelength, such as 1550 nm. Each optical multiplexer 445 also separates the upstream data signals sent on a third optical wavelength, such as 1310 nm, from the downstream optical signals. Each optical multiplexer 445 sends the upstream data signals sent using the third wavelength to respective optical receivers 440 .
Even though the tap multiplexer 430 and the 3 k optical multiplexer 445 share similar nomenclature, and even though their functions are somewhat analogous, the two devices work much differently. As is understood by one of ordinary skill in the art, a multiplexer is any device that combines two or more signals. The tap multiplexer 430 works in the electrical domain to combine signals to and from the optical transmitter 435 and the optical receiver 440 . On the other hand, 3λ optical multiplexer 445 operates in the optical domain, and combines downstream signals from optical transmitter 435 and splitter 480 , with upstream signals transmitted to optical receiver 440 . In essence, the 3λ optical multiplexer 445 is the device that directs the three optical signals in the appropriate directions.
Optical signals entering and leaving the data service hub 400 are interfaced by way of the combined signal Input/Output ports 450 that are coupled to respective optical waveguides 160 . The optical waveguides 160 are connected to optical taps or splitters as illustrated in FIG. 1 .
In an exemplary embodiment of the present invention, as illustrated in FIG. 4A , multiple idle pattern replacement devices 425 A are connected between the tap routing device 433 and the tap multiplexers 430 . Each idle pattern replacement device 425 A monitors the downstream electrical output of the tap routing device 433 .
In an exemplary embodiment of the present invention, the idle pattern replacement device 425 A monitors this electrical data and when it detects either an idle pattern or no data, it inserts substitute data that is later converted from the electrical domain into the optical domain at a first optical wavelength in order to avoid SRS optical interference between downstream optical data signals at the first optical wavelength and downstream video signals at a second optical wavelength. The downstream optical data signals and downstream optical video signals are sent through the combined signal input/output port 450 over an optical waveguide 160 to optical splitters 130 .
In an exemplary embodiment of the present invention, the tap routing device 433 , idle pattern replacement device 425 A, and tap multiplexer 430 may all be incorporated on a single commercial chip.
FIG. 4B is a block diagram illustrating the operating environment of a data service hub 400 in accordance with an alternative exemplary embodiment of the present invention. As illustrated in FIG. 4B , the idle pattern replacement device 425 B, is located in the tap multiplexer 430 . The tap multiplexer 430 can comprise a buffer (not illustrated) in this exemplary embodiment. In this alternative exemplary embodiment, the idle pattern replacement device 425 B is implemented through hardware or software (or both) to produce an alternative idle code pattern as shown in FIG. 9 and discussed below.
FIG. 5 illustrates the Optical Splitter 130 and the Subscriber Optical Interface 140 according to one exemplary embodiment of the present invention. Optical signals enter the Combined Signal input/Output Port 505 , and from there propagate to the Optical Tap or Splitter 130 . There are multiple outputs from the Optical Tap or Splitter 130 , one for each Subscriber Optical Interface 140 served by the instant Optical Tap 130 . These are connected by Drop Fibers 150 .
The Subscriber Optical Interface 140 comprises a three wavelength (3λ) Optical Multiplexer 445 , which separates the three optical wavelengths, 1310 mn, 1490 nm, and 1550 nm, as did the corresponding device in the Data Service Hub 400 . The 1550 nm broadcast signal is routed to an Analog Optical Receiver 525 , and from there to a Modulated RF Unidirectional Signal Output 535 which connects to the subscriber's TVs and other suitable appliances known to one of ordinary skill in the art.
The 1490 nm downstream data is routed to a Digital Optical Receiver 540 then to a processor 550 , which manages data signals and interfaces to Telephone Input/Outputs 555 and Data interfaces 560 .
Referring now to FIG. 6 , this figure is a block diagram illustrating the operating environment of the idle pattern replacement device 425 A in accordance with an exemplary embodiment of the present invention. Clock synchronization that usually must take place is not illustrated in FIG. 6 , but this is well-known to one of ordinary skill in the art.
The idle pattern replacement device 425 A comprises a downstream data shift register 640 operating in the electrical domain, which accepts data 620 from the tap routing device 433 . As is understood by one of ordinary skill in the art, data at this point is often handled in parallel format, whereby a number of bits (typically 8, 16, 32, or 64) are transferred simultaneously, or in parallel. Thus, downstream data shift register 640 is comprised of several sets of connected storage devices 625 that may comprise flip-flops, which are well known to one of ordinary skill in the art. For each bit in the parallel data transfer, data is shifted horizontally across the downstream data shift register 640 . The purpose of the downstream data shift register 640 is to delay the start of each packet long enough to determine whether real data, or non-idle code data, is present, and if not, to allow random data to be inserted. If true data is present, then it is passed through to switches 645 and sent to the tap multiplexer 430 .
If no data is being sent from the tap routing device 433 , this no-data condition is detected by the no-data detector 630 . The no-data detector 630 is coupled to each of the first stage storage devices in downstream data shift register 640 , to allow it to detect when no data is present. Depending on the exemplary embodiment, a no-data condition can be represented by all 0s or 1s in the first stage of the shift register, or it can be represented by a unique data pattern, such as idle code. It could also be represented by the lack of a clock signal to shift data into the downstream data shift register 640 when the tap routing device 433 does not produce any idle code. In such an exemplary embodiment when the tap routing device 433 does not produce any idle code, the no-data detector 630 determines if an absence of data condition exists in which there is a lack of a clock signal or through pattern matching. When the no-data detector 630 is looking for the absence of data, it uses pattern matching to detect the absence of data. The absence of data typically comprises all 0s or 1s, which is well to known to one of ordinary skill in the art.
If the embodiment of the system is such that when no data is present, a fixed pattern of data 620 appears from the tap routing device, such as an idle code pattern, then the no-data detector 630 comprises a pattern recognition circuit known to one of ordinary skill in the art. The no-data detector 630 determines when the data pattern representing no real data or idle code pattern is present. Such a pattern recognition device can comprise a series of exclusive OR gates, for example, with an input from each exclusive OR gate connected to a 1 or a 0, depending on the pattern to be recognized. Furthermore, there are also software techniques for recognizing a pattern, like idle code patterns, which utilize the same process implemented in software that are well known in the art.
So long as data is present, then the no-data detector 630 controls the data selection switch control 635 to keep the data selection switches 645 in the positions shown so that the data is transmitted to the tap multiplexer 430 . In this position, input data is supplied to the tap multiplexer 430 after a delay represented by the number of storage devices 610 connected horizontally in the downstream data shift register 640 .
If a no-data condition is detected, then the data selection switches 645 are thrown to the opposite position, which connects the output to the replacement data shift register 615 . This replacement data shift register 615 is similar to the downstream data shift register 640 except that it is loaded from a data initializer 605 . The replacement shift register 615 contains data, such as inventive idle code, that is put in when no data is being transmitted, in order to prevent the tap multiplexer 430 from generating any conventional idle code patterns in exemplary embodiments in which the tap routing device 433 does not produce idle code patterns. As noted above, conventional idle code will cause the SRS problems as described above between downstream optical data signals of a first optical wavelength and downstream optical video signals at a second optical wavelength.
The data initializer 605 can be as simple as fixed pre-programming of the state of the storage devices 625 in the replacement data shift register 615 . It can also be a microprocessor that can load data that is either pre-determined or downloaded or generated randomly by the microprocessor. A number of implementations are known to one of ordinary skill in the art and not beyond the scope of the invention.
The actual data loaded into the replacement data shift register 615 can be of a number of types. One type of data can be random numbers preceded by a code that tells the subscriber optical interface to ignore the data that follows in an Ethernet frame. Another type of data can be random data sent to a non-existent Ethernet MAC address, as is understood by one of ordinary skill in the art.
According to another exemplary embodiment of the present invention, random data is sent to a pre-determined set of non-existent MAC addresses such that there is minimal concentration of signal power at any one frequency. The set of non-existent MAC addresses can be selected from the range of MAC addresses that are assigned to each idle pattern replacement device 425 A. Alternatively, the same set of non-existent MAC addresses can be assigned to all idle pattern replacement devices 425 A. According to another exemplary aspect, an alternate idle code pattern, that complies with IEEE's 802.3ah standard, can be transmitted. All of these types of data can lessen the SRS optical interference and improve the quality of video transmissions.
The length of both the downstream data shift register 640 and the replacement data shift register 615 can be identical. The downstream data shift register 640 usually must delay any real data arriving after a period of no data, until the replacement data shift register 615 has shifted out its entire data. A normal Ethernet idle pattern is 20 bytes long, but the minimum length for a complete Ethernet frame is 64 bytes.
Thus, when an idle condition is detected and if the embodiment is such that random data is being sent to a non-existent MAC address, the output to the tap multiplexer 430 must comprise the 64 bytes of the packet being sent to the non-existent MAC address. If a real data packet comes along before the end of this 64 byte word, then the real data must be delayed in the downstream data shift register 640 until the end of the data being sent to the non-existent MAC address. The switches 645 are then thrown to the position shown, and the real data is shifted out.
If the random data being sent to the non-existent MAC address has all been shifted out and still there is no real data to be sent, then the Data Initializer 605 loads the Replacement Data Shift Register 615 with a new set of random data and a non-existent MAC address, and the process begins again. Because of this possibility (multiple packets of random data sent to non-existent MAC addresses sequentially), according to one exemplary embodiment, it is preferred to use a plurality of random non-existent MAC addresses, to prevent a common address from forcing a spectral peak. As soon as new real data is presented to Downstream Data Shift Register 640 , then at the completion of the current random data packet being sent to the non-existent MAC address, the real data is transmitted. A Communications Path 655 between the No-data Detector 630 and the Data Initializer 605 facilitates coordination between the data initializer 605 and the no-data detector 630 of the Idle Pattern Replacement Device 425 A.
Referring now to FIG. 7 , this Figure is a flow chart depicting an exemplary method 700 for reducing the effect of SRS by generating non-repetitive substitute data in accordance with an exemplary embodiment of the present invention. In Step 710 , the idle pattern replacement device 425 A receives input from the tap routing device 433 . In step 720 , the idle pattern replacement device 425 A examines the input data to determine whether an idle code pattern is being transmitted or whether there is no data. The operation of detecting an idle code pattern can be performed by a pattern match to analyze two bytes of the data and determine whether the data matches the idle pattern.
If the idle pattern replacement device 425 A determines that an idle pattern is not being transmitted in Step 720 , the data is transmitted to the tap multiplexer 430 in Step 750 . This data is transferred through Downstream Data Shift Register 640 . However, if the idle pattern replacement device 425 A determines that an idle pattern (or no data, depending on the embodiment) is being transmitted in Step 720 , the idle pattern replacement device will need to transmit substitute non-repetitive data to the tap multiplexer 430 . First, the idle pattern replacement device 425 A will determine if real data from a previous packet is being held within the Downstream Data Shift Register 640 in Step 730 . If the Downstream Data Shift Register 640 contains real data from a previous packet, that data will be transmitted to the tap multiplexer 430 in Step 750 . If the buffer does not contain real data from a previous packet, the Data Initializer 605 will generate substitute data in Routine 740 , which will be transmitted to the tap multiplexer 430 in Step 750 , by way of Replacement Data Shift Register 615 .
In an alternative exemplary embodiment, in Step 710 , the idle pattern replacement device 425 B of FIG. 4B receives input from the tap routing device 433 . In step 720 , the idle pattern replacement device 425 B examines the input data to determine whether an idle code pattern is being transmitted. The operation of detecting an idle code pattern can be performed by a pattern match to analyze one or more bytes of the data and determine whether the data matches the idle pattern. If the idle pattern replacement device 425 B determines that an idle pattern is not being transmitted in Step 720 , the data is transmitted to the tap multiplexer 430 in Step 750 ; otherwise, the idle pattern replacement device will need to transmit an alternative idle code pattern to the tap multiplexer 430 .
In Step 730 , the idle pattern replacement device 425 B will determine if any real data from a previous packet is stored in a buffer. If the idle pattern replacement device 425 B determines that any real data from a previous packet is stored in a buffer in Step 730 , the data is transmitted to the tap multiplexer 430 in Step 750 ; otherwise, the method proceeds to Step 740 to generate an alternative idle code pattern.
In Step 740 , the idle code replacement device 425 B generates an alternative idle code pattern and transmits the alternative idle code pattern to the tap multiplexer 430 in Step 750 . More specific details related to the generation of an alternative idle code pattern are shown in FIG. 9 and discussed below.
FIG. 8 is a flow chart depicting a first exemplary Routine 740 A for reducing the effect of SRS by generating non-repetitive random data and transmitting it to a non-existent MAC address in accordance with an exemplary embodiment of the present invention. In Step 810 , the idle pattern replacement device 425 A has determined in Step 730 that it must generate substitute data because no real data is available. In Step 820 , the idle pattern replacement device 425 A creates a predetermined Ethernet header.
The header is based on a group of non-existent or reserved MAC addresses stored in the Data Initializer 605 . The creation of Ethernet headers are well known in the art. Next, in Step 830 , the idle pattern replacement device 425 A generates forty (40) bytes of random substitute data. In Step 840 , the idle pattern replacement device 425 A performs a cyclical redundancy check (CRC) based on the previously created header and random data. Performing a CRC is an optional step because it does not matter whether this packet of substitute data is actually delivered to an actual MAC address, as it is just random data, but the CRC is part of the Ethernet standard. Finally, in step 850 the data is passed to the tap multiplexer 430 for transmission.
Combining the Ethernet header, random substitute data, and CRC from Routine 740 A can add up to sixty-four (64) bytes of data that is to be transmitted to the tap multiplexer 430 . Only two (2) bytes of data must be read to determine whether an idle pattern is being transmitted. Therefore, in method 700 , two (2) bytes of idle pattern data could be sent that could trigger Routine 740 to begin creating sixty-four (64) bytes of data to be transmitted to the tap multiplexer 430 . In the meantime, bytes of real data could be transmitted from the optical routing device 433 to the idle pattern replacement device 425 A.
However, instead of immediately transferring the real data to the tap multiplexer 430 , the real data is held in a buffer until the entire sixty-four (64) bytes of random substitute data is transmitted to the tap multiplexer 430 . It should be noted that in the exemplary method 700 , the No-data Detector 630 is continuously monitoring the incoming data to determine whether idle pattern data or real data is being transferred. The continuous monitoring of Data 620 allows any real data that immediately follows any idle pattern data to be stored, or buffered, in Downstream Data Shift Register 640 until all random substitute data is transmitted to the tap multiplexer 430 . Furthermore, the buffer allows the continuous storage of random substitute data that can immediately be transferred to the tap multiplexer 430 when an idle pattern is detected.
FIG. 9 is a flow chart depicting an alternate exemplary method 740 B for reducing the effect of SRS by modifying the idle transmission pattern in accordance with an alternate exemplary embodiment of the present invention. As previously discussed, the IEEE 802.3ah standard defines two different idle codes: (1) /I1−/ (running disparity from negative to positive) and /I1+/ (running disparity from positive to negative); and (2) /I2/ (normal running disparity). Idle codes /I1−/ and /I1+/ must be transmitted as a pair to keep the disparity consistent with the requirements of the standard. This relates to keeping the number of 1s and 0s transmitted equal. One of ordinary skill in the art knows that it is imperative to keep the number of 1s and 0s transmitted equal, to remove any dc component from the data. The continuous transmission of the /I2/ code group, as defined by the standard, has a significant effect on interference from SRS. Therefore, to overcome the effects of the SRS optical interference, the continuous transmission of the I2 code group can be eliminated without violating the 802.3ah standard.
In Step 910 , the idle code replacement device 425 B has determined in Step 720 that it must generate substitute data because an idle pattern code is being transmitted and there is no waiting data available in a buffer in Step 730 . If there is waiting data in a buffer, it is sent to the tap multiplexer 430 before the routine of FIG. 9 is entered.
In Step 920 , the last frame transmitted is checked to see if it had a positive running disparity. If so, Step 920 is exited through the YES path and a single /I1+/ is transmitted to reverse the running disparity as required by the IEEE 802.3ah standard. After Step 920 , the method proceeds to Step 940 . Furthermore, Step 940 is also entered if the result of Step 920 is NO. In Step 940 , a random bit, either a 1 or a 0, is generated, with equal probability of the random bit being 1 or 0. In Step 950 , that random bit is examined to see if it is a 1 or a 0. If the random bit is a 0, then Step 950 is exited at the YES outlet, and a normal idle pattern, /I2/ is transmitted in Step 960 . If the random bit is a 1, then Step 950 is exited at the NO outlet, and a pair of idle patters, /I1+/ followed by /I1−/, are transmitted in Step 970 .
After transmitting either /I2/ in Step 960 or the pair /I1+/ and /I1−/ in Step 970 , the routine returns to Step 750 . In Step 750 , the idle pattern is passed to Tap Multiplexer 430 , then control passes back to Step 710 , where the incoming data is again examined to see if there is real data to be transmitted, or whether another idle code must be generated.
FIG. 10 is a block diagram illustrating the relevant portions of an alternative operating environment of a data service hub 400 in accordance with an exemplary embodiment of the present invention. Data is received from the logic interface 415 at an L2 (Layer 2, meaning in this case Ethernet) switch fabric 1030 . Data received from the logic interface 415 will typically comprise either real data or an absence of data. The L2 switch fabric 1030 uses pattern matching to detect the absence of data. The absence of data typically comprises all 0s or 1s, which is well to known to one of ordinary skill in the art. This switch fabric may be part of Tap Routing Device 433 . In this case, the L2 Switch Fabric 1030 simply represents another port on the switch that is part of the Tap Routing Device 433 , with the new port being used to accept data from CPU 1010 . As the L2 switch fabric 1030 continues to receive data from the network, the CPU 1010 , or other special purpose circuitry, continuously produces bytes of random information data 1020 . The CPU 1010 transmits the bytes of random information data 1020 to the L2 switch fabric 1030 . The L2 switch fabric 1030 processes the data received from the logic interface 415 and the random information data 1020 and transmits the appropriate data to the tap routing device 433 , in accordance with an exemplary method discussed in FIG. 11 below.
Referring now to FIG. 11 , this figure is a flow chart depicting an alternative exemplary method 1100 for reducing the effect of SRS by generating non-repetitive random data and transmitting it to a non-existent MAC address in accordance with an exemplary embodiment of the present invention. In Step 1110 , data is transmitted from the logic interface 415 to an L2 switch fabric 1030 . In Step 1120 , the CPU 1010 , or other special purpose circuitry, continuously generates bytes of random information data 1020 , assigning the lowest possible priority to that data 1020 . In Step 1130 , the CPU 1010 transmits the bytes of random information data 1020 to the L2 switch fabric 1030 . As well known in the art, Ethernet frames allow priority information to be inserted with the data that is being transmitted. Therefore, according to this exemplary embodiment, the random information data 1020 transmitted from the CPU 1010 is set to the lowest priority value for Ethernet frames.
In Step 1140 , the L2 switch fabric 1030 selects between normal incoming data from 415 or random information data 1020 from the CPU 1010 . The L2 switch fabric 1030 always processes the data such that higher-priority data is transmitted before lower priority data is transmitted. The random information data 1020 from the CPU 1010 is sent as the lowest-priority data, and thus, the only time it will be transmitted is when there is no data available from the logic interface 415 . In Step 1150 , the L2 switch fabric 1030 transmits the data with the higher priority value to the tap routing device 433 . The data with higher priority will always be the data from the logic interface 415 if there is any real data to transmit, so that the only time the random information data 1020 from the CPU 1010 will be transmitted is if there is no data from the logic interface 415 ready to be transmitted.
Therefore, when no real data is being received from the logic interface 415 , the L2 switch fabric 1030 will forward the previously created random information data 1020 to the tap routing device 433 . Similar to FIG. 8 , along with the creation of the random information data 1020 , the CPU 1010 will also create an Ethernet header frame and perform a cyclical redundancy check (CRC) based on the previously created Ethernet header frame and random data. However, when real data is being received from the logic interface 415 , it is transferred to the tap routing device 433 because it is assigned a higher priority than the random information data 1020 .
Referring now to FIG. 12 , this figure illustrates a graph 1200 representing the power spectrum of an idle Ethernet link. The Ethernet link is the link from the Optical Transmitter 435 to Digital Optical Receiver 540 . As well known in the art, the Ethernet link could be any other Ethernet link that uses idle frames, such as 1 Gb/s fiber optic links. However, in this example, the Ethernet link is conforming to a particular standard, the IEEE 802.3ah standard, which uses the exemplary alternate idle code strategy as illustrated in FIG. 9 . The x-axis of the graph 1200 denotes frequency in MHz while the y-axis denotes power measured in decibels (dB). The link transmits the /I1 − /I1 + / patterns with probability 0.33. The graph 1200 shows the spectral peaks of the traditional idle pattern 1210 using short horizontal bars and the spectral peaks of the alternate idle pattern 1230 and the improvement 1220 between the two. The alternate idle code approach provides significant improvement over the conventional idle code. As shown, the graph represents the power spectrum of an idle Ethernet link measured in the electrical domain representing the SRS reduction in the optical domain. However, it is clear to one of ordinary skill in the art, that the idle code pattern modification as disclosed in the present invention will provide significant improvement over the conventional idle code in both the electrical and optical domains. Therefore, the invention can reduce any interference between video and data signals that occur due to idle code transmissions in either the electrical or optical domains (or both).
While, it is not easy to show the effect of the embodiment of FIGS. 10 and 11 , it is clear to one of ordinary skill in the art that the improvement will be even more dramatic than the improvement illustrated in FIG. 12 because random data is being transmitted, and as is understood by one of ordinary skill in the art, random data has no spectral peaks such as 1210 in FIG. 12 . On the other hand, the embodiment of FIGS. 10 and 11 involves a more complex modification to Tap Routing Device 433 , and involves a longer time during which real data cannot be transmitted should it present itself during transmission of the countermeasure taught in this Patent Application.
It should be understood that the foregoing relates only to illustrative exemplary embodiments of the present invention, and that numerous changes may be made therein without departing from the scope and spirit of the invention as defined by the following claims. | Optical networks as defined by the IEEE 802.3ah standard suffer from Stimulated Raman Scattering (SRS) that causes data transmission at a first optical wavelength to interfere with broadcast video transmission at a second optical wavelength in single mode optical fibers. The problem is exacerbated when data is not being transmitted across the network; and instead, an idle pattern transmission is being transmitted in order to keep the network synchronized. The repetitive nature of the idle pattern transmission leads to the SRS optical interference effect. This optical interference effect is mitigated when countermeasures are implemented to modify the idle pattern transmissions or to transmit random data in place of the idle pattern transmissions. | 7 |
The present invention relates to energizing circuits for traveling-wave-tubes and, more particularly, to an energizing circuit for compensating for the voltage droop in the T.W.T. cathode experienced during the pulse time of the T.W.T.
STATE OF THE PRIOR ART
As is well known, during the time of response of a traveling wave tube (hereinafter T.W.T.) to an input pulse, a drop in the voltage level is experienced between the body and cathode connections of the T.W.T. This drop is characterized as a "voltage droop"; its effect is to produce variations in the phase and amplitude output characteristics of the T.W.T. In most applications, and particularly in radar transmitters, it is very important that the voltage droop between the T.W.T. body and cathode be kept small during the pulse time in order to maintain low phase and amplitude distortion. The body of the T.W.T. is alternatively known as the shell and occasionally as the anode, as that element is shown and described in Rambo U.S. Pat. No. 3,150,331. Numerous configurations of T.W.T.'s are known in the art and their distinctions from conventional vacuum tubes having envelopes of non-conductive material, e.g., glass, are well recognized. Whereas in conventional vacuum tubes, the envelope is not considered a part of the electrical circuit of the tube, in the case of a T.W.T., the casing, or envelope, or shell may itself be a conductor and is considered as an electrical component, or electrode, of the tube.
In the prior art, a technique for minimizing the droop is to connect an energy storage capacitor between the cathode and the body of the T.W.T., which capacitor is charged from the cathode supply during interpulse intervals, thereby to afford an additional energy source during the pulse time, or pulse intervals. However, for large peak body currents and long pulse times, this technique requires an excessively large capacitor for limiting the voltage droop to an acceptable level.
Typical applications impose limitations on the acceptable physical size of the cathode energy supply capacitor and frequently limit it to a size inadequate to afford the necessary compensation. In addition, the charge storage capability of the capacitor must be selected with due consideration for the amount of energy stored therein such that safety limits are not exceeded in the T.W.T. under arcing conditions. As a result, adequate compensation frequently cannot be provided and thus degradation of the phase and amplitude output characteristics of the T.W.T. must be accepted in the system.
SUMMARY OF THE INVENTION
Briefly, the foregoing defects and limitations of the prior art droop compensation techniques are overcome by the T.W.T. circuit of the present invention. The invention comprises the feeding back a sample of the body current of the T.W.T. to control the input modulation pulse so that its voltage tracks the droop of the cathode charging capacitor. By this means, an extremely flat current pulse is obtained from the T.W.T.
OBJECTS OF THE INVENTION
An object of the present invention is to remove the normally attendant phase and amplitude distortion in radar transmissions due to voltage droop in a T.W.T. circuit.
A further object of the present invention is to essentially eliminate varying current pulses caused by T.W.T. voltage droop.
Other objects, advantages, and novel features of the present invention will become apparent from the following detailed description of the invention when considered in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic circuit diagram of the T.W.T. energizing circuit of the present invention.
FIG. 2a is a graphical representation of the voltage droop at the cathode of a T.W.T. during pulse time.
FIG. 2b is a graphical representation of the tracking of the voltage droop at the grid of the T.W.T.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 illustrates a typical traveling wave tube (T.W.T.) 10 having a cathode 12, a grid 14, a collector 16, and an rf input - output helix 18. The cathode 12 is coupled to a highly negative charging circuit comprising a high voltage d.c. source 20, a resistor 24, and a storage capacitor 22. The collector is connected to a fixed voltage source herein illustrated to be ground. The grid 14 of the T.W.T. is biased with respect to the cathode 12 by a direct current source 36 through a resistor 38 to normally maintain the T.W.T. in a cutoff or quiescent state. The r.f. signals to be amplified are connected to the terminal 26 of the helix 18 and the r.f. output is taken from the terminal 28 protruding from the other end of the helix 18 (These connections are typically made by way of a standard shorted quarter-wave stub so that a co-axial cable-to-waveguide coupling is effected). A modulating pulse is coupled to the grid 14 of the T.W.T. by way of a pulse source 30, an amplifier 32, and a d.c. blocking capacitor 34.
In normal operation of the T.W.T. 10, the grid modulator produces a positive pulse on the grid 14 which places the T.W.T. in a conductive state for the duration of the grid pulse thereby causing the r.f. signal propagating through the helix 18 to be amplified. In prior art devices, where a T.W.T. is used in the amplification of r.f. signals, the pulse conduction in the T.W.T. causes a droop in the cathode voltage which produces a phase lag in the r.f. signals in the helix. This voltage droop is illustrated, by way of example, in FIG. 2a for a floating deck circuit floating at -10,000 volts. In order to have the deck float at this voltage the power supplies 20 and 36 must supply -10,000 volts to the cathode and -10,050 volts to the grid. The storage capacitor 22 and the blocking capacitor 34 are thus both charged to approximately -10,000 volts. Upon the arrival at the grid 14 of a +100 volt pulse from the grid modulation source 30 the grid potential rises to -9950 volts causing an electron current to flow from the cathode 12 through the helix 18 to the grounded collector 16. As this electron current is drawn from the cathode 12, the cathode's -10,000 volt potential begins to drop thus discharging the storage capacitor 22. This cathode voltage drop toward positive potential is illustrated by the FIG. 2a wherein the cathode voltage 48 is juxtaposed against a dash-line representation of a constant voltage pulse at the grid. The voltage droop at the cathode is significant because it varies the grid-to- cathode voltage potential which, in turn, varies the shape of the electron current pulse propagating through the helix 18. In the present example, a voltage droop of only 100 volts or 1 per cent of the floating voltage would cause the tube to cut itself off. The cathode droop can be reduced somewhat by increasing the size of the capacitor 22 but it is generally impractical to make any substantial increase in capacitor size as discussed previously. Yet, a droop of only 50 to 80 volts or 0.5 to 0.8 per cent of the floating potential of -10,000 volts creates a phase change that is intolerable for most r.f. systems, such as radar and the like.
The present invention obviates this voltage droop problem by providing a feedback signal from the helix 18 to control the modulation pulse to the grid in accordance with the voltage droop of the cathode 12. This concept is reduced to practice in the present circuit merely by substituting a differential amplifier 32 for the original amplifier 32 and applying the grid modulation pulse from the modulator 30 to the negative terminal of the amplifier 32 and applying a portion of the body current via a line from the helix 18 to the positive terminal of the amplifier 32. The output of the differential amplifier 32 is then the difference between these two signals. This is shown in FIG. 2b wherein the modulation pulse is shown to track the voltage droop of FIG. 2a. As the voltage at the cathode increases, the voltage at the grid increases approximately equally. Thus, the grid-cathode potential difference is maintained approximately constant thereby maintaining the body current approximately flat. The precision with which the grid can be made to track the cathode voltage variation can be made arbitrarily close by merely increasing the loop gain up to the limit of the stability and dynamic range of the amplifier 32.
Although the T.W.T. used to explain the present inventive feedback circuit utilizes a helix as its slow-wave circuit for propagating the radio frequency signals to be amplified down the tube at approximately the velocity of the electron beam, the invention is not limited thereto. A ring bar tube or a coupled cavity tube such as is made by Varian Associates or various other equivalent devices could be used as the slow-wave circuit. Thus the body current samples for the feedback could be taken with equal facility from these devices. The body current sample could even be taken from the body itself if so desired.
Obviously, many modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that, within the scope of the appended claims, the invention may be practiced otherwise than as specifically described. | A TWT energizing circuit for compensating for the voltage droop at a TWT hode comprising the use of a differential amplifier which takes a modulation pulse at one of its inputs and a feedback signal comprising a sample of the body current from the TWT helix at the other of its inputs and applies a signal representative of the difference therebetween to the TWT grid. The above-described feedback circuit forces the grid voltage to track the cathode voltage thus maintaining a constant grid-cathode voltage drop. | 6 |
BACKGROUND
This invention relates to conveyors and more particularly to a Discharge Conveyor for receiving palletized cartons from a carton palletizer and for automatically placing such palletized cartons onto a wheeled vehicle or truck for movement thereby away from the carton palletizer.
Pallet loaders are devised for automatically stacking cartons in interlocking relation upon a pallet for movement as a unit to a place of storage, rehandling and shipping by other means of transportation. Such palletizers are well known in the art as exemplified by U.S. Pat. No. 2,769,179 or U.S. Pat. No. 2,883,074, as well as my co pending application Ser. No. 418,945 filed Nov. 26, 1973, now U.S. Pat. No. 3,856,158.
Heretofore, the pallets with cartons thereon had to be taken from the palletizer by a fork-lift and placed thereby onto flat bed dollies, trucks and the like for movement to a place of use or storage. In some establishments, the palletized cartons are preferably placed on individual flat bed hand trucks for movement in tandem fashion like a train of cars pulled by a draft vehicle. The time consumed in transferring each loaded pallet from the palletizer onto such hand trucks by means of a fork-lift can be very expensive and time consuming. It is such a problem that the present invention seeks to alleviate by the provision of a Discharge Conveyor assembly between a palletizer and individual flat-bed hand trucks which are suitably placed to receive palletized cartons directly and automatically from the palletizer without the need of fork-lift equipment.
STATEMENT OF THE INVENTION
It is an object of the present invention to provide a discharge conveyor for receiving a pallet loaded with cartons directly from a palletizer.
It is another object to provide such discharge conveyor with a pallet plate onto which palletized cartons can be moved to an area overlying a tunnel within which the flat bed of a hand truck may be placed.
It is another object to support the pallet plate at an elevation common to the discharge end of a palletizer and slightly above the surface of the flat bed of the hand truck.
It is still another object to provide means within the tunnel below the pallet plate for aligning the truck bed with the palletized cartons supported on the pallet plate.
It is yet another object to provide means for raising and/or lowering the pallet plate to the level of the top surface of the flat bed of the hand truck therebeneath; and means for moving the pallet loaded with cartons along the pallet plate and against a stop block on the hand truck whereby the hand truck is moved out of the tunnel beneath the pallet plate simultaneously with movement of the palletized cartons from the pallet plate onto the flat bed of the hand truck.
This invention further contemplates the provision of means for automatically controlling the movement of palletized cartons along the discharge conveyor as well as lowering the pallet plate as aforesaid in timed relation to arrival of pallets on the pallet plate and for elevating the latter to reset it for receipt of the next palletized carton and hand truck to be loaded.
These and other objects of the present invention will become apparent from a reading of the following specification and claims in the light of the accompanying three sheets of drawing in which:
FIG. 1 is a side elevational view of the Discharge Conveyor assembly unit of the present invention arranged between a pallet loader and a cart;
FIG. 2 is a plan view of the Discharge Conveyor assembly of FIG. 1 foreshortened but at larger scale, and with a cart disposed beneath the discharge end of the conveyor for receiving a pallet loaded with cartons therefrom;
FIG. 3 is a longitudinal section through FIG. 2 taken along line 3--3 therein;
FIG. 4 is a cross section through FIG. 3 taken along line 4--4 therein at larger scale with respect thereto;
FIG. 5 is a section through FIG. 4 as seen from line 5--5 therein;
FIG. 6 is side elevation of a portion of FIG. 4 as seen from line 6--6 thereof;
FIG. 7 is a perspective view of the Discharge Conveyor assembly;
FIG. 8 is a fragmentary elevation of the drive mechanism of the Discharge Conveyor;
FIG. 9 is a schematic diagram of the components of the apparatus locating switches and controls thereon; and
FIG. 10 is a wiring diagram of the control circuit.
GENERAL DESCRIPTION
Referring to FIG. 1 in the drawings, a pallet loader designated A is disposed to discharge palletized cartons P in the direction of arrow a onto a discharge conveyor B for further movement in the same direction and ultimate deposit onto the flat bed of a hand cart C. Neither the pallet loader A nor the cart C form a part of the present invention other than the environment between which the discharge conveyor B of the present invention affects an automatic transfer of palletized cartons from the loader A to the cart C.
In the present disclosure, the pallet loader A is shown to have an off ramp consisting of a short length roller conveyor R extending therefrom for receiving and supporting a unit of palletized containers P discharged from the pallet loader A. In the absence of such short length of roller conveyor R the discharge conveyor B of the present invention may have its receiving end E disposed to receive each unit of palletized cartons P directly from the pallet loader A. In either event, the discharge conveyor B has one end thereof disposed to receive palletized cartons for movement toward its opposite end D for discharge onto the cart C which in the present disclosure, is shown to be a flat-bed hand truck.
These flat-bed hand trucks C are used extensively in warehouses and plants because of their stability and safe support for a stack of cartons arranged in interlocked relation on a four by four pallet of conventional design. Briefly, these carts C consist of a sturdy flat bed F having four wheels W, two of larger diameter at one end and two caster type wheels T at the opposite end adjacent a handle H on upstanding standards S on the cart C. The individual carts C can be easily moved by hand or may be coupled one to another in tandum fashion for connection train-like to a draft vehicle for safe transmittal to other locations. Having thus described the environmental aspects in which the Discharge Conveyor of the present invention is most suited for use, a description of the latter follows.
DETAILED DESCRIPTION
Referring now to FIGS. 7, 2, 3 and 4, the discharge conveyor B comprises of frame 10 consisting of parallel side plates 11 and 12 supported on four legs 13, 13' and 14, 14' on opposite side plates 11 and 12, respectively. These legs 13, 13' and 14, 14' each have leveling pads 15 from which threaded rods 16 extend upwardly through base flanges 17 of each leg for adjustment by suitable threaded nuts 18. The side plates 11 and 12 are joined in spaced parallel relation by a cross bar 19 having its ends welded to the innermost pair of legs 13' and 14'. A cross web 20 also ties the side plates 11 and 12 in spaced relation along with a drive shaft 21 as well as a rocker shaft 22 which is journaled in suitable bearings 22' on the side plates 11 and 12.
The upper surface of the discharge conveyor B is divided into two zones I and O (in and out). The in zone I begins at the end E of the frame 10 and has a series of rollers 23 extending transversely between side walls 11 and 12 in the form of an ordinary free roller conveyor. The out zone O of the Conveyor B has a pallet support plate 24 which extends from the zone I to the discharge end D of the Conveyor B.
The pallet support plate 24 is normally supported with its top surface disposed in a horizontal plane tangent to the upper surface of the rollers 23 of the in zone I. By this arrangement, each unit of palletized cartons P rolling down the off ramp R of the pallet loader A arrives fully on the rollers 23 of the in zone I of the discharge conveyor B.
Each unit of palletized cartons P is moved along the Discharge Conveyor B by a sweep bar 25 extending transversely of the conveyor B and movable from end to end thereof. The sweep bar 25 has its ends mounted on suitable bearings formed as part of a sweep bar chain connector 26 at each side 11 and 12 of the frame 10. The chain connectors 26 are each secured to one link of a pair of chains 27 and 27' disposed to ride upon chain guide rails 28 and 28', respectively. The chain guide rails 28 and 28' are mounted in offset relation to and exteriorly of each of the side plates 11 and 12 as best illustrated in FIG. 4. The chains 27 and 27' which are closed-loop or endless are trained around drive sprockets 29-29' keyed to the drive shaft 21 and idler sprockets 30-30'. The drive shaft 21 is disposed at the entrance end E of the frame 10 and the idler sprockets 30-30' are at the opposite discharge end D of the frame 10. These sprockets are in alignment with the respective chain-guide rails 28 and 28' on each side of the frame 10. The upper reach of each chain 27 and 27' is thus maintained in a horizontal plane with its rollers riding the upper edge of the respective guide rail 28 and 28' as the case may be. The lower reach of each chain which would normally hang in a catenary curve is prevented from doing so by a shallow channel 31-31' supported on the side walls 11 and 12 at each side of the frame 10. The lower reach of each chain 27 and 27' is thus supported parallel to its upper reach and in a plane slightly above the axis of the drive shaft 21 (FIGS. 3, 7 and 8).
The channel 31 and 31' end a short space distance from the drive sprockets 29-29' and the chains 27-27' are trained over idler sprockets 32-32' mounted in the side walls 11 and 12 in such space to facilitate a good circumferential grip of the chains with the teeth of the drive sprockets 29-29'. As best seen in FIGS. 2 and 8, it will be noted that the chains 27-27' partially circumscribe the drive sprockets 29 and 29' in substantially tangent relation to a curved lead corner 33-33' vertically above the drive sprockets. Moreover, the sweep bar 25 carried by the chains 27-27' is disposed to pass between the last roller on the off ramp R of loader A and the first roller 23 on the in zone I of the discharge conveyor B.
The chains 27 and 27' are driven by an electric motor 34 through suitable drive connections with the drive shaft 21 as illustrated in FIG. 8. In view of the manner in which the chains 27-27' are supported at their lower reaches, the motor 34 is preferably a reversable motor in a control circuit later to be explained. For the present, it will be seen that the sweep bar 25 engages the backmost edge e of a pallet P (FIG. 3) supported on the in zone I rollers 23 for movement thereover toward the discharge end D of the Conveyor B. Each palletized carton P is thus transferred to the out zone O for support upon the pallet support plate 24 therein.
As previously pointed out, the pallet support plate 24 is normally suppported with its top surface disposed in a horizontal plane substantially tangent to the upper surface of the rollers 23 in Zone I. Therefore, there will be no tipping of the column of cartons stacked upon a pallet as it is transferred to the pallet support plate 24. After each unit of palletized cartons P is safely lodged on the pallet support panel or plate 24, the latter is lowered slightly to a level substantially at the top surface of the flat bed F of a cart C about to receive the unit of palletized cartons P. This alleviates any drop-off or tilting of the cartons stacked upon a pallet. Moreover, it provides a tunnel like space below the pallet support plate 24 wherein the flat bed F of a cart C can be disposed for the receipt of a unit of palletized containers in accordance with the present invention.
Means for lowering and/or raising the pallet support plate 24 between its limits comprises a parallelogram lift mechanism 35. The lift mechanism 35 included the aforementioned rocker shaft 22 and four rocker arms 36-36' and 37-37'. Two of these rocker arms, 36-36', are keyed to the rocker shaft 22 (FIG. 4) and the other two, 37-37' are each independently supported on stud shafts 38 and 38', respectively, mounted in axial alignment on the inner faces of the outermost pair of legs 13 and 14 at the discharge end D of the frame 10 (FIGS. 3 and 7). The four rocker arms 37-37' and 38-38' are maintained in parallel relation by being pivotally connected as at 39 to wagon guide bars 40 and 41, respectively. The pivotal connections 39 are at a comparable radial distance from the rocker shaft 22 and the stud shafts 38-38' to support the wagon guide bars 40 and 41 in parallel horizontal relation adjacent opposite sides 11 and 12 of the frame 10. The wagon guide bars 40 and 41 are thus arranged in spaced horizontal relation to receive and guide the flat bed F of a cart C within the tunnel-like space below the pallet support plate 24.
The upper end of each of the four rocker arms 37-37' and 38-38' has a roller wheel 42 mounted thereon by means of a roller bearing pin 43. The axes of the roller bearing pins 43 are each disposed an identical radial distance from the axis of rockability of the rocker arms 37-37' and 38-38'. By this arrangement, the four roller wheels 42 are set to engage the lower surface of the pallet support plate 24 for moving the latter up and down dependent upon the disposition of the four rocker arms 37-37' and 38-38'. It should here be noted that the pallet support plate 24 is guided up and down movement vertically by means of pallet plate guides 44 at four corners of the support plate 24. The pallet plate guides 44 are welded to the inner surface of the side walls 11 and 12 to assure against displacement of the pallet support plate 24 lengthwise of the frame 10 by reason of skidding movement of a pallet loaded with cartons along the upper surface of plate 24 by the sweep bar 25.
As best seen in FIG. 4, the pallet support plate 24 is reinforced lengthwise by angle iron rails 45-46 at its side edges. These angle iron rails 45-46 have their horizontal flanges welded to the underside of the support plate 24 to serve as a bearing surface between the latter and the respective roller wheels 42. Moreover, the vertically disposed flanges of the angle iron rails 45-46 are disposed in proximity to the respective side walls 11 and 12 for guidance thereby laterally during up and down movement of the pallet support plate 24 therebetween.
As best seen in FIGS. 2 and 7, wagon guide bars 40 and 41 extend outwardly of the frame 10 beyond the discharge end D of the frame 10. The extreme ends 47 of the guide bars 40 and 41 are flared divergingly and laterally crosswise of the frame 10 for guiding the flat bed F of a cart C into axial alignment longitudinally of the frame 10 and beneath the pallet support plate 24.
The cart C is rolled back into the tunnel-like space beneath the pallet support plate 24 while the latter is held in raised position by the parallelogram mechanism 25. Once a pallet P loaded with cartons becomes fully supported on the pallet support plate 24, the latter is lowered to its other limit of movement by action of the rocker shaft 22 under the influence of an air cylinder 50. The air cylinder 50 is of the double acting type controlled by a solenoid operated valve in turn operated by a dual acting switchengageable by the sweep bar 25.
The switches mounted on one side wall 11 of the frame 10 in a region where the sweep bar 25 has passed the inner end zone I and arrived above the pallet support plate 24 in zone O. In other words, as soon as a unit of palletized cartons P is fully supported on the plate 24, the air cylinder 50 is operated to withdraw its piston rod 51. The piston rod 51 has its free end pivotally connected as at 52 to the extreme end 53 of a lever 54 having its opposite end keyed to the rocker shaft 22 (FIGS. 6 and 7). By this action, the lever 54 is moved an angular distance sufficient to rock the rocker shaft 22 and the parallelogram mechanism 35 accordingly. This moves the four rocker arms 37-37' and 38-38' in unison from full to dotted line positions as illustrated in FIGS. 3, 5 and 7. The roller wheels 42 and the several rocker arms 37-37' and 38-38' are thus lowered in unison. The pallet support plate 24 with a unit of palletized cartons P thereon is thus lowered vertically to the level of the top surface of the truck bed F of the cart C disposed in the tunnel space beneath the plate.
The base of the pallet P on the support plate 24 is now at a level such as to skid off the plate 24 and directly onto the cart C. The leading edge l of the pallet P thus engages a cross block X on the top surface of the flat bed F of the truck C such that the cart is moved simultaneously with and by the oncoming unit of palletized cartons P. The cart C is therefore moved out of the tunnel simultaneously with the discharge of the pallet from the plate 24 under the influence of the sweep bar 25. Therefore, no skidding motion occurs between the base of the pallet and the upper surface of the flat bed F of the cart C as the unit of palletized cartons P moves off of the discharge end D of the support plate 24 and onto the cart.
Refer now to FIG. 9 depicting the mechanical aspects schematically with control mechanisms and to FIG. 10 showing a wiring diagram of the control circuit coardinated with the control mechanism of FIG. 9. In FIG. 10 the wiring diagram has been illustrated with separate lines I, IB, IR, II, III, IV and V for purposes of clarity. The entire control circuit is interlocked with the palletizer A by a relay 59 in line V. In this manner the discharge conveyor B can only operate when the palletizer is in operation and the sweep bar 25 is at start position to close the start switch 60.
In addition to the interlock relay 59 the control circuit also includes a photo electric cell 61 disposed to be impinged by a light beam across the entrance end E of the discharge conveyor in a conventional manner.
For purpose of explaining the operation, it will be assumed that the sweep bar 25 is at a start position at the entrance E of the discharge conveyor B and that the support plate 24 is in "up" position by operation of the lift mechanism 34, the rocker shaft 22 under the influence of the air cylinder 50.
Now when a unit of palletized containers P comes from the palletizer onto the entrance end E of the discharge conveyor it obstructs the light beam to the photo cell 61 and cuts off current through line I, and opens circuit in line V through photo cell 62 to lock relays 63 and 64 in circuit. However, current cannot flow through the feed winding of motor 34 until the unit of palletized containers P has fully passed the light beam and arrived on the rollers 23 at the entrance end E of the discharge conveyor, thereafter current flows to the feed winding of motor 34 through all of the switches in line I which are in current conducting condition.
The motor 34 is rotated clockwise FIG. 10 to move chains 27-27' and sweep bar 25 toward the discharge end D of the conveyor B. The unit of palletized cartons P is thus moved onto the support plate 24 and when fully thereon, will engage the feeler arm of a mid switch 65 in line I. This breaks circuit to the feed winding of motor 34 to stop the chains 27-27' and sweep bar 25. The unit of palletized carton P is now at rest upon the fully elevated pallet support plate 24.
It should here be noted that the feed winding of the motor 34 is also controlled by a pair of limit switches 66 and 67 in lines I and IB associated with the elevator-lift mechanism 35. The limit switch 66 in line I is normally closed when the pallet support plate 24 is in uppermost position while the limit switch 67 in line IB is normally open until the elevator-lift mechanism 35 has lowered the pallet support plate to fully down position. A third switch 68 (in line II) associated with the limit switch 66 is normally open, but closed only when the elevator-lift mechanism 35 has been lowered towards its bottom limit. A fourth switch 69 (in line III) is associated with switch 68 and is normally closed when the elevator is up position and open when the elevator-lift mechanism is completely down.
By this arrangement current may flow through line III provided there is a cart C disposed below the plate 24. The presence of a cart C in proper position to receive a unit of palletized cartons P is detected by a safety switch 70 (in line III) having a feeler arm (FIG. 9) adopted to be engaged by a cart.
A bank of relays 71, 72, 73 and 74 are under the control of the rocker shaft 22 by means of a yoke 75 (FIG. 9) thereon changing the positions of four sets of switches 66, 67, 68 and 69 dependent upon the up or down position of the elevator mechanism 35. The relays 71 and 74 (lines I and III respectively) are normally locked in closed condition by the locking relays 63 and 64. The relays 72 and 73 (lines IR and II respectively) are normally open until reversed by the release of locking relays 63 and 64.
With the relays 71, and 74 locked in closed circuit condition and a cart C disposed to close safety switch to current flowing through line III operates a two way solenoid 76 to open valve 77 to cause the piston in cylinder 50 (FIG. 9) to be drawn to the left. This rocks the rocker shaft 22 and yoke 75 counter clockwise lowering the support plate 24.
The support plate 24 with a unit of palletized cartons P thereon is then lowered to rest upon the top surface of the flat bed of the cart C which the elevator-lift mechanism 35 may continue to move beyond such condition until the flow of fluid in the cylinder 50 again becomes equalized and at rest.
At this stage the switches 66 and 69 open and the switches 67 and 68 close under the control of the yoke 75 and rocker arm 22. Thus current can now flow through switch 67 (line IB) to by-pass the mid switch 65 in line I and cause the motor 34 to continue to operate through its feed winding. The sweep bar 25 thereby continues to move toward the discharge end of the conveyor B. The unit of palletized cartons P is thus skidded along the support plate 24 and ultimately out the flat bed of the cart C which is simultaneously rolled out from under the support plate by the pallet engaging the block X on the cart.
When the pallet is finally fully off of the support plate 24 and sweep bar 25 engages the feeler arm of a limit switch 78 (line I) on the discharge end of the conveyor B. This stops the motor 34 from further operation through its feed winding. A normally open secondary switch 79 (line IV) associated with the switch 78 becomes momentarily closed to release the holding relays 63 and 64. This changes the bank of relays 71, 72, 73 and 74 to open relays 71 and 74 and to close relays 72 and 73. Relay 73 and switch 68 in line II now being closed, current flows into the two way solenoid 76 via valve 80 to urge the piston in cylinder 50 to the right (FIG. 9). This rocks rocker shaft 22 clockwise to operate the elevator lift mechanism 35 to raise the support plate 24. A secondary switch 81 associated with the start switch. 60 is closed when the sweep bar 25 is away from starting position. Secondary switch 81, in line IR of the circuit thus permits current to flow through the now closed relay 72 in the cam controlled bank of relays. Thus current flows through the return winding of the reversable motor 34 to reverse the chains 27-27' and move the sweep bar 25 back to start position. By that time the elevator-lift mechanism 34 will have completed its rise to reset the yoke 75 and four sets of switches 66, 67, 68 and 69 to start condition. This resets the relay switches, 71, 72, 73 and 74 to normal starting condition as shown in the diagram (FIG. 10). The apparatus is now ready to repeat the operation as aforesaid. | A cart loading conveyor for receiving palletized cartons at one level from a pallet loader and for lowering the same to the flat bed surface of a cart, truck and the like for deposit thereon in a manner avoiding tilting of the interlocked stack of cartons on the pallet during skidding of the pallet onto the flat bed of such truck. A discharge conveyor having a tunnel-like cart receiving zone beneath a pallet support plate arranged for up and down movement between a level for receiving units of palletized cartons at higher level and for lowering the latter vertically to the level of the top surface of the flat bed of such cart whereby a unit of palletized cartons discharging from the support plate is transferred to such cart in a non-tilted condition similtaneously with the moving of the cart out of such tunnel-like zone. | 1 |
This is a division of application Ser. No. 137,228 filed Apr. 4, 1980, now U.S. Pat. No. 4,342,494, issued Aug. 3, 1982.
TECHNICAL FIELD
This invention relates to electrical connectors and more particularly to a method and apparatus for making a contactless electrical connection.
BACKGROUND OF THE INVENTION
Many electrical contacts are known in the prior art for terminating a conductor for mating. One such contact is shown in U.S. Pat. No. 3,725,844 and entitled "Hermaphroditic Electrical Contact". Other contacts are shown in U.S. Pat. Nos. 4,120,556 and 4,072,394. Such prior art contacts provide an adequate termination for an electrical conductor but have the disadvantage that they require separate manufacture and installation to each conductor. Separate manufacture and installation is undesirable in many instances.
It has been proposed that the conductor termination be eliminated and that with suitable preparation of the conductor, and a rather minor part, that the conductor itself can be an integral contact. Such a system is disclosed in U.S. patent application Ser. No. 890,339 and entitled "Electrical Connector Assembly", the specification and drawings thereof incorporated herein by reference. Even this system has the undesirable feature that an additional part is necessary to be manufactured and assembled to the conductor before the conductor can be its own contact. The manufacture of a system requiring additional components involves additional expenditure. Further, the system disclosed in the referenced "Electrical Connector Assembly" application presupposes that the conductor will be of a fixed size to be secured within the passage. This is not always the case and might present a problem.
Accordingly, the prior art contacts known in the art, have limitations and disadvantages. One disadvantage is that they must be securely fastened to the electrical wire strand. As the number of interconnections required between units to be mated increases, the integrity of electrical interconnection between each strand and contact becomes questionable. A more desirable electrical interconnection joins only a minimum number of electrical terminations.
DISCLOSURE OF THE INVENTION
The present invention overcomes the limitations and disadvantages of the prior art contacts and contactless conductors by providing an assembly which is easy to manufacture and prepare and provides a connector assembly which is relatively inexpensive while providing a quality contact and coupling for a conductor.
The present invention is characterized by a insulated conductor wire (50) which has had a forward portion of insulator (51) removed to expose a plurality of conductive strands (52). The conductive strands (or conductor) are formed into a loop (56) in the forward region rearwardly of the ends (53) and having overlapping portions (57) which are secured together. The strands are straightened and the ends (53) thereof provided with an acutely angled end surface (54) at a uniform forward distance. The looped conductor is then inserted into a channel (33) of a molded housing (20) base portion (30) and over a projection (60) disposed in a loop cavity (62) between front and rear faces (32, 31) of the base, the projection positioning the conductor therein and providing strain relief therefor. A cover portion (40) is affixed over the housing to secure the conductor wire therein.
Other objects and advantages of the present invention will be apparent to one skilled in the art in view of the following detailed description of the invention and the claims and the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a contactless electrical connector assembly according to the invention;
FIG. 2 shows an electrical conductor wire having a forward portion of insulation removed to expose a plurality of conductive strands;
FIG. 3 shows the conductor wire of FIG. 2 with the conductive strands formed into a loop;
FIG. 4 shows a molded insulative housing according to one embodiment of the invention;
FIG. 5 shows the housing of FIG. 4 receiving the conductor wire of FIG. 3;
FIG. 6 shows another molded insulative housing according to the invention;
FIG. 7 shows the insulative housing of FIG. 6 receiving the electrical conductor wire of FIG. 2;
FIG. 8 shows yet another molded insulative housing according to the invention;
FIG. 9 shows the insulative housing of FIG. 8 receiving the electrical conductor wire of FIG. 3;
FIG. 10 is a side view in section of the insulative housing of FIG. 8.
FIG. 11 is a side view in section taken along line XI--XI of FIG. 9;
FIG. 12 shows yet another molded insulative housing according to the invention.
FIG. 13 shows a conductive ring according to the invention, and
FIG. 14 shows the ring of FIG. 13 assembled with the conductor wire of FIG. 2.
DETAILED DESCRIPTION OF THE INVENTION
Turning first to FIG. 1, a contactless electrical connector assembly 10 is shown assembled and comprises an insulating body 20 enclosing a multi-stranded electrical conductor wire 50.
FIG. 2 shows the conductor wire 50 including a plurality of conductive strands 52 protectively surrounded by an outer insulative jacket 51. A forward portion of the insulation has been removed to expose a forward end 53 of the strands. When a manufacturer supplies the multi-stranded conductor wire 50 the conductive strands within the jacket are normally twisted and hence must be combed into axial alignment for use herein.
FIG. 3 shows the conductive strands 52 formed into a loop 56 defining a loop aperture 58 within the forward end region having overlapping portions 57, the overlapping portions being secured together by a suitable method such as soldering or welding. The untwisted, exposed forward end 53 of each conductive strand is provided with an acutely angled end surface at a uniform forward distance from the insulative jacket. One device for untwisting and cutting the strands to provide the angled end surfaces is disclosed in a concurrently filed patent application disclosure 370-78-0380 and entitled "Method of Making Contactless Connector."
FIG. 4 shows the insulating body 20 according to one aspect of this invention. The body 20 is a unitary structure and includes a base 30 and a cover 40 integrally joined together by a contiguous hinge 22 longitudinally extending along the full length of one side of each body half. The insulating body is preferably molded in a known manner from a synthetic polymeric material having adequate insulating and strength characteristics upon being molded or formed as will occur to those skilled in the art. The hinge 22 of the preferred embodiment may be formed with reduced thickness so as to provide increased flexibility facilitating repeated opening or closing of the cover 40 relative to the base 30.
The base 30 includes a top surface 39, a rear face 31, a front face 32 and a wire receiving channel 33 extending between the faces, channel 33 including enlarged recesses 34, 35 adjacent each respective face 31, 32. As shown, recess 34 defines an undercut on surface 39 for receiving the insulated portion of the conductor wire and includes an abutment 36 for limiting the inward position of the conductor wire and a pair of barbs 37 extending outwardly from a wall of the recess to retain the conductor wire in the recess and to the base. Recess 35 defines another undercut on surface 39 for receiving the angled ends of the conductor wire and defines a cavity for receiving a mateable end of another connector (not shown) to complete an electrical interconnection.
Similarly, cover 40 includes a top surface 49, a rear face 41, a front face 42 and a wire receiving channel 43 extending between the faces 41, 42, channel 43 including recess 44, 45 adjacent each respective face 41, 42. Recesses 44 and 45 define undercuts in surface 49 for receiving the insulated portion and the angled ends of the wire respectively. Recess 44 includes an abutment 46 and, depending on the application, may or may not include wire retaining barbs 47.
Latching means serve to secure the cover 40 to the base 30 and includes a latch 38 and a latch receiver 48.
Preferably, and in accord with the present invention, base 30 further includes a projection or strain relief post 60 disposed intermediate the recesses 34, 35 and adjacent the wire receiving channel 33, the post extending generally perpendicularly upward from the top surface 39 of the base 30 and located within a post cavity 62 adjacent to and contiguous with the channel 33. Post 60 and post cavity 62 are sized to accommodate the loop portion 56 of the electrical conductor wire, aperture 58 of the loop 56 fitting snugly around the post 60 and loop 56 fitting within the post cavity 62. Cover 40 includes a bore 64 adapted to receive the end of post 60 when the cover is latched onto the base thereby providing rigidity to the post and to the connection.
FIG. 5 shows the electrical conductor wire 50 being secured into the base 30 of the housing 20 with the insulation portion 51 being received in the rear recess 34 and retained by the barbs 37, the loop 56 being fit about the projection 60 and within the post cavity 62 and the angled wire ends 53 extending into the front (mating) recess 35. The housing 20 and conductor 50 are now ready to be assembled into the electrical connector assembly 10 shown in FIG. 1.
FIG. 6 shows another embodiment wherein an insulative base 70 includes a wire receiving channel 71 having a front recess 72, a rear recess 73 and a wire passage extending between the recesses, the wire passage including an offset strain relief portion 74 intermediate the front and rear recesses. The strands of the conductor wire 52 are bent to conform with and fit into the offset portion 74. A slot 75 transverse to the channel 71 receives a staple 76 or other suitable means for securing the strands to the base 70.
FIG. 7 shows the base 70 having the conductive wire strands fitted within the off-set and the staple 76 securing the wire to the base.
FIG. 8 shows another embodiment wherein a base 80, similar to base 40, includes a top surface 80a, a front face 82, a rear face 81, a conductor receiving channel 83, extending between the faces, a loop post 84 disposed between the faces and further includes a flange 85 disposed in the channel between the post 84 and the front face 82, the flange extending perpendicularly to the base 80 and including a bore 86 for receiving the conductive strands of the conductor wire, the bore being substantially axially aligned with the conductor receiving channel.
FIG. 9 shows base 80 of FIG. 8 receiving the conductor wire and having the conductive strands disposed in the bore 86 of the strain relief flange 85.
FIGS. 10 and 11 show the flange 85 in section, the bore 86 including an inwardly flaring portion 87 for receiving the bundle of conductive strands and a second constant diameter portion 88 which faces the front face 82. The constant diameter portion 88 of the flange holds the strands in alignment when the strands mate with another connector.
FIG. 12 shows yet another embodiment according to this invention wherein a base 90 includes a shroud or male member 91 extending from the front face 92 of the base for inter-mating with a female connector, such as could be formed by recesses 35, 45 of the insulating body 20.
FIG. 13 shows a securement member 100 having a sleeve portion 101 and a ring portion 102 extending transversely to the sleeve, the sleeve being adapted to be inserted about the axially aligned combed plurality of conductive strands 52 of the conductor 50. As shown in FIG. 14, the sleeve is crimped or otherwise secured to the strands to provide strain relief to the bundle and the combination used with, for example, the base 30 of FIG. 4. The securement member 100 may be of conductive or of non-conductive material. If the housing channel were properly sized, the sleeve alone would be sufficient for retention and the ring portion eliminated.
When the strands have been assembled into a bundle, each forward end portion of the strand is axially aligned and disposed in generally parallel side-by-side relation, the bundle end defining a mateable "hermaphroditic" electrical contact. Although for purposes of illustration and strand ends have been shown extending beyond the front mating face of the housing, typically the ends would be protectively enclosed within the recesses or shrouds.
While FIG. 1 shows an electrical connector having only one contactless conductive (wire) member, it is to be understood that a plurality of conductive (wire) members could be provided in side-by-side relation. Further, although a hinged member secured the based and the cover in FIG. 3, the two body halves could be ultrasonically bonded together if desired.
OPERATION
To provide a contactless electrical connector 10 in accord with the present invention, one illustrative method will now be described. First, provide or form an insulative connector body 20 having two mateable body halves, such as a base 30 and a cover 40, and having a conductor receiving channel 33, 43 the channel being formed either in one body only or with each body half including a portion of the wire receiving channel, the portions on one half being adapted to confront with the portions on the other half when the halves are mated to form a contact receiving and retaining channel. Between front and rear faces of the body, provide a projection 60 within a recess cavity 62. Take a plurality of conductive strands 52, such as would be provided in a multi-stranded electrical conductor wire 50, remove a forward end portion of the insulation of the wire to expose the strands. Bend the conductor rearwardly of the forward end of the strands into a loop to develop an overlapping portion 57. Secure the overlapping portions together as by welding thereby forming a rigid loop. Arrange the forward end of the strands into axial alignment and cut the forward ends of the strands so as to provide them with acutely angled ends. Although any suitable apparatus will suffice, a wire cutter is disclosed in the above referenced "Method of Making Contactless Connector". Insert the conductor wire with loop into the channel of one connector half so that the strands extend through the channel and the loop is disposed about the projection. Finally, secure the connector body halves together to form a completed electrical connector assembly. | An electrical connector assembly (10) and method of making wherein the connector does not require a separate contact but comprises end strands (52) of a multistranded electrical conductor (wire 50). The strands (52) are formed into a loop (56) having overlapping portions (57) and the overlapping portions are secured together by a weld. The forward portion of the strands (52) are straightened into axial alignment and the ends (53) of each strand cut and provided with angled end surfaces (54). The conductor (wire) so prepared is inserted into a molded housing (20) having two mating halves (30, 40), at least one of which is provided with a channel (33) including a loop cavity (62) and a projection (60). The loop (56) of the conductor is mounted over the projection and the two connector halves secured together to complete the connector assembly. | 7 |
TECHNICAL FIELD
[0001] The present invention relates to a content recommendation system, a content recommendation method, a content recommendation apparatus, a program, and an information storage medium, and more particularly to a content recommendation technique.
BACKGROUND ART
[0002] In recent years, a user can enjoy a desired content chosen from among an enormous number of contents using a communication network such as the Internet. Since there are an enormous number of available contents, various kinds of recommendation techniques have been suggested. For example, a technique for calculating a degree of similarity between a preference vector representing a feature of the content preferred by an user, and a feature vector of each of contents while recommending the user the content with the high degree of similarity, so called content-based filtering is one of the examples (see Japanese Patent Application Laid-Open No. 2001-160955).
SUMMARY OF INVENTION
Technical Problem
[0003] However, such recommendation techniques in the past focused only the degree of similarity between specific pieces of information, and the specific pieces of information tended to be recommended intensively by the user. This brought an issue that the user may get bored the recommendation itself.
[0004] The present invention is made in view of the above issues, and it is an object of the present invention to provide a content recommendation system, a content recommendation method, a content recommendation apparatus, a program, and an information storage medium capable of recommending contents that continuously interests a user.
SOLUTION TO PROBLEM
[0005] In order to solve the above issues, a content recommendation system according to the present invention includes attribute value storage means for storing an attribute value of each of one or a plurality of attributes for each of a plurality of contents, feature vector storage means for storing a feature vector representing a feature of each of the contents, preference vector obtaining means for obtaining a preference vector representing a feature of contents preferred by an user, a first content selection means for selecting a part of a given group of the contents according to a successively generated condition of the attribute value of the one or the plurality of attributes, a second content selection means for selecting a part or all of the group according to a degree of similarity between the feature vector and the preference vector of each of the contents belonging to the given group of the contents, and content presenting means for presenting the user the contents which are selected by applying the first content selection means and the second content selection means in an overlapping manner to the plurality of contents.
[0006] Further, a content recommendation method according to the present invention includes a preference vector obtaining step for obtaining a preference vector representing a feature of contents preferred by an user, a first content selection step for referring to attribute value storage means for storing an attribute value of each of one or a plurality of attributes for each of a plurality of contents, and selecting a part of a given group of the contents according to a successively generated condition of the attribute value of the one or the plurality of attributes, a second content selection step for referring to feature vector storage means for storing a feature vector representing a feature of each of the contents, and selecting a part or all of the group according to a degree of similarity between the feature vector and the preference vector of each of the contents belonging to the given group of the contents, and a content presenting step for presenting the user the contents which arc selected by applying the first content selection means and the second content selection means in an overlapping manner to the plurality of contents.
[0007] Further, a content recommendation apparatus according to the present invention includes preference vector obtaining means for obtaining a preference vector representing a feature of contents preferred by an user, first content selection means for selecting a part of a given group of contents according to a successively generated condition of an attribute value of attributes of the one or the plurality of contents, second content selection means for selecting a part or all of a group according to a degree of similarity between a feature vector and the preference vector of contents belonging to the given group of contents, and list generation means for generating a list of contents selected by applying the first content selection means and the second content selection means in an overlapping manner to a plurality of contents.
[0008] Further, a content recommendation method according to the present invention includes a preference vector obtaining step for obtaining a preference vector representing a feature of contents preferred by an user, a first content selection step for selecting a part of a given group of contents according to a successively generated condition of an attribute value of attributes of one or a plurality of contents, a second content selection step for selecting a part or all of a group according to a degree of similarity between a feature vector and the preference vector of contents belonging to the given group of the contents, and a list generation step for generating a list of contents selected by applying the first content selection step and the second content selection step in an overlapping manner to a plurality of contents.
[0009] Further, a program according to the present invention includes preference vector obtaining means for obtaining a preference vector representing a feature of contents preferred by an user, first content selection means for selecting a part of a given group of contents according to a successively generated condition of an attribute value of attributes of one or a plurality of contents, second content selection means for selecting a part or all of a group according to a degree of similarity between a feature vector and the preference vector of each of contents belonging to the given group of the contents, and list generation means for generating a list of contents selected by applying the first content selection means and the second content selection means in an overlapping manner to a plurality of contents.
[0010] Further, an information storage medium according to the present invention causes a computer to function as preference vector obtaining means for obtaining a preference vector representing a feature of contents preferred by an user, first content selection means for selecting a part of a given group of contents according to a successively generated condition of an attribute value of attributes of one or a plurality of contents, second content selection means for selecting a part or all of the group according to a degree of similarity between a feature vector and the preference vector of each of the contents belonging to the given group of the contents, and list generation means for generating a list of contents selected by applying the first content selection means and the second content selection means in an overlapping manner to a plurality of contents.
[0011] Further, one embodiment of the present invention, the first content selection means selects a part of the plurality of the contents, the second content selection means selects a part or all of the contents selected by the first content selection means, and the content presenting means presents the user the contents selected by the second content selection means.
[0012] Further, one embodiment of the present invention the content recommendation system further includes related condition generation means for successively obtaining a condition for the attribute values of the one or the plurality of attributes, and successively generating another condition related to the condition based on the obtained condition. The first content selection means selects a part of the given group of the contents according to the condition successively generated by the related condition generation means,
[0013] Further, one embodiment of the present invention, the condition is to be determined based on random digits. For example, the content recommendation system may further include preference distribution storage means for storing a degree of the user's preference with respect to each attribute value of the attributes for each of the attributes, and condition determining means for selecting attribute values of one or a plurality of attributes according to a probability based on the degree of the user's preference stored in the preference distribution storage means, and determining the condition to be used by the first content selection means according to the selected attribute values. At this time, the content recommendation system may further include operation information obtaining means for obtaining the user's operation information with respect to the content presented by the contents presenting means, and preference distribution update means for updating storage contents in the preference distribution storage means, based on the operation information obtained by the operation information obtaining means.
BRIEF DESCRIPTION OF DRAWINGS
[0014] FIG. 1 is an overall configuration diagram illustrating a content recommendation system according to an embodiment of the present invention.
[0015] FIG. 2 is a hardware configuration diagram illustrating a server.
[0016] FIG. 3 is a perspective view illustrating an external appearance of a game system used as a user apparatus.
[0017] FIG. 4 is a hardware configuration diagram illustrating a game machine.
[0018] FIG. 5 is a configuration diagram illustrating first metadata.
[0019] FIG. 6 is a configuration diagram illustrating second metadata.
[0020] FIG. 7 is an operation flow diagram illustrating a content recommendation system according to an embodiment of the present invention.
[0021] FIG. 8 is a diagram schematically illustrating theme template data.
[0022] FIG. 9 is a diagram schematically illustrating theme preference distribution data.
[0023] FIG. 10 is a diagram schematically illustrating attribute value preference distribution data.
[0024] FIG. 11 is a configuration diagram illustrating theme group data.
[0025] FIG. 12 is a diagram schematically illustrating an attribute value conversion dictionary.
[0026] FIG. 13 is a functional block diagram illustrating a user apparatus.
[0027] FIG. 14 is a functional block diagram illustrating a server and a database.
[0028] FIG. 15 is a modified operation flow diagram illustrating a content recommendation system according to an embodiment of the present invention.
[0029] FIG. 16 is an external view illustrating a portable game machine.
[0030] FIG. 17 is a hardware configuration diagram illustrating a portable game machine.
[0031] FIG. 18 is a hardware configuration diagram illustrating a general-purpose personal computer.
DESCRIPTION OF EMBODIMENTS
[0032] An embodiment of the present invention will be hereinafter explained in detail with reference to drawings.
[0033] FIG. 1 is an overall configuration diagram illustrating a content recommendation system according to an embodiment of the present invention. As shown in this figure, this content recommendation system 10 is connected to a data communication network 18 such as the Internet, and includes a server 14 (first content recommendation apparatus) capable of mutual data communication and a plurality of user apparatuses 12 (second content recommendation apparatus). The server 14 includes a database 14 a . For example, the user apparatus 12 may be a computer system installed in each home such as a personal computer, a computer game system, and a home server, and a portable machine such as a portable game machine. The user apparatus 12 accesses the server 14 , and receives a list of songs recommended to a user of the user apparatus 12 . The user apparatus 12 requests the server 14 to provide song data included in the list, receives the song data, and play the songs. On the other hand, for example, the server 14 is constituted by a computer system such as a known server computer, and transmits, to each user apparatus 12 , a list of songs recommended to the user of the user apparatus 12 . In addition, the server 14 transmits individual song data in response to a request of each user apparatus 12 . In this example, the present invention is applied to recommendation of songs. However, the present invention is not limited thereto. It is to be understood that the present invention may be applied to recommendation of various kinds of contents, e.g., a motion image such as a movie, a still image such as a picture, and a document such as a novel.
[0034] FIG. 2 is a figure illustrating an example of hardware configuration of the server 14 . As shown in this figure, the server 14 includes a processor 70 , a memory 71 , a hard disk drive 73 , a medium drive 74 , and a communication interface 76 , which are connected to a bus 72 so as to mutually exchange data. The memory 71 includes a ROM and a RAM. The ROM stores various kinds of system programs.
[0035] The RAM is mainly used for a work area of the processor 70 . The hard disk drive 73 stores a program for distributing songs and distributing a list of recommended songs, and the database 14 a is structured for distributing songs and distributing a list of recommended songs. The medium drive 74 is a device for reading data stored in a computer-readable medium 75 such as a CD-ROM and a DVD-RAM, or writing data to the computer-readable medium 75 . The communication interface 76 controls data communication via the communication network 18 with the user apparatus 12 . The processor 70 controls each unit of the server 14 according to a program stored in the memory 71 , the hard disk drive 73 , or the medium 75 .
[0036] Subsequently, the user apparatus 12 will be explained in detail. FIG. 3 is an external view illustrating a computer game system used as the user apparatus 12 . This computer game system includes a game machine 200 , an operation device 202 , and a television monitor 204 . The game machine 200 is a computer game system, which executes not only game programs but also various kinds of programs such as a Web browser and movie/music player programs. The program may be read from various kinds of computer-readable media such as various kinds of optical disks, internal or external hard disk drives, and semiconductor memories, or may be downloaded via a computer network such as the Internet. The operation device 202 is wirelessly communicatively connected to the game machine 200 or communicatively connected thereto via a wire.
[0037] The game machine 200 includes a disk insertion slot 206 compatible with optical disks, a USB connection terminal 208 , and the like. The disk insertion slot 206 is configured such that optical disks such as a BD (Blu-ray disk, trademark), a DVD-ROM, and a CD-ROM can be loaded in the slot. A touch sensor 210 is used to instruct the game machine 200 to unload a disk. A touch sensor 212 is used to instruct the game machine 200 to turn the power on or off. A power switch, an audio and video output terminal, an optical digital output terminal, an AC power input terminal, a LAN connector, an HDMI terminal, and the like (not shown) are provided at the rear side of the game machine 200 .
[0038] The game machine 200 is also provided with a multimedia slot for receiving multiple types of detachable semiconductor memories. Multiple slots, not shown, are exposed to receive respectively different types of semiconductor memories, when a lid 214 arranged on the front surface of the game machine 200 is opened.
[0039] The operation device 202 is driven by a not-shown battery, and includes a plurality of buttons and keys with which a user makes operation inputs. When the user operates the buttons and keys on the operation device 202 , the operation contents are transmitted to the game machine 200 wirelessly or by a wire.
[0040] The operation device 202 has an arrow key 216 , joy sticks 218 , and a group of operation buttons 220 . The arrow key 216 , the joy sticks 218 , and the group Of operation buttons 220 are arranged on a top surface 222 of the casing. The four types of operation buttons 224 , 226 , 228 , and 230 are marked with different symbols in different colors in order to distinguish them from each other. More specifically, the operation button 224 is marked with a red circle, the operation button 226 is marked with a blue cross, the operation button 228 is marked with a purple square, and the operation button 230 is marked with a green triangle. A rear surface 232 of the casing of the operation device 202 is provided with a plurality of LEDs, not shown.
[0041] The user holds a left side grip portion 234 b with the left hand, and a right side grip portion 234 a with the right hand when operating the operation device 202 . The arrow key 216 , the joy sticks 218 , and the group of operation buttons 220 are arranged on the top surface 222 of the casing so that they can be operated by the user who is holding the left side grip portion 234 b and the right side grip portion 234 a with the right and left hands.
[0042] An LED button 236 is also provided on the top surface 222 of the casing. The LED button 236 is used, for example, to display a particular menu screen on the television monitor 204 with the game machine 200 . It also has the functions of indicating the battery level of the operation device 202 with the lighting status of the LED. For example, the LED is lit in red during charging, lit in green when fully charged, and blinks in red when the battery level is low.
[0043] The arrow key 216 is configured such that it can be pressed in four directions, i.e., up, down, right, and left directions, eight directions, i.e., up, down, right, and left directions and four directions therebetween, or in any direction. For example, the arrow key 216 is used to move in up, down, right and left directions a cursor on a screen of the television monitor 204 , and scroll various kinds of information on the screen. Respectively different functions are allocated to the group of operation buttons 220 by an application program.
[0044] The joy joystick 218 has a stick supported in such a manner that the stick can be inclined in any direction, and has a sensor for detecting the amount of inclination. The stick is designed to return to a neutral position with the aid of an urging means such as a spring. The stick returns back to the neutral position when not operated. When the stick is inclined, the amounts of inclinations in a plurality of reference directions arc converted into digital values, and the values are transmitted to the game machine 200 as an operation signal.
[0045] The operation device 202 further includes a select button 240 , a start button 238 , and the like. The start button 238 is used, e.g., when the user instructs the game machine 200 to start a program, and starts/pauses playing a movie or music. On the other hand, the select button 240 is used, e.g., when the user selects one of items of the menu displayed on the television monitor 204 .
[0046] Now, the internal circuit configuration of the game machine 200 will be explained. As shown in FIG. 4 , the game machine 200 includes, as its principal components, a main CPU 300 , a GPU (graphic processing unit) 302 , an input/output processor 304 , an optical disk reproduction unit 306 , a main memory 308 , a mask ROM 310 , and a sound processor 312 . The main CPU 300 performs signal processing and control of various internal components based on various kinds of programs. The GPU 302 performs image processing. The input/output processor 304 performs interfacing or processing between the GPU 300 and some of the components in the apparatus and components outside of the apparatus. In addition, the input/output processor 304 may have functions for executing application programs, so that the game machine 200 has compatibility with other game machines.
[0047] The optical disk reproduction unit 306 reproduces an optical disk, such as a BD, DVD or CD, storing an application program or multimedia data. The main memory 308 serves as a work area for the main CPU 300 and a buffer for temporarily storing data read from an optical disk. The mask ROM 310 stores operating system programs to be executed mainly by the main CPU 300 and the input/output processing unit 304 . The sound processor 312 performs audio signal processing.
[0048] The game machine 200 further includes a CD/DVD/BD processor 314 , an optical disk reproduction driver 316 , a mechanical controller 318 , a hard disk drive 334 , and a card-type connector (e.g., PC card slot) 320 . The CD/DVD/BD processor 314 performs, e.g., error correction processing (e.g., CIRC (cross interleave Reed-Solomon coding)), expansion decoding processing, and so on, to a disk reproduction signal read from a CD, DVD, or BD by the optical disk reproduction unit 306 and then amplified by an RF amplifier 328 , thereby reproducing data recorded on the CD, DVD, or BD. The optical disk reproduction driver 316 and the mechanical controller 318 perform rotation control of a spindle motor of the optical disk reproduction unit 306 , focus/tracking control of an optical pickup, loading control of a disk tray, etc.
[0049] For example, the hard disk drive 334 stores saved data for programs and game programs read by the optical disk reproduction unit 306 , or stores data such as photos, moving images, and music acquired via the input and output processor 304 . The card-type connector 320 is a connection port for, e.g., a communication card, an external hard disk drive, or the like.
[0050] These internal components are connected with each other mainly through bus lines 322 , 324 , and the like. The main CPU 300 and the GPU 302 are connected through a dedicated bus. Additionally, the main CPU 300 and the input/output processor 304 are connected through a high-speed BUS. Likewise, the input/output processor 304 , the CD/DVD/BD processor 314 , the mask ROM 310 , the sound processor 312 , the card-type connector 320 , and the hard disk drive 334 are connected through the high-speed BUS.
[0051] The main CPU 300 executes an operating system program for the main CPU 300 stored in the mask ROM 310 to control the operation of the game machine 200 . Further, the main CPU 300 reads various kinds of programs and other data from an optical disk such as a BD, DVD-ROM, or CD-ROM and loads the programs into the main memory 308 . Furthermore, the main CPU 300 executes the programs loaded to the main memory 308 . Alternatively, the main CPU 300 downloads various kinds of programs and other data via the communication network, and executed the downloaded programs.
[0052] The input/output processor 304 executes an operating system program for the input/output processor stored in the mask ROM 310 to control data input/output with the operation device 202 , a memory card 326 , the USB connection terminal 208 , Ethernet (registered trademark) 330 , an IEEE1394 terminal, not shown, and the PC card slot. Data input/output with the operation device 202 and the memory card 326 are controlled via the interface 232 including a multimedia slot and a wireless communication port.
[0053] The GPU 302 has a function of a geometry transfer engine for executing coordinate conversion and so on, and a function of a rendering processor. The GPU 302 draws an image in a frame buffer, not shown, according to rendering instructions given by the main CPU 300 . For example, in the case where programs stored on an optical disk use 3 D graphics, the GPU 302 calculates, in a geometry operation process, the coordinates of polygons to constitute a three-dimensional object. Further, the GPU 302 makes, in a rendering process, an image that may be obtained by shooting the three-dimensional object by a virtual camera. The GPU 302 writes the thus obtained image into the frame buffer. The GPU 302 then outputs a video signal corresponding to the stored image to the television monitor 204 . Thus, an image is displayed on a screen 204 b of the television monitor 204 .
[0054] The sound processor 312 has an ADPCM (Adaptive Differential Pulse Code Modulation) decoding function, an audio signal reproducing function, and a signal modulating function. The ADPCM decoding function is a function for generating waveform data from sound data encoded with ADPCM. The audio signal reproduction function is a function for generating an audio signal for, e.g., sound effects, from waveform data stored in a sound buffer incorporated in or externally connected with the sound processor 312 . Internal speakers 204 a , 204 a of the television monitor 204 output sound represented by an audio signal. The signal modulating function is a function for modulating waveform data stored in the sound buffer.
[0055] When the game machine 200 is turned on, the operating system programs for the main CPU 300 and the input/output processor 304 are read from the mask ROM 310 . These operating system programs are executed by the main CPU 300 and the input/output processor 304 . Thus, the main CPU 300 centrally controls each component of the game machine 200 . On the other hand, the input/output processor 304 controls signal input/output between elements such as the controller 202 , and the memory card 326 , and the game machine 200 . Also, by executing the operating system program, the main CPU 300 performs initialization such as operation check and so on. The main CPU 300 then controls the optical disk reproduction unit 306 to read an application program for a game and the like from an optical disk. After loading the application program in the main memory 308 , the main CPU 300 executes the program. By executing the application program, the main CPU 300 controls the GPU 302 and the sound processor 312 following the operator's instructions received through the operation device 202 and the input/output processor 304 to control image display and production of a sound effect, a music sound, or the like.
[0056] The content recommendation system 10 applies two kinds of filters in an overlapping manner to select songs recommended to a user from among many songs. FIG. 5 is a figure schematically illustrating first metadata using a first filter. FIG. 6 is a figure schematically illustrating second metadata using a second filter. Any one of them is stored in the database 14 a . As shown in FIG. 5 , the first metadata includes a music ID and a plurality of attribute values of attributes. The music ID is information for identifying each of many songs recommended by the content recommendation system 10 to the user. A plurality of attributes suitable for representing features of each song are prepared in advance, and these attribute values of attributes are given to each song. Regarding attributes and attribute values, in a case where the attribute is a style of song, examples of attribute values include rock music, pop music, classical music, jazz music, and the like. In a case where the attribute is a year when an artist was born and a year when an artist made debut, examples of attribute values include 1950, 1960, 1970, and the like. In a case where the attribute is a year when a song was rated in hit chart, examples of attribute values include 1999, 2000, 2001, and the like. In a case where the attribute is a nationality of an artist, examples of attribute values include Japan, America, and the like. In a case where the attribute is a sex of an artist, examples of attribute values include male and female. Some of attribute values of attributes may be input as a result of analytic processing performed by a computer. However, most of the attributes are desirably input by a person.
[0057] As shown in FIG. 6 , the second metadata includes a music ID and a plurality of feature quantities of features. Examples of features include a tempo of a song, the degree how much a sound having a particular frequency is included in a song, and the degree how many times a particular keyword appears in an explanatory text of a song. These feature quantities may be input as a result of analytic processing performed by a computer. In the explanation below, a vector whose component is the feature quantity of a feature is described as a feature vector.
[0058] In the content recommendation system 10 , in view of user's preference, a condition of an attribute value (attribute value condition) is successively changed by a random number, so that a song whose first metadata satisfies the attribute value condition is extracted from many songs using the first filter. Subsequently, the degree of similarity between a preference vector representing a feature of the song preferred by the user and a feature vector of each song is calculated for each song thus extracted. A predetermined number of songs having a higher degree of similarity are determined, in the descending order of the degree of similarity, as songs which are to be recommended to the user. Like the feature vector of each song, the preference vector is a vector whose component is the feature quantity of a feature as shown in FIG. 6 . These preference vectors may be generated by composing the feature vectors of songs preferred by the user. The degree of similarity between vectors may be an angle between both of the vectors. In this case, the smaller the formed angle is, the higher the degree of similarity is. According to the present embodiment, various types of songs are successively presented to the user, and contents continuously interesting to the user can be recommended.
[0059] FIG. 7 is an operation flow diagram of the content recommendation system 10 . First, in the content recommendation system 10 , theme data is selected by the user apparatus 12 (S 201 ). The theme data includes a theme template ID and an attribute value serving as a parameter of a theme template identified by the theme template ID. As shown in FIG. 8 , the theme template is a template for generating a condition of each attribute value (attribute value condition) of a song, and attribute values of attributes specified by the theme template is given as parameters, whereby an attribute value condition of the song is obtained. In FIG. 8 , attributes of “year when an artist was born” and “style” are specified, and for example, “1980” and “rock music” are given to these attributes, whereby an attribute value condition indicating that “the year when the artist was born is 1980's, and the style is rock music” is obtained. In the above first filter, reference is made to the first metadata as shown in FIG. 5 , and songs satisfying the attribute value condition thus determined are selected from among many songs.
[0060] A plurality of theme templates are generated by a person in advance, and the theme template ID is information for identifying each theme template. As shown in FIG. 9 , for each theme template ID, the user apparatus 12 stores the degree of user's preference of the theme template identified by the theme template ID (the degree how much the user prefers it), i.e., theme preference distribution data. The user apparatus 12 generates a random number, and successively selects each theme template ID according to a probability based on the degree of preference. Then, the attribute specified by the theme template identified by the selected theme template ID is obtained, and an attribute value of the attribute in question is selected. Also at this occasion, the attribute value of each attribute is selected according to a random number based on the degree of attribute. In other words, as shown in FIG. 10 , for all the attributes, the user apparatus 12 stores the degree of user's preference for each attribute value, i.e., attribute value preference distribution data. The user apparatus 12 generates a random number, and selects an attribute value of the attribute specified according to a probability based on the degree of preference. Thereafter, the user apparatus 12 transmits, to the server 14 , the preference vector and the theme data of the user stored in advance (S 202 ).
[0061] The server 14 applies a change to the theme data received from the user apparatus 12 (S 401 ). In other words, the database 14 a stores theme group data as shown in FIG. 11 . The theme group data includes IDs of a plurality of common theme templates and a group ID. When the server 14 obtains a theme template ID included in theme data, the server 14 refers to the theme group data, and selects one of theme template IDs which belongs to the same group as the obtained theme template ID based on a random number. Then, the attribute specified by the theme template identified by the theme template ID thus selected is obtained, and the attribute value is determined. At this occasion, as shown in FIG. 12 , the database 14 a stores an attribute value conversion dictionary including many pairs of attributes and attribute values, each associated with one or more pairs of other attributes and attribute values. The server 14 refers to the attribute value conversion dictionary to convert the attribute value of each attribute included in theme data received from the user apparatus 12 into the attribute value of the attribute newly obtained. Thus, the server 14 generates another theme data related to the theme data received from the user apparatus 12 . Thereafter, an attribute value condition is obtained from theme data thus generated. Then, while referring to the first metadata, songs satisfying the obtained attribute value condition are selected from among many songs managed by the database 14 a (S 402 ). When the songs are selected in this manner, songs can be selected in a more unexpected manner, compared with a case where songs are selected simply using the theme data transmitted from the user apparatus 12 .
[0062] Subsequently, the server 14 calculates the degree of similarity between the preference vector received from the user apparatus 12 and the feature vector of each song selected in S 402 , and selects a predetermined number of songs having a higher degree of similarity in the descending order of the degree of similarity (S 403 ). Then, a list of songs including music IDs of the predetermined number of songs is replied to the user apparatus 12 (S 404 ). When the user apparatus 12 receives a music list, the user apparatus 12 transmits one of music IDs included in the music list to the server 14 (S 203 ), and the server 14 reads data of songs identified by the music ID from the database 14 a , and replies the data (S 405 ). The user apparatus 12 plays data of the song thus replied (S 204 ), and the internal speakers 204 a , 204 a of the television monitor 204 output songs. At this occasion, information such as the title and the name of the artist of the currently played may be displayed on the screen 204 b of the television monitor 204 . When the songs of all the music IDs included in the music list are played as described above, the user apparatus 12 executes the processing of S 201 again.
[0063] Now, the functional configurations of the user apparatus 12 and the server 14 will be explained. FIG. 13 is a functional block diagram of the user apparatus 12 . FIG. 14 is a functional block diagram of the server 14 . The functional blocks as shown in these figures are achieved by causing the user apparatus 12 and the server 14 to respectively execute programs. Each program is previously stored in a readable information storage medium in the user apparatus 12 or the server 14 , and may be installed to the user apparatus 12 and the server 14 via the medium. Alternatively, it may be downloaded from another computer via the data communication network 18 .
[0064] As shown in FIG. 13 , the user apparatus 12 includes a theme selection unit 41 , a theme preference distribution data storage unit 42 , a theme preference distribution data learning unit 43 , a request unit 44 , an attribute value determination unit 45 , an attribute value preference distribution data storage unit 46 , an attribute value preference distribution data learning unit 47 , a preference vector storage unit 48 , a theme template storage unit 49 , a preference vector learning unit 50 , an operation unit 51 , and a music reproduction unit 52 .
[0065] First, the theme preference distribution data storage unit 42 is mainly constituted by the hard disk drive 334 or the memory 308 , and stores theme preference distribution data as shown in FIG. 9 . The theme preference distribution data learning unit 43 is mainly constituted by the main CPU 300 and the memory 308 . The theme preference distribution data is updated according to the contents of operation performed on the operation unit 51 . More specifically, for a predetermined number of songs or more included in the music list transmitted from the server 14 , processing is performed to increase the degree of user's preference associated with the ID of the template used for generating the music list in the server 14 , when (1) where s song is played to the end without performing a skip operation (positive situation 1 ) and when (2) a particular operation is performed to indicate that the song is preferred by the user (positive situation 2 ). In other words, when the positive situation 1 or 2 occurs with respect to the song in the music list generated by the theme template, the degree of preference of the theme template is increased. On the contrary, for a predetermined number of songs or more, processing is performed to decrease the degree of user's preference associated with the ID, when (1) playback of the song is interrupted by performing skip operation (negative situation 1 ) and when (2) a operation of characteristic is performed to indicate that the song is not preferred by the user (negative situation 2 ). In other words, when the negative situation 1 or 2 occurs with respect to the song in the music list generated by the theme template, the degree of preference of the theme template is decreased. The theme selection unit 41 is mainly constituted by the main CPU 300 and the memory 308 . The theme selection unit 41 refers to the theme preference distribution data stored in the theme preference distribution data storage unit 42 to successively select each theme template ID according to a probability based on the degree of preference. More specifically, the theme selection unit 41 has a range of random values in association with each theme template ID, and the size of the range is set according to the degree of preference. The theme selection unit 41 generates a random number, and selects a theme template ID associated with the range to which the random number belongs.
[0066] The attribute value preference distribution data storage unit 46 is mainly constituted by the hard disk drive 334 or the memory 308 , and stores the attribute value preference distribution data as shown in FIG. 10 . The attribute value preference distribution data learning unit 47 updates the attribute value preference distribution data according to the contents of operation performed on the operation unit 51 and the attribute values of music data stored in the user apparatus 12 . More specifically, when any one of the above positive conditions occurs with respect to a predetermined number of songs or more in the music list transmitted from the server 14 , a pair of attributes and attribute values which are necessary conditions in the attribute value condition used for generating the music list in the server 14 are obtained, and processing is performed to increase the degree of user's preference associated with the obtained attribute value in the attribute value preference distribution data relating to the obtained attribute. On the contrary, when any one of the above negative conditions occurs with respect to a predetermined number of songs or more, processing is performed to decrease the degree of user's preference associated with the attribute value in the attribute value preference distribution data.
[0067] When any one of the above positive conditions occurs with respect to the song currently played in the user apparatus 12 , the first metadata of the song in question is obtained from the server 14 . Then, processing is performed to increase the degree of user's preference associated with the attribute value of the attribute included in the obtained first metadata in respective attribute value preference distribution data. On the contrary, when any one of the above negative conditions occurs, the first metadata of the song in question is obtained from the server 14 . Then, processing is performed to decrease the degree of user's preference associated with the attribute value of the attribute included in the obtained first metadata in respective attribute value preference distribution data.
[0068] Further, the attribute value preference distribution data learning unit 47 is mainly constituted by the main CPU 300 and the memory 308 . The attribute value preference distribution data learning unit 47 searches all the music data stored in the hard disk drive 334 and other storage devices arranged in the user apparatus 12 of the user owned by the user, and obtains the first metadata of each song from the server 14 . Then, processing is performed to increase the degree of user's preference associated with the attribute value of the attribute included in the obtained first metadata in respective attribute value preference distribution data. By doing so, respective attribute value preference distribution data can be made according to the songs owned by the user, and reflect a variety of user's preferences about songs, whereby various kinds of songs can be recommended to the user. In this case, respective attribute value preference distribution data are updated according to music data stored in the storage device arranged on the user apparatus 12 . When the music data of the songs owned by the user are stored in another computer connected to the data communication network 18 of the server 14 and the like, respective attribute value preference distribution data may be updated according to the music data of the user stored in the another computer.
[0069] The theme template storage unit 49 is mainly constituted by the hard disk drive 334 or the memory 308 , and stores many theme templates as shown in FIG. 8 . The attribute value determination unit 45 is mainly constituted by the main CPU 300 and the memory 308 . When the attribute value determination unit 45 receives the theme template ID from the theme selection unit 41 , the attribute value determination unit 45 reads the theme template identified by the theme template ID from the theme template storage unit 49 to check attribute (the name of attribute) specified therein. Then, the attribute value preference distribution data of each attribute specified from the attribute value preference distribution data storage unit 46 . Thereafter, the attribute value determination unit 45 refers to the attribute value preference distribution data having been read, and selects an attribute value of each attribute according to a probability based on the degree of preference. More specifically, the attribute value determination unit 45 has a range of random values in association with each attribute value, and the size of the range is set according to the degree of preference. The attribute value determination unit 45 generates a random number, and selects an attribute value associated with the range to which the random number belongs.
[0070] The preference vector storage unit 48 is mainly constituted by the hard disk drive 334 or the memory 308 , and stores preference vector of the user. The request unit 44 is mainly constituted by the main CPU 300 , the memory 308 , the input/output processor 304 , and the Ethernet 330 . The preference vector and the theme data are paired, and transmitted to the server 14 . The theme data includes the theme template ID output from the theme selection unit 41 and the attribute value of each attribute output from the attribute value determination unit 45 .
[0071] The preference vector learning unit 50 is mainly constituted by the main CPU 300 and the memory 308 , and updates the preference vector based on the contents of operation performed with the operation unit 51 . More specifically, when any one of the above positive conditions occurs with respect to the song currently played in the user apparatus 12 , the preference vector learning unit 50 obtains the second metadata of the song in question from the server 14 . Then, the preference vector is updated so as to bring the current preference vector closer to the feature vector represented by the obtained second metadata. On the contrary, when any one of the above negative conditions occurs, the metadata of the song in question is obtained from the server 14 , and the preference vector may be updated so as to bring the current preference vector away from the feature vector represented by the obtained second metadata.
[0072] The music reproduction unit 52 is mainly constituted by the main CPU 300 , the memory 308 , the sound processor 312 , the input/output processor 304 , and the Ethernet 330 . The music reproduction unit 52 receives a music list from the server 14 , and transmits music IDs included in the music list to the server 14 in order. Then, the music reproduction unit 52 receives music data corresponding to the music ID from the server 14 , and reproduces the music data. The operation unit 51 is configured to include the operation device 202 . The operation unit 51 is used to instruct the music reproduction unit 52 to skip a currently-played song, explicitly indicate that the song is a user's favorite song, or explicitly indicate that the song is a song which is not preferred by the user.
[0073] Subsequently, as shown in FIG. 14 , the server 14 includes a server main body 14 b and a database 14 a . The server main body 14 b is arranged with a request reception unit 21 , a first filter 22 including a theme data change unit 22 a and a music list generation unit 22 b , a second filter 23 , music list reply unit 24 , and a music distribution unit 25 . On the other hand, the database 14 a is arranged with a theme group data storage unit 31 , a theme template storage unit 32 , an attribute value conversion dictionary storage unit 33 , a first metadata storage unit 34 , a second metadata storage unit 35 , and a music data storage unit 36 .
[0074] First, the theme group data storage unit 31 is mainly constituted by the hard disk drive 73 or the memory 71 , and stores the theme group data as shown in FIG. 11 . The theme template storage unit 32 stores the theme template as shown in FIG. 8 . The attribute value conversion dictionary storage unit 33 is mainly constituted by the hard disk drive 73 or the memory 71 , and stores the attribute value conversion dictionary as shown in FIG. 12 . The first metadata storage unit 34 is mainly constituted by the hard disk drive 73 or the memory 71 , and stores the first metadata as shown in FIG. 5 . Further, the second metadata storage unit 35 is mainly constituted by the hard disk drive 73 or the memory 71 , and stores the second metadata as shown in FIG. 6 . Further, the music data storage unit 36 is mainly constituted by the hard disk drive 73 , and stores data of many songs (music data) associated with identification information of the songs, i.e., music IDs.
[0075] The request reception unit 21 is mainly constituted by the processor 70 , the memory 71 , and the communication interface 76 , and receives the preference vector and the theme data from the user apparatus 12 . The theme data change unit 22 a is mainly constituted by the processor 70 and the memory 71 . The theme data change unit 22 a refers to the theme group data stored in the theme group data storage unit 31 , and selects one of theme template IDs which belong to the same group as the theme template ID included in the received theme data according to a random number. Further, the theme template of the selected theme template ID is read from the theme template storage unit 32 , and checks the attribute specified by the theme template. Then, the attribute value conversion dictionary stored in the attribute value conversion dictionary storage unit 33 is looked up, and the attribute value of each attribute included in the received theme data is converted to an attribute value of each specified attribute. The theme template ID thus newly selected and the converted attribute value of each attribute are given to the music list generation unit 22 b as theme data.
[0076] The music list generation unit 22 b is mainly constituted by the processor 70 and the memory 71 . The music list generation unit 22 b refers to the first metadata stored in the first metadata storage unit 34 , and selects a song attached with the received attribute value of each attribute. Then, the music list generation unit 22 b outputs a list of music IDs of these songs.
[0077] The second filter 23 is mainly constituted by the processor 70 and the memory 71 , and receives a list of music IDs from the music list generation unit 22 b , and receives the preference vector from the request reception unit 21 . Then, the feature vector stored in the second metadata storage unit 35 is read in association with each music ID included in the list, and the degree of similarity between each feature vector and the preference vector is calculated. Then, the songs are sorted by the degree of similarity, and a predetermined number of songs are selected in the descending order of the degree of similarity. Then, a list of IDs of the songs thus selected is output. The music list reply unit 24 replies the thus obtained list to the user apparatus 12 .
[0078] The music distribution unit 25 is mainly constituted by the processor 70 , the memory 71 , and the communication interface 76 . The music distribution unit 25 receives the music ID from the music reproduction unit 52 of the user apparatus 12 , reads the music data stored in the music data storage unit 36 in association with the music ID, and replies the music data to the user apparatus 12 .
[0079] The content recommendation system 10 as described above applies the first filter 22 and the second filter 23 in an overlapping manner to select some of many contents, and causes the user apparatus 12 to reproduce and output the selected contents in order. The first filter 22 selects songs according to attribute value conditions successively generated by the theme selection unit 41 , the attribute value determination unit 45 , and the theme data change unit 22 a . The second filter 23 selects songs according to the degree of similarity between the feature vector of each song and the preference vector of the user. Therefore, various songs can be recommended to the user, compared with a case where songs are selected simply using a preference vector. In particular, since the attribute value condition is determined based on a random number, songs can be recommended to the user in an unexpected manner. Further, the first filter 22 extracts some of many songs, and thereafter, the processing of the second filter 23 is executed on some of the songs. Therefore, the amount of calculation necessary for recommending songs can be reduced.
[0080] Further, the theme data are generated upon stochastically selecting a theme template according to the theme preference distribution data and stochastically selecting an attribute value according to the attribute value preference distribution data. Therefore, various kinds of theme data can be generated according to the user's preference. Since songs are selected using these various kinds of theme data, various kinds of songs can be recommended to the user. Further, the theme data change unit 22 a uses the theme group data and the attribute value conversion dictionary to change the theme data received from the user apparatus 12 to another theme data. Accordingly, the first filter 22 can select songs according to the theme template and the attribute value which are not yet stored in the user apparatus 12 . Therefore, the degree of unexpectedness and diversity in song selection can be increased.
[0081] Further, in the content recommendation system 10 , the attribute value preference distribution data are updated according to the attribute values of the songs owned by the user. Therefore, even though the user has various kinds of preferences in music, various kinds of songs can be recommend according to the various kinds of preferences.
[0082] The present invention is not limited to the above embodiment. Various modifications may be applied. For example, the content recommendation processing may not be shared by the user apparatus 12 and the server 14 . One computer may select songs recommended to the user. On the contrary, the content recommendation processing may be shared by many computers. In the explanation above, the attribute value preference distribution data are updated based on the contents of operation performed with the operation unit 51 . However, the attribute value preference distribution data may be updated based on only the songs owned by the user. Alternatively, instead of using the second filter 23 , songs selected by the first filter 22 may be recommended to the user as they are.
[0083] Alternatively, first, the server 14 may select songs with the second filter, and thereafter, the user apparatus 12 may further select songs from among the selection result (narrowing down) with the first filter. FIG. 15 illustrates this modified operation flow diagram. In the content recommendation system 10 according to the modification, first, the user apparatus 12 transmits user's preference vector to the server 14 (S 501 ).
[0084] The server 14 calculates the degree of similarity between the preference vector received from the user apparatus 12 and each feature vector of all or some of the songs stored in the music database 36 , and selects a predetermined number of songs having a higher degree of similarity in the descending order of the degree of similarity (S 601 ). Then, a music list including the music IDs of the predetermined number of songs is replied to the user apparatus 12 (S 602 ). When the user apparatus 12 receives the music list, theme data are selected (S 502 ). The method for selecting theme data is the same as FIG. 7 . Then, the user apparatus 12 obtains an attribute value condition based on the theme data selected in S 502 . Thereafter, while referring to the first metadata, songs satisfying the obtained attribute value condition are selected from among the songs included in the music list received from the server 14 , and the music IDs of the songs thus selected are included in the music list (S 503 ). Thereafter, finally, one of the music IDs included in the music list is transmitted to the server 14 (S 504 ). Then, the server 14 reads data of the song identified by the music ID from the database 14 a , and replies the data (S 603 ). The user apparatus 12 reproduces the data of the song thus replied (S 505 ), and the internal speakers 204 a , 204 a of the television monitor 204 output music. When the songs of all the music IDs included in the music list are reproduced in this manner, the user apparatus 12 executes the processing of S 201 again. When the processings are thus performed, the load of the processings of the server 14 can be reduced.
[0085] Alternatively, selection of songs based on the first metadata may be shared by the user apparatus 12 and the server 14 . For example, when the attribute value condition includes a plurality of AND conditions (product set), the server 14 may select songs satisfying some of the conditions, and the user apparatus 12 may select songs satisfying the remaining conditions from among the songs included in the selection result. The user apparatus 12 may determine, based on the remaining conditions, the order of reproduction of the songs included in the selection result given by the server 14 or the songs further satisfying the remaining conditions.
[0086] Alternatively, songs reproduced by the user apparatus 12 or the server 14 may exclude songs which the user does not like. In a case where an operation is performed with the operation device 202 to explicitly indicate negative evaluation during reproduction of a song (particular operation indicating that the user does not like the song) or an operation is performed to give an instruction of pausing reproduction, the user apparatus 12 causes the music ID of the song to be included in a disliked music list stored in the hard disk drive 334 . When the user apparatus 12 receives the music list from the server, and the music list includes a music ID of the song listed in the disliked music list, the song may not be allowed to be reproduced. Alternatively, when the disliked music list of each user is managed by the server 14 , and a music list is generated in the server 14 , the music list may not include the music ID of the song listed in the disliked music list.
[0087] Instead of generating the disliked music list, a classifier (SVM: Support Vector Machine) may be used to determine whether the user likes or dislikes each song. For example, classifier software is installed to the user apparatus 12 . In a case where an operation is performed with the operation device 202 to explicitly indicate negative evaluation during reproduction of a song (particular operation indicating that the user does not like the song, or an operation is performed to give an instruction of pausing reproduction, or in a case where an operation is performed with the operation device 202 to explicitly indicate favorable evaluation during reproduction of a song (particular operation indicating that the user likes the song), or the song is played until the end of the song without interruption, this fact is input to the classifier, so that the classifier learns the user's preference. Then, for each song having the music ID included in the music list transmitted from the server 14 , the classifier may determine whether the user likes a song or not, and the song disliked by the user may not be allowed to be reproduced.
[0088] The user apparatus 12 may be achieved with various kinds of hardware. For example, the user apparatus 12 may be achieved with the portable game machine. FIG. 16 illustrates an external appearance of a portable game machine. The portable game machine 400 reproduces digital contents such as moving images, still images and music, and executes a game program and the like. Each content is read from an external storage medium detachable from the portable game machine 400 , or is downloaded via data communication. The external storage medium according to this embodiment is a small optical disk 402 such as a UMD (Universal Media Disc) and a memory card 426 . The optical disk 402 and the memory card 426 respectively are mounted on a drive device (not shown) provided in the portable game machine 400 . The optical disk 402 is not only capable of storing music data and still image data but also storing moving image data such as a movie having a relatively large data size. The memory card 426 is a small memory card which can also be detachably installed in a digital camera or a cell phone. The memory card 426 primarily stores still image data, moving image data, audio data, and the like, generated by the user by using another device or data exchanged with other devices.
[0089] The portable game machine 400 is provided with a liquid crystal display 404 , operation unit members such as an arrow key 416 , an analog stick 418 , buttons 420 , and the like. The user holds the right and left ends of the portable game machine 400 with both hands. The arrow key 416 or the analog stick 418 is operated primarily by the left thumb to specify up/down/left/right movement. The buttons 420 are used primarily by the right thumb to provide various instructions. Unlike the arrow key 416 and the buttons 420 , a home button 436 is provided at a position not likely to be pressed by any finger when the left and right ends of the portable game machine 400 are held with both hands, thereby preventing erroneous operations. The liquid crystal display 404 displays a menu screen and a reproduction screen of each content. The portable game machine 400 is also provided with communication functions achieved via a USB port and a wireless LAN, for data exchange with other devices using the USB port and the wireless LAN. The portable game machine 400 is further provided with a select button 440 , a start button 438 , and the like. The start button 438 is used, e.g., when the user instructs the portable game machine 400 to start a game, start reproduction of contents such as a movie or music, or pause the game or the playback of the movie or music. The select button 440 is used to select a menu item displayed on the liquid crystal display 404 .
[0090] FIG. 17 illustrates an internal circuit configuration of the portable game machine 400 . The portable game machine 400 includes a control system 540 including a CPU 541 , peripheral devices, and the like, a graphics system 550 including a GPU 552 and the like for drawing an image in a frame buffer 553 , a sound system 560 including a SPU (sound processing unit) 561 and the like for generating music sounds, sound effects, and the like, an optical disk control unit 570 for controlling an optical disk 402 storing an application program, a wireless communication unit 580 , an interface unit 590 , an operation input unit 502 , a bus connected to each of the above units, and the like.
[0091] The sound system 560 includes an SPU 561 for generating, e.g., music sounds and sound effects under the control of the control system 540 , a sound buffer 562 in which waveform data and the like are recorded by this SPU 561 , and a speaker 544 for outputting, e.g., music sounds and sound effects which are generated by the SPU 561 .
[0092] The SPU 561 has an ADPCM decoding function for reproducing sound data encoded with ADPCM, a reproduction function for generating e.g., sound effects, by reproducing waveform data stored in the sound buffer 562 , and a modulation function for modulating and reproducing waveform data stored in the sound buffer 562 .
[0093] The optical disk control unit 570 includes an optical disk device 571 for reproducing data such as programs recorded in an optical disk, a decoder 572 for decoding recorded data attached with, e.g., Error Correction Code (ECC), and a buffer 573 increasing the speed of reading data from the optical disk by temporarily storing data read from the optical disk device 571 . The decoder 572 is connected to a sub-CPU 574 .
[0094] The interface unit 590 includes a parallel I/O interface (PIO) 591 and a serial I/O interface (S 10 ) 592 . These are interfaces connecting the memory card 426 and the portable game machine 400 .
[0095] The operation input unit 502 provides an operation signal according to user's operation to the CPU 541 . The wireless communication unit 580 wirelessly communicates via an infrared port or a wireless LAN. Under the control of the control system 540 , the wireless communication unit 580 transmits data to another apparatus and receives data from another apparatus directly or via a wireless communication network such as the Internet.
[0096] The graphics system 550 includes a geometry transfer engine (GTE) 551 , a GPU 552 , a frame buffer 553 , an image decoder 554 , and a display unit 404 .
[0097] The GTE 551 has a parallel computing mechanism for executing multiple computations in parallel. The GTE 551 performs high-speed calculation of coordinate conversion, light-source calculation, calculation of matrix and vector, and the like in response to calculation request given by the main CPU 541 . Then, based on the calculation result of the GTE 551 , the control system 540 defines a three-dimensional model as a combination of basic unit figures (polygons) such as a triangle and a quadrangle, and transmits a drawing instruction corresponding to each polygon for drawing a three-dimensional image to the GPU 552 .
[0098] The GPU 552 draws a polygon in the frame buffer 553 according to a drawing instruction given by the control system 540 . Further, the GPU 552 performs flat shading, Gouraud shading for determining the color in the polygon by interpolating the color at the apexes of the polygon, and texture mapping for pasting textures stored in a texture region of the frame buffer to the polygon.
[0099] The frame buffer 553 stores an image drawn by the GPU 552 . This frame buffer 553 is constituted by a so-called dual port RAM. The frame buffer 553 can perform, at a time, drawing operation of the GPU 552 , transfer from the main memory 543 , and reading operation for display. This frame buffer 553 includes not only a display region for outputting as a video output but also a CLUT region storing a Color Look Up Table (CLUT) which is looked up by the GPU 552 to draw a polygon and the like and the texture region storing textures. These CLUT region and the texture region are dynamically changed according to changes of display region and the like.
[0100] Under the control of the control system 540 , the display unit 3 displays an image stored in the frame buffer 553 . Under the control of the CPU 541 , the image decoder 554 decodes image data of still images or moving images stored in the main memory 543 and compressed and encoded by orthogonal transformation such as discrete cosine transform under the control of the CPU 541 , and stores the decoded image data to the main memory 543 .
[0101] The control system 540 includes the CPU 541 , a peripheral device control unit 542 for performing, e.g., control of direct memory access (DMA) transfer and interruption control, the main memory 543 made of a RAM, and a ROM 544 . The ROM 544 stores programs such as an operating system and the like for controlling the respective units of the portable game machine 400 . The CPU 541 controls the overall portable game machine 400 by reading the operating system stored in the ROM 544 to the main memory 543 and executing the operating system having been read. The user apparatus 12 can also be achieved using the portable game machine 400 as described above.
[0102] The user apparatus 12 can also be achieved using a general-purpose personal computer. FIG. 18 illustrates an internal circuit configuration of the general-purpose personal computer.
[0103] The general-purpose personal computer includes, as its principal components, a main CPU 600 , a graphics processing unit 602 , an input unit 604 , an output unit 605 , a drive 614 , a main memory 608 , and a ROM 610 . The main CPU 600 controls signal processing and internal constituent elements based on programs such as an operating system and an application. The GPU 602 performs image processing.
[0104] These units are connected with each other via a bus line 622 . The bus line 622 is further connected to an input/output interface 632 . The input/output interface 632 is connected to a storage unit 634 such as a hard disk and a nonvolatile memory, an output unit 605 including a display and a speaker, an input unit 604 including a keyboard, a mouse, a microphone, and the like, a peripheral device interface such as USB and IEEE1394, a communication unit 630 including a network interface for a wired or wireless LAN, and a drive 614 for driving a removable recording medium 626 such as an own plane disk, an optical disk, or a semiconductor memory.
[0105] The main CPU 600 controls the overall operation of the personal computer by executing the operating system stored in the storage unit 634 . Further, the main CPU 600 executes various kinds of programs read from the removable recording medium 626 and loaded to the main memory 608 or downloaded via the communication unit 630 .
[0106] The GPU 602 has functions of a geometry transfer engine and a rendering processor. The GPU 602 performs drawing processing according to a drawing instruction given by the main CPU 600 , and stores a display image to a frame buffer, not shown. The GPU 602 converts the display image stored in the frame buffer into a video signal, and outputs the video signal. The user apparatus 12 can also be achieved with the personal computer as described above. | A content recommendation system including a step which selects some from a plenty of music compositions in accordance with attribute conditions successively generated, a step which further selects a part or all of the selected music compositions in accordance with the similarity degree between the feature vector of each of the selected music compositions and the user preference vector, and a step which presents the selected music composition to the user. | 6 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims priority under 35 USC 119 to Japanese Patent Application No. 2009-015385 filed on Jan. 27, 2009 the entire contents of which are hereby incorporated by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to a splash guard mechanism suitable for a brake system for a vehicle, in particular, for an ATV (All Terrain Vehicle).
[0004] 2. Description of Background Art
[0005] Vehicle are equipped with a brake system. In an ATV capable of traveling on an unpaved ground such as dirt or moor, it is necessary to strengthen measures against, particularly, the entry of mud into a brake system. Such measures have been proposed for example, in JP-A No. 2008-57707, see FIG. 11.
[0006] A related art will be described with reference to FIG. 11 of JP-A No. 2008-57707. Referring to FIG. 11, dirt (72) such as mud and gravel is deposited on a smallest-diameter portion (32 a ) of a rim, as shown in FIG. A1 (the bracketed reference signs are those transferred from JP-A No. 2008-57707, hereinafter described in the same manner). The smallest-diameter portion (32 a ) of the rim is a rotating body, and a brake disc guard (33) is a nonrotating body. A flange (38) extends from the brake disc guard (33) to the near side of the drawing.
[0007] When the smallest-diameter portion (32 a ) of the rim rotates in the direction shown by arrow F, a part of the dirt (72) falls down. The rest of the dirt (72) reaches an upper portion as shown in FIG. B1, and then is scraped off by a scraper (36) in FIG. C1.
[0008] The brake disc guard (33) includes a lower portion (41) that is widely cutout. The dirt (72) having fallen down in FIG. 11 sub-FIGS. A1, B1, and C1, is ejected to the far side of the drawing through the large opening of the lower portion (41).
[0009] That is to say, JP-A No. 2008-57707 discloses a splash guard mechanism for a vehicle in which the brake disc guard (33) is provided so as to prevent the entry of mud and gravel into a brake disc (30) provided in a wheel, and the lower portion (41) is provided with a cutout so as to easily eject therethrough mud and gravel having entered the brake disc (30).
[0010] However, a vehicle such as an ATV may travel on grass. Although grass having entered the brake disc (30) is also ejected through the cutout of the lower portion (41), grass is likely to become tangled therein as compared with mud and gravel. Therefore, the ejection of the grass becomes more difficult. For this reason, the entry of grass into the brake disc (30) is preferably suppressed as much as possible.
SUMMARY AND OBJECTS OF THE INVENTION
[0011] Accordingly, an object of an embodiment of the present invention is to provide a splash guard mechanism capable of preventing the entry of grass in addition to mud and gravel in a vehicle such as a an ATV (All Terrain Vehicle).
[0012] According to an embodiment of the present invention, a splash guard mechanism for a vehicle, mounted on a brake system stored in a concave portion is provided on each wheel for the wheels to prevent entry of mud from the outside into the brake system. A substantially disc-shaped plate portion covers the brake system to close the concave portion. A first cutout portion is formed by cutting out a lower portion of the plate portion. A grass removal portion extends from the plate portion toward a vehicle center, with at least a portion thereof overlapping with a vehicle front portion of the first cutout portion.
[0013] According to an embodiment of the present invention, the grass removal portion is formed in a substantially triangular shape with an apex protruding toward the vehicle center in a plan view. A steep oblique portion having a sharp inclination is provided in the vicinity of the apex on a front oblique side of the substantially triangular shape, and an edge of the front oblique side is bent downward.
[0014] According to an embodiment of the present invention, a knuckle is connected to the wheel through a wheel hub. When arm connectors of a suspension are provided on the knuckle, the apex is disposed on a vehicle front side of the arm connectors.
[0015] According to an embodiment of the present invention, the substantially disc-shaped plate portion includes a guide portion extending outwardly of the vehicle from the plate portion to guide mud deposited on a rim, and is formed in a C-shape with a portion thereof cutout. The second cutout portion is disposed so as to face the vehicle front side and contains a brake caliper. A front end of the guide portion is disposed above the second cutout portion with the grass removal portion being disposed below the second cutout portion.
[0016] According to an embodiment of the present invention, a bent portion, formed by bending downward the edge of the front oblique side, extends to the vicinity of the rim, and a lower edge surface of the bent portion is formed along a bottom surface of the rim.
[0017] According to an embodiment of the present invention, the plate portion is provided with the grass removal portion extending toward the vehicle center. Therefore, grass growing on the ground or in water, or the like, can be pushed out toward the vehicle center by the grass removal portion. By the pushing operation, the grass is separated from the first cutout portion of the plate portion. In other words, according to the present invention, it is possible to provide a splash guard mechanism capable of preventing the entry of grass, in addition to mud and gravel, in a vehicle such as an ATV (All Terrain Vehicle).
[0018] According to an embodiment of the present invention, while the vehicle travels forward, grass is received by the front oblique side. The grass is pushed toward the vehicle center along the oblique side to be flicked away toward the vehicle center by the steep oblique portion provided in the vicinity of the apex and having a sharp inclination. As a result, the grass is largely away from the first cutout portion. However, some of the grass can immediately return by an elastic action. The returned grass abuts on the rear oblique side to move slowly to the plate portion along the rear oblique side.
[0019] In addition, an edge of the front oblique side is bent downward. The bent portion allows an increase in rigidity of the grass removal portion. Further, since the bent portion is provided substantially vertically with respect to the ground, the grass can be readily pushed out.
[0020] According to an embodiment of the present invention, the apex of the grass removal portion is disposed on the vehicle front side of the arm connectors of the arms of the suspension. That is to say, the grass removal portion is provided at such a position to avoid interference with the arms of the suspension, thereby allowing enlargement of the grass removal portion and increasing flexibility in shape design.
[0021] According to an embodiment of the present invention, the substantially disc-shaped plate portion is formed in a C-shape with a portion thereof cutout, and the second cutout portion is disposed so as to face the vehicle front side and can contain a brake caliper. Also, a front end of the guide portion is disposed above the second cutout portion, and the grass removal portion is disposed below the second cutout portion. Commonly, a rear upper portion of a tire is covered with a fender or the like, and a front portion thereof is open to thereby facilitate access from the outside. Since the brake caliper, the front end of the guide portion, and the grass removal portion are disposed in front of the tire constructed in this manner, the removal of mud and gravel remaining therein without being ejected can be further facilitated.
[0022] According to an embodiment of the present invention, a bent portion, formed by bending downward the edge of the front oblique side, extends to the vicinity of the rim, and a lower edge surface of the bent portion is formed along a bottom surface of the rim. With this structure, it is possible to reduce the spacing between the lower edge surface of the bent portion and the rim, and prevent the entry of mud, gravel, and grass into the concave portion of the wheel through the spacing.
[0023] Further scope of applicability of the present invention will become apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] The present invention will become more fully understood from the detailed description given hereinbelow and the accompanying drawings which are given by way of illustration only, and thus are not limitative of the present invention, and wherein:
[0025] FIG. 1 is a left side view of a vehicle with a splash guard mechanism of the present invention;
[0026] FIG. 2 is a view illustrating the structure of a front wheel and a suspension;
[0027] FIG. 3 is a perspective view of a wheel seen from the vehicle center;
[0028] FIG. 4 is a front view of the splash guard mechanism according to the present invention;
[0029] FIG. 5 is a view taken in the direction of arrow 5 - 5 of FIG. 4 ;
[0030] FIG. 6 is a sectional view taken along the line 6 - 6 of FIG. 4 ;
[0031] FIG. 7 is a perspective view of the splash guard mechanism according to the present invention;
[0032] FIG. 8 is a view illustrating the operation of a grass removal portion of the present invention;
[0033] FIG. 9 is a sectional view taken along the line 9 - 9 of FIG. 8 ;
[0034] FIG. 10 is a rear view of the splash guard mechanism according to the present invention;
[0035] FIG. 11 is a perspective view with the splash guard mechanism mounted;
[0036] FIG. 12 is a sectional view taken along the line 12 - 12 of FIG. 11 ;
[0037] FIG. 13 is a sectional view taken along the line 13 - 13 of FIG. 11 ;
[0038] FIG. 14 is a sectional view taken along the line 14 - 14 of FIG. 11 ;
[0039] FIG. 15 is a sectional view taken along the line 15 - 15 of FIG. 11 ; and
[0040] FIG. 16 is a sectional view taken along the line 16 - 16 of FIG. 11 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0041] An embodiment of the present invention will hereinafter be described with reference to the accompanying drawings. In the following description, it is to be noted that “front,” “rear,” “left,” and “right” denote directions viewed from the occupant's position, and the drawings should be seen according to the direction of reference signs.
[0042] FIG. 1 is a left side view of a vehicle with a splash guard mechanism of the present invention. In this embodiment, an ATV (All Terrain Vehicle) is used as an example of a vehicle 10 . The vehicle 10 is a four-wheeled vehicle including an engine 12 and a transmission 13 in the center of a body frame 11 , driving front wheels 16 through a front gearbox 15 by a front drive shaft 14 extending forward from the transmission 13 , and driving rear wheels 19 through a rear gearbox 18 by a rear drive shaft 17 extending rearward from the transmission 13 . Also, the vehicle 10 is a saddle-ride type vehicle in which an occupant sits astride a seat 21 disposed on an upper central portion of the body frame 11 to operate a steering wheel 22 .
[0043] On the body frame 11 , a fuel tank 23 is disposed between the seat 21 and the steering wheel 22 . Also, a radiator 24 is disposed above the front wheels 16 . Each of the front wheels 16 is supported in a vertically movable manner by a suspension including an upper arm 25 and a lower arm 26 . A support structure of the front wheels 16 will be described in detail in the next drawing.
[0044] FIG. 2 is a view illustrating the structure of the front wheel and the suspension. The upper arm 25 and the lower arm 26 extend outwardly of the vehicle from cross members 27 and 28 serving as one element of the body frame (body frame 11 in FIG. 1 ) to be connected to a knuckle 32 through ball joints 29 and 31 , respectively. The connecting portion of the ball joint 31 to the knuckle 32 is referred to as an arm connector 33 .
[0045] A front wheel axle 36 is attached to the knuckle 32 through a bearing 34 and a rotating cylinder 35 . Further, the front wheel 16 is attached to a flange 37 extending from a vehicle-exterior side edge of the rotating cylinder 35 by a bolt.
[0046] The front wheel 16 is composed of a tire 38 and a wheel 39 for supporting the tire 38 . The wheel 39 is composed of a disc 42 having a bolt hole 41 , and a rim 43 joined to the outer periphery of the disc 42 . The tire 38 is fitted to the rim 43 . As is clear from the drawing, the disc 42 is connected to the rim 43 at a position deviating to the vehicle outer side from the center in the vehicle width direction of the rim 43 . Therefore, a large concave portion 44 is provided toward the vehicle center from the disc 42 .
[0047] In the large concave portion 44 , a brake system 48 composed of a brake disc 46 , a brake caliper (reference sign 47 in FIG. 3 ) and the like is stored, and a splash guard mechanism 50 covering the brake disc 46 to close the concave portion 44 is disposed. Although the detailed structure of the splash guard mechanism 50 will be described later, the splash guard mechanism 50 is connected to the knuckle 32 , and thus, non-rotatable. On the other hand, the brake disc 46 is connected to the flange 37 , and therefore rotated along with the front wheel 16 through a constant-velocity joint 49 extending from the front gearbox 15 .
[0048] FIG. 3 is a perspective view of a wheel seen from the vehicle center. The splash guard mechanism 50 , the brake caliper 47 , and the brake disc 46 are stored in the concave portion 44 of the wheel 39 . A splash guard holder 51 is formed integrally with the knuckle 32 , and the splash guard mechanism 50 is held by the splash guard holder 51 . Here, a plurality of splash guard holder 51 are formed, however, the other splash guard holder 51 is located behind the knuckle 32 and cannot be seen in the drawing. Also, brackets 52 and 52 extend from the knuckle 32 , and the brake caliper 47 is supported by the brackets 52 and 52 . The brake caliper 47 is disposed in a second cutout portion 53 provided on the splash guard mechanism 50
[0049] Next, the structure of the splash guard mechanism 50 will be described in detail. FIG. 4 is a front view of the splash guard mechanism according to the present invention. When viewed from the vehicle center, the splash guard mechanism 50 is composed of a substantially disc-shaped plate portion 55 including the second cutout portion 53 to be formed in a C-shape. A guide portion 56 extends from the plate portion 55 to the far side of the drawing, that is, outwardly of the vehicle. A first cutout portion 57 is formed by cutting out a lower portion thereof. A grass removal portion 60 extends from the plate portion 55 to the near side of the drawing, that is, toward the vehicle center, with at least a portion thereof overlapping with a vehicle front portion 58 of the first cutout portion 57 . The splash guard mechanism 50 constructed in such a manner, is connected to the splash guard holders (splash guard holder 51 in FIG. 3 ) provided on the knuckle 32 using a plurality of bolt holes 59 (three in this embodiment) arranged so as to surround the large second cutout portion 53 .
[0050] FIG. 5 is a view taken in the direction of arrow 5 - 5 of FIG. 4 . The grass removal portion 60 is formed in a substantially triangular shape with an apex 61 protruding downwardly in the drawing, that is, toward the vehicle center, in plan view. A front oblique side 62 of the substantially triangular shape is provided with a steep oblique portion 63 having a sharp inclination, in the vicinity of the apex 61 . An edge of the front oblique side 62 is bent to the far side of the drawing, as shown by the dashed line.
[0051] FIG. 6 is a sectional view taken along the line 6 - 6 of FIG. 4 . The guide portion 56 extends from the plate portion 55 to the right of the drawing, that is, outwardly of the vehicle. Also, the grass removal portion 60 extends from a lower portion of the plate portion 55 to the left of the drawing, that is, toward the vehicle center. A bent portion 64 is bent from the front oblique side 62 of the grass removal portion 60 thereby to be formed.
[0052] FIG. 7 is a perspective view of the splash guard mechanism according to the present invention. A rear oblique side 67 of the grass removal portion 60 overlaps with the vehicle front portion 58 of the first cutout portion 57 . The grass removal portion 60 constructed in this manner, includes the bent portion 64 formed by bending downward an edge of the front oblique side 62 .
[0053] FIG. 8 is a view illustrating the operation of the grass removal portion of the present invention. Along with the forward movement of the vehicle, the grass removal portion 60 substantially triangle-shaped in plan view moves in the direction shown by arrow ( 1 ). Grass 66 growing on the ground or in water, moves relatively in the direction shown by arrow ( 2 ) along the front oblique side 62 to be pushed out in the direction shown by arrow ( 3 ), by the steep oblique portion 63 . When the grass 66 is not springy, the grass 66 returns slowly in the direction shown by arrow ( 4 ). Ideally, the grass 66 outreaches the first cutout portion 57 .
[0054] When the grass 66 is springy, the grass 66 is immediately returned in the direction shown by arrow ( 5 ). Thereafter, the grass 66 moves slowly in the direction shown by arrow ( 6 ) along the rear oblique side 67 formed to be gently-inclined. Therefore, the grass 66 becomes less likely to enter the first cutout portion 57 .
[0055] FIG. 9 is a sectional view taken along the line 9 - 9 of FIG. 8 . The grass 66 is pushed by the bent portion 64 , thereby avoiding injury to the grass 66 . Also, a lower edge surface 65 of the bent portion 64 is kept horizontal. Since the grass 66 stands substantially erect on the ground, the horizontally provided lower edge surface 65 allows the grass 66 to be prevented from being cut.
[0056] FIG. 10 is a rear view of the splash guard mechanism according to the present invention. When viewed from the vehicle-exterior side, the guide portion 56 extends about 180 degrees in the counterclockwise direction along the rim 43 from the vicinity of an edge, on the right of the drawing, of the first cutout portion 57 . At an upper position on the guide portion 56 , a triangular baffle plate 68 (baffle plate 68 shown by the imaginary line in FIG. 6 ) is provided between the guide portion 56 and the plate portion 55 . Also, the front end of the guide portion 56 is a scraper 69 , and the spacing between the rim 43 and the guide portion 56 becomes smaller by the scraper 69 .
[0057] The rim 43 on which mud 70 is deposited, rotates in the counterclockwise direction along with the forward movement of the vehicle. On the other hand, the splash guard mechanism 50 does not rotate. The mud 70 is scraped off by the baffle plate 68 to fall down, and then is ejected from the first cutout portion 57 to the far side of the drawing. Remaining mud 71 passing over the baffle plate 68 is scraped off by the scraper 69 to fall down, and then is ejected from the first cutout portion 57 to the far side of the drawing.
[0058] Referring back to FIG. 3 , the right side of the drawing is the vehicle front side, and the brake caliper 47 is disposed at the vehicle front side of the center (the same as the center of the axle) of the wheel 39 . It is common that a rear upper portion of a tire is covered with a fender or the like, and a front portion thereof is open to thereby facilitate access from the outside. Since the brake caliper 47 is disposed at a front portion of the tire constructed in this manner, the removal of mud and gravel jammed in the brake caliper 47 can be further facilitated.
[0059] Also, the front end (the scraper 69 in FIG. 10 ) of the guide portion 56 is disposed above the second cutout portion 53 , and the grass removal portion 60 is disposed below the second cutout portion 53 . Since the front end of the guide portion 56 and the grass removal portion 60 are disposed in front of the tire, the removal of mud and gravel remaining therein without being ejected can be further facilitated.
[0060] Furthermore, the apex 61 of the grass removal portion 60 is disposed on the vehicle front side of the arm connectors 33 of the arms of the suspension. That is to say, the grass removal portion 60 is provided at such a position to avoid interference with the arms (upper arm 25 and lower arm 26 in FIG. 2 ) of the suspension, thereby allowing enlargement of the grass removal portion 60 and increasing flexibility in the shape design.
[0061] Also, in FIG. 2 , the rim 43 is formed in a cone shape gently broadened toward the vehicle center. As compared with a cylindrically-shaped one, the cone-shaped rim 43 further facilitates the ejection of dirt (such as mud, gravel, and grass) having entered the concave portion 44 because the dirt spirals into a conic surface thereof when the rim 43 rotates. This ejection is performed by the first cutout portion (first cutout portion 57 in FIG. 3 ) provided on the far side in the drawing of the bent portion 64 . Therefore, the bent portion 64 does not interfere with such ejection.
[0062] Meanwhile, since the bent portion 64 can be provided sufficiently close to the rim 43 , the entry of mud and the like can be prevented. In addition, by providing the bent portion 64 , the rigidity of the grass removal portion (grass removal portion 60 in FIG. 3 ) can be increased.
[0063] Next, a relative position between the rim 43 and the grass removal portion 60 will be further described in detail. As shown in FIG. 11 , a lower edge 73 (particularly, the lower edge surface 65 ) of the grass removal portion 60 is formed along a bottom surface 45 of the rim 43 , and its detailed description will be given with reference to FIGS. 12 to 16 showing sectional views of FIG. 11 .
[0064] As shown in FIG. 12 , a spacing C 1 between the lower edge 73 of the grass removal portion 60 and the bottom surface 45 of the rim 43 is sufficiently small. As shown in FIGS. 13 and 14 , spacings C 2 and C 3 between the lower edge surface 65 of the bent portion 64 and the bottom surface 45 of the rim 43 are sufficiently small. Since the spacings C 1 to C 3 are small, the entry of grass and gravel can be suppressed.
[0065] On the other hand, in FIG. 15 in which no bent portion 64 is provided, a spacing C 4 between the rear oblique side 67 and the bottom surface 45 of the rim 43 is large. In the same manner, in FIG. 16 in which no bent portion 64 is provided, a spacing C 5 between the first cutout portion 57 and the bottom surface 45 of the rim 43 is sufficiently large. Since the spacing C 4 and C 5 are large, the ejection of the entered grass, mud, and gravel can be effectively performed.
[0066] The splash guard mechanism according to the present invention is suitable for ATVs, however, may be used in normal vehicles.
[0067] The invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the following claims. | A splash guard mechanism for preventing the entry of grass, in addition to mud and gravel, in a vehicle such as a an ATV (All Terrain Vehicle). A disc-shaped splash guard mechanism covers a brake disc stored in a concave portion of a wheel to thereby prevent the entry of dirt such as mud, gravel, and grass into the brake disc. If the dirt enters the brake disc, the dirt is ejected from a first cutout portion provided on a lower portion of the splash guard mechanism. Additionally, a grass removal portion substantially triangle-shaped in plan view is provided on a lower portion of the splash guard mechanism. The grass removal portion protrudes toward a vehicle center to push grass on the ground outward and away from the first cutout portion. Since the grass is only pushed out, the grass is prevented from being cut and entering the brake disk. | 1 |
BACKGROUND OF INVENTION
In connection with the retail sale of jewelry, a particular problem arises when the jewelry to be sold consists of small elements. For instance, in the case of ear rings, the assemblage and the parts are sometimes quite small. When the ear ring is of the type that is used with pierced ears, the ornament portion is usually provided with a stem which is intended to pass through the ear lobe and a clutch that mounts on the stem at the rear of the lobe. Since the ear rings are normally sold in pairs, there are several problems that arise. First of all, the jewelry must be displayed at the point of sale, so that the display package must be attractive. Secondly, the display package must be simple and rugged to withstand the ordeal of handling by the prospective customers, as well as during shipping, storage, and arrangement by the retailer.
A common method of displaying ear rings at the point-of-sale is by mounting them on a card that is then suspended on a rack; the mounting on the card takes place by using the stem and clutch in the manner shown in the patent of Feibelman U.S. Pat. No. 4,281,469 and the patent of Barbato U.S. Pat. No. 4,718,554 and Robertson U.S. Pat. No. 4,944,389. Another method of mounting the stem-type ear rings is by driving the stem into a soft body of material and enclosing the clutches in a separate cell, as shown in the patent to Garganese U.S. Pat. No. 4,697,705.
When any of these constructions are used in connection with the display of stem-type ear rings, a particular problem arises, particularly in the case of inexpensive jewelry; the assembly of the display packages in the factory involves considerable hand labor to assemble first the stem with the ornament on the display card and then placing the small clutch on the stem. This is not only a tedious operation, but it adds considerable expense to the unit because of the labor cost. Some of the constructions, furthermore, are less than secure and are likely to result in loss during shipment, storage, and handling. It is particularly important that the clutches do not become separated from the ornament and stem. Other constructions are less than attractive for display in the jewelry store.
These and other difficulties experienced with the prior art devices have been obviated in a novel manner by the present invention.
It is, therefore, an outstanding object of the invention to provide a display card for demonstrating jewelry having stems and pins in an attractive manner.
Another object of this invention is the provision of a display card for ear rings for pierced ears, in which the ornament and stem do not become separated from the clutches.
A further object of the present invention is the provision of a display card in which the clutches are secured in a manner, such that they cannot be removed without destroying the package.
A still further object of the invention is the provision of a display card which is simple and rugged in construction, which is easy to manufacture from readily-obtainable materials, and which is capable of a long life of service with a minimum of care.
It is a further object of the invention to provide a display card in which assembly with stem-type jewelry involves very little manual labor.
With these and other objects in view, as will be apparent to those skilled in the art, the invention resides in the combination of parts set forth in the specification and covered by the claims appended hereto.
SUMMARY OF THE INVENTION
In general, the invention consists of a display card for use with an ear ring having an integral stem and a separate clutch, which has a main panel with a front face surface on which the ornament appears. The stem extends through an aperture in the panel and a clutch is mounted on the stem against the rear surface of the panel. A locking sheet is pressed against major portions of the rear surface and serves to press the shield element against the rear surface, while the stem extends through the sheet.
More specifically, the clutch may consist of a peripheral shield, or other integral enlarged surface. The shield generally consists of a clear polymer disk with a central aperture that engages the clutch body. In one version of the invention, the locking sheet is folded over the back surface of the main panel and cemented to it. In another version the locking sheet is a thin, clear polymer sheet that is shrink-wrap applied to the main panel and in a further version the locking sheet is a flocked sheet cemented to the main panel.
BRIEF DESCRIPTION OF THE DRAWINGS
The character of the invention, however, may be best understood by reference to one of its structural forms, as illustrated by the accompanying drawings, in which:
FIG. 1 is a perspective view of a display card incorporating the principles of the present invention,
FIG. 2 is a front elevational view of the display card,
FIG. 3 is a side elevational view of the display card,
FIG. 4 is a sectional view of the invention taken on the line 4--4 of FIG. 2,
FIG. 5 is a front elevational view of a modification of the invention,
FIG. 6 is a sectional view of the invention taken on the line 6--6 of FIG. 5,
FIG. 7 is a rear elevational view of another modified form of the invention,
FIG. 8 is a sectional view taken on line 8--8 of FIG. 7, and
FIG. 9 is a sectional view of the invention, taken on the line 9--9 of FIG. 7.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring first to FIGS. 1-3, which best show the general features of the invention, the display card, indicated generally by the reference numeral 10, is shown in use with an ear ring 11 having an integral stem 12 and a separate clutch 13. A main panel 14 is provided with a front face surface 15 on which the ornament appears. The stem 12 extends through an aperture 16 in the main panel 14 and an enlarged surface in the form of a shield element 17, forming part of the clutch, lies against the rear surface 18 of the panel.
A locking sheet 19 lies against the major portions of the rear surface and serves to press the shield element 17 portion of the clutch against the rear surface 18. The main panel 14 is provided at its upper edge with a hook portion 22 to facilitate suspension from a display rack. The locking sheet 19 consists of an integral extension of the main panel 14 that is folded back to lie against the rear surface 18 and to be cemented to it. The locking sheet is provided with an aperture 23 through which the clutch and stem protrude.
The two apertures 16 in the main panel are congruent with the two apertures 23 in the locking sheet. Furthermore, the shield element 17, which is in the form of a disk, is larger than either of the apertures. The aperture 16 in the main panel is sufficiently large so that the face of the clutch is exposed, while the aperture 23 in the locking sheet is larger than the clutch. Both the ornament and the clutch extend from their respective apertures, while being held in place by the shield which is clamped between the main panel and the locking sheet.
The operation and advantages of the invention will now be readily understood in view of the above description. To begin with, the display card 10 is assembled during manufacture by placing the clutches in the apertures 23. With the main panel 14 in a horizontal position, the locking sheet 19 (which has been supplied with a coating of cement) is folded against the rear surface 18 of the panel. When this has been done, a portion of the clutch 13 protrudes through the apertures 23 in the sheet. The shield element 17 is, therefore, locked between the main panel and the locking sheet. In most cases, the shield is firmly fixed to the clutch, so that the clutch cannot be removed without destroying the assemblage. In other words, the clutches are not available for use until after the sale, at which time the locking sheet 19 is peeled from the back of the main panel. The completed card with the clutches can now be delivered to carding assembly where the ear ring stem is pressed into the clutch with the ornament resting on the main panel (to produce a completed display) which is accomplished with very little manual labor as it is not necessary to create the second movement of mounting a clutch on a stem while holding the card and ornament. The cost of labor is substantially reduced.
FIGS. 5 and 6 show a modification of the invention in which the display card 110 is shown with a flocked insert 119. The main panel 114 has a front face surface with a recess that is formed therein and into which the insert 119 may be received. The clutches 113 have a shield or enlarged end wall 121 and are received in slight depressions in the recess and are retained therein by the insert 119 which is secured to the main panel 114 as by an adhesive (similar to that shown in FIG. 4). Flocked sheet 119 overlies the clutches which are held in place against the rear surface 118 of the main panel 114.
In this form of the invention, the main panel is preferably made from a polymer that can be easily thermoformed, while the flocked insert may be any base material onto which flock may adhere.
FIGS. 7 and 8 show another form of the invention in which the display card 210 is used with a pair of ear rings 211, each of which has a stem 212 and a clutch 213. The front face surface 215 of a main panel 214 is formed of relatively heavy paper stock and is pierced as at 216 to permit the stems of the ear ring to pass through. The clutches 213 which have shield elements or enlarged surfaces 217 are pressed against the rear surface 218 of the main panel at the piercings and are held in place by a locking sheet 219, which is in the form of a thin, clear film of a polymer. The locking sheet may be applied by using the shrink wrap method and is sucked tightly into contact with the rear surface, while being pulled tightly over the clutches 213. When the stems of the earrings are inserted, they will pierce the sheet. The upper edge of the main panel is provided with a hook portion 222 that permits the display card to be suspended from a display rack in a store.
In this form of the invention, a semi-circular cut which is concentric with the axis of the clutch 213 may be made through the main panel and the locking sheet to provide a hinged portion to accept hoop earrings that are displayed on the front face of the card. It will be appreciated that the hinged portions will contain the clutches that are secured in place by the locking sheet.
It is obvious that minor changes may be made in the form and construction of the invention without departing from the material spirit thereof. It is not, however, desired to confine the invention to the exact form herein shown and described, but it is desired to include all such as properly come within the scope claimed. | Apparatus for displaying ear rings for use with pierced ears, including a front panel on which an ear ring ornament appears and a locking panel located at the rear of the front panel for holding a clutch in place. | 0 |
BACKGROUND OF THE INVENTION
The present invention relates to a printing apparatus.
As well known in the art, some of printing apparatuses perform color printing with using color toners supplied from toner cartridges. In many of printing apparatuses of this kind, the amounts of residual toners (hereinafter, referred to as residual toner amounts) in color toner cartridges are displayed in a display of a control panel to inform the operator of a timing when the color reproducibility of a color image is deteriorated or that when a toner cartridge is to be replaced.
FIG. 9 shows an example of a control panel 30 which displays residual toner amounts of toner cartridges in a display 31 disposed together with plural buttons on the upper face of the control panel 30 . In the vicinity of the right side of the lower edge of the display 31 , four oval indicators 32 colored respectively by CMYK (cyan, magenta, yellow and black) colors are arrayed. In the display 31 and above the four indicators 32 , bar graphs respectively showing residual amounts of toners of colors indicated by the indicators are displayed. From the indicators 32 and the bar graphs, the operator can immediately recognize the residual toner amounts of the respective colors.
Some of printing apparatuses are configured so that color printing and monochrome printing are switched over in accordance with the combination of colors of toners of toner cartridges which are set in the apparatus. When four toner cartridges respectively filled with CMYK toners are set, for example, a printing apparatus of this kind operates in a color printing mode, and, when four toner cartridges filled with toners of K are set, operates in a monochrome printing mode.
When the above-mentioned method of displaying residual toner amounts is applied to a printing apparatus of this kind, in the monochrome printing mode, residual toner amounts of four toner cartridges for K are displayed respectively in the form of the bar graphs in the display 31 of the control panel 30 . In this case, the colors of the toners the residual amounts of which are actually indicated by the bar graphs do not coincide with the colors of the indicators 32 , whereby the operator is confused.
In order to provide the user with a message indicating that the toner cartridge is to be replaced with a new one, there is installed a residual toner amount detector which detects that there is no amount of residual toner in a toner cartridge.
Recently, in order to reduce the production cost of a printing apparatus of such a kind, there is adopted a configuration where a residual toner amount detector which is not highly accurate is installed, or that where a residual toner amount detector is not installed. Instead, an amount of consumed toner is calculated by counting the number of actually printed dots.
In both the configurations where a residual toner amount detector which is not highly accurate is installed, and where a residual toner amount detector is not installed, however, the accuracy of detecting the residual toner amount is not so high. Consequently, there is a problem in that a message indicating that the toner cartridge is to be replaced with a new one would be displayed although a considerable amount of toner remains in the toner cartridge.
It is well-known a printing apparatus in which a toner cartridge for supplying toner to a photosensitive drum is sequentially changed one by one every time when printing is performed on a unit number of sheets.
When a residual toner amount detector is not installed on such a printing apparatus, the printing apparatus cannot judge whether toner remains in a cartridge or not. In a case where a toner cartridge is sequentially changed one by one every time when printing is performed on a unit number of sheets, there is a problem in that a situation may occur where printing must be performed with using a toner cartridge in which toner is consumed up.
SUMMARY OF THE INVENTION
It is therefore an object of the invention to prevent the operator from being confused by displaying of a residual toner amount in a display even when a printing mode is switched in accordance with the combination of colors of toners charged in toner cartridges.
It is also an object of the invention to enable the actual residual toner amount to be known even in the case where a residual toner amount detector has accuracy which is not high, or where a residual toner amount detector is not installed.
It is also an object of the invention to provide a printing apparatus which enables printing with toner in only a toner cartridge in which toner remains even when a sensor for detecting the residual toner amount of a toner cartridge is not installed.
In order to achieve the above objects, according to the invention, there is provided a printing apparatus, comprising:
a plurality of chambers, adapted to accommodate a plurality of cartridges each containing toner to be used for printing;
a mode changer operable to change an operation mode of the printing apparatus in accordance with a combination of respective colors of toner in the cartridges accommodated in the chambers;
a first detector, operable to detect a residual amount of toner in each of the cartridges;
a second detector, operable to detect the respective colors of toner in the cartridges when the operation mode is changed;
a controller, operable to generate an image data including a plurality of first identifiers each indicative of the residual amount of toner in one of the cartridges, and a plurality of second identifiers each indicative of one of the colors of toner and associated with one of the first identifiers; and
a display, adapted to display the image data.
With this configuration, a user is prevented from being confused by displaying of the residual toner amount in the display even when the operation mode is switched in accordance with the combination of colors of toner filled in the cartridges.
The image data may include a plurality of third identifiers each indicative of a position of one of the chambers and associated with one of the first identifiers.
The controller may be operable to calculate an average residual amount of toner in the cartridges when the second detector detects that the same color of toner is contained in all of the cartridges accommodated in the chambers. The image data may include a third identifier indicative of the average residual amount.
Each of the second identifiers may be an alphabetical character or a color of the associated one of the first identifiers.
According to the invention, there is also provided a printing apparatus, comprising:
a plurality of chambers, adapted to accommodate a plurality of cartridges each containing toner;
a print engine, adapted to perform printing on a print medium with the toner in the respective cartridges accommodated in the chambers;
a judge, determining whether it is necessary to check residual toner amounts of the respective cartridges; and
a controller, operable to cause the print engine to print a test image on the print medium when the judge determines that it is necessary to check the residual toner amounts,
wherein the test image includes a plurality of patterns each of which is to be located at different positions on the print medium and is associated with one of the chambers.
With this configuration, when a pattern a density of which is reduced exists in the test image, a user can judge that the actual residual toner amount in the cartridge which is loaded in the chamber corresponding to the pattern is reduced.
Therefore, it is possible to know the actual residual toner amount even in the case where a residual toner amount detector has accuracy which is not high, or where a residual toner amount detector is not installed.
The test image may include a plurality of identifiers each indicative of a position of one of the chambers and associated with one of the patterns.
The printing apparatus may further comprise a calculator, calculating a residual toner amount in each of the cartridge by counting the number of toner dots printed on the print medium. The judge may determine that it is necessary to check the residual toner amounts, when the calculated residual toner amount in at least one of the cartridges becomes lower than a prescribed value.
The printing apparatus may further comprise a detector, detecting a residual toner amount in each of the cartridge. The judge may determine that it is necessary to check the residual toner amounts, when the detected residual toner amount in at least one of the cartridges becomes lower than a prescribed value.
The judge may be activated when at least two of the chambers are occupied by the cartridges.
According to the invention, there is also provided a printing apparatus, comprising:
a plurality of chambers, adapted to accommodate a plurality of cartridges each containing toner;
a print engine, including a plurality of developing devices each of which is adapted to visualize an electrostatic latent image on an image carrier with the toner in associated one of the cartridges accommodated in the chambers;
a storage, storing a plurality of flags each of which is associated with one of the developing devices, and adapted to be switchable between an enabling state or a disabling state;
a controller, operable to drive the print engine so as to operate at least one of the developing devices that is associated with one of the flags which is in the enabling state; and
a first switcher, adapted to receive an instruction from a user, and operable to switch each of the flags to one of the enabling state and disabling state.
With the above configuration, a user can set a developing device to which a cartridge having a reduced amount of toner is attached, as a developing device which cannot operate. Even when a residual toner amount detector is not installed, therefore, toner in only a cartridge in which toner remains can be used in printing.
The printing apparatus may further comprise: a detector, operable to detect that a cartridge replacement is performed at each of the chambers; and a second switcher, operable to switch at least one of the flags which is associated with one of the chambers that the cartridge replacement is detected, to the enabling state.
The printing apparatus may further comprising a judge, determining whether it is necessary to check residual toner amounts of the respective cartridges. The controller may be operable to cause the print engine to print a test image on a print medium when the judge determines that it is necessary to check the residual toner amounts. The test image may include a plurality of patterns each of which is to be located at different positions on the print medium and is associated with one of the chambers.
The test image may include a plurality of identifiers each indicative of a position of one of the chambers and associated with one of the patterns.
BRIEF DESCRIPTION OF THE DRAWINGS
The above objects and advantages of the present invention will become more apparent by describing in detail preferred exemplary embodiments thereof with reference to the accompanying drawings, wherein:
FIG. 1 is a block diagram showing an internal configuration of a printing apparatus according to a first embodiment of the invention;
FIG. 2 is a plan view of a control panel of the printing apparatus;
FIG. 3 is a schematic view showing the inside of the printing apparatus;
FIG. 4 is a plan view of a display in a control panel of the printing apparatus, showing a case that a color mode is selected;
FIG. 5 is a plan view of the display in the control panel, showing a case that a 4-cartridge monochrome mode is selected;
FIG. 6 is a plan view of a display in the control panel, showing a case that a 1-cartridge monochrome mode is selected;
FIG. 7 is a plan view of a test pattern image printed by a printing apparatus according to a second embodiment of the invention, when a 4-cartridge monochrome mode is selected;
FIG. 8 is a plan view of the test pattern image, showing a case that a residual toner amount in a toner cartridge loaded in a cartridge chamber for cyan is lower than a prescribed value; and
FIG. 9 is a plan view of a display in a control panel of a related-art printing apparatus.
DETAILED DESCRIPTION OF THE EMBODIMENTS
Embodiments of the invention will be described below in detail with reference to the accompanying drawings.
A printing apparatus 10 according to a first embodiment receives a print request from a host computer which is not shown or a camera device which is not shown, and operates in response to the request. As shown in FIG. 1 , the apparatus comprises a control panel 11 , a print engine 12 , and a controller 13 .
The control panel 11 is a device which obtains from the operator instructions related to a process to be executed, and which is disposed in the upper face of the printing apparatus 10 . As shown in FIG. 2 , the upper face of the control panel 11 comprises interface components which are required in operation, such as an LCD 111 , buttons 112 , and LEDs 113 . The interface components 111 to 113 are attached to the casing, and connected to a control circuit on a board in the control panel, via signal lines which are not shown. The board is connected to the controller 13 shown in FIG. 1 via a cable which is not shown.
The print engine 12 is a mechanism which actually performs printing on a sheet. As described later in detail, the print engine 12 can perform color printing and monochrome printing.
The controller 13 performs a process of controlling the driving of the print engine 12 on the basis of the print request from the host computer or camera device which is not shown, and various other processes on the basis of instructions obtained through the control panel 11 .
As principal components, the controller 13 comprises on a printed circuit board a network interface 131 , a USB interface 132 , a RAM 133 , a video signal generator 134 , a ROM 135 , a memory controller 136 , an interface 137 , an EEPROM 138 , and a CPU 139 .
The network interface 131 is a unit which receives the print request from the host computer which is not shown, and specifically a communication interface port such as a LAN board. The USB interface 132 is a unit which receives the print request from the camera device which is not shown, and specifically a communication interface port which controls data communication in accordance with the USB standard. The camera device is a device which can obtain image data of a still picture, and which is provided with a USB port, and specifically a digital still camera, a digital video camera, a camera-equipped mobile phone, or the like.
The RAM 133 is a memory which is used for temporarily storing the print request transmitted from the host computer or camera device which is not shown, and also for, based on the print request, producing print data to be supplied to the print engine 12 .
The video signal generator 134 converts the print data to be supplied to the print engine 12 , to an electric signal the form of which can be processed by a scanning unit 123 (see FIG. 3 ) in the print engine 12 .
The ROM 135 is a nonvolatile memory which stores programs for controlling the printing apparatus 10 , and font data that are used when print data are produced from the print request.
The memory controller 136 is a circuit for controlling: DMA transfer of the print request which is received from the host computer or camera device which is not shown, via the network interface 131 or the USB interface 132 ; that of the print data in the RAM 133 to the video signal generator 134 ; and writing of the programs and data in the ROM 135 into the RAM 133 .
The interface 137 controls transmission and reception of various signals with respect to units in the control panel 11 , and those of various signals with respect to units in the print engine 12 .
The EEPROM 138 is a rewritable memory for recording various settings of printing, and various information relating to use results. The various information relating to use results includes the following information for each of toners which will be described later: the residual toner amount in a toner cartridge 21 ; an average of ratios of the number of dots which are actually printed to the total dot number of one page; and an average of the number of dots which are required in consumption of 1% of the toner amount.
The CPU 139 is a processor which integrally controls various portions in accordance with the programs installed in the ROM 135 , thereby conducting a print control process which causes the print engine 12 to perform printing in accordance with the print request transmitted from the host computer or camera device which is not shown, and a process in which instructions for a process to be executed are obtained from the user through an operation on the control panel 11 .
As shown in FIG. 3 , the print engine 12 incorporates a photosensitive drum 121 , a charging unit 122 , the scanning unit 123 , a rotary developing unit 124 , a transfer belt unit 125 , a secondary transferring unit 126 , and a fusing unit 127 .
The photosensitive drum 121 is a cylindrical drum in which a photoconductive material is deposited on the surface, and which is rotated about the central axis.
The charging unit 122 removes (discharges) static electricity possessed by the surface of the photosensitive drum 121 , removes (cleans) toners adhering to the surface by a rubber blade or the like, and gives (charges) static electricity to the surface.
The scanning unit 123 scans the surface of the photosensitive drum 121 with a laser beam which is on/off modulated on the basis of the print data, to partially remove static electricity on the surface, thereby forming an electrostatic latent image. A signal for on/off modulating the laser beam is supplied from the video signal generator 134 .
The rotary developing unit 124 conveys toner from the toner cartridge 21 to the photosensitive drum 121 in order to cause toner to adhere to the surface of the photosensitive drum 121 . The configuration of the rotary developing unit 124 will be described later in detail.
The transfer belt unit 125 rotates a transfer belt which serves as an intermediate transfer medium (intermediate member), and which receives toner from the surface of the photosensitive drum 121 . When color printing using color components of CMYK is to be performed, the transfer belt unit 125 performs a primary transfer process in which a toner image is transferred from the photosensitive drum 121 to the transfer belt in a superposed manner, that is, four times of transfer operations are performed for an image of one page.
The secondary transferring unit 126 is a unit which, when a toner image of one page is transferred to the transfer belt of the transfer belt unit 125 , secondarily transfers the toner image to a printing sheet. The secondary transferring unit 126 comprises a clutch roller which cooperates with one roller for rotating the transfer belt to clamp the transfer roller and the sheet. When secondary transfer is not performed, the clutch roller is caused to idly rotate.
The fusing unit 127 heats toner attached to the sheet as a result of the secondary transfer, thereby fusing the toner to the sheet.
The rotary developing unit 124 incorporates a cartridge rotor 124 rt , a CSIC reader 124 rd , a C-developing roller 124 dc , an M-developing roller 124 dm , a Y-developing roller 124 dy , a K-developing roller 124 dk , and a motor driver 124 md.
The cartridge rotor 124 rt has a framework structure which is substantially cylindrical, and is rotatable about the central axis. Inside the cartridge rotor 124 rt , cartridge chambers 124 C, 124 M, 124 Y, 124 K having a structure for loading the toner cartridge 21 which is substantially columnar are formed respectively at four symmetrical positions which have the central axis of the rotor as an axis of symmetry.
Each of the cartridge chambers 124 C, 124 M, 124 Y, 124 K comprises a sensor which, when the toner cartridge 21 is loaded, detects the residual amount of toner in the toner cartridge 21 . Information indicative of the residual toner amount detected by the sensor is transmitted from the sensor to the CPU 139 through the interface 137 .
The CSIC reader 124 rd reads in a non-contact manner information recorded in a CSIC (not shown) which is installed on each of the toner cartridges 21 loaded in the cartridge chambers 124 C, 124 M, 124 Y, 124 K. The CSIC reader is placed in the vicinity of the cartridge rotor 124 rt . The CSIC which is not shown stores information related to the color of toner charged in the toner cartridge 21 on which the CSIC is installed. The information read from the CSIC which is not shown is transmitted as color identifying information from the CSIC reader 124 rd to the CPU 139 through the interface 137 .
The four developing rollers 124 dc , 124 dm , 124 dy , 124 dk are devices which visualize an electrostatic latent image formed in the surface of the photosensitive drum 121 , and incorporated at symmetrical positions in the four cartridge chambers 124 C, 124 M, 124 Y, 124 K respectively. Specifically, each of the developing rollers 124 c , 124 dm , 124 dy , 124 dk provides static electricity to toner which is in the toner cartridges 21 loaded in the corresponding one of the cartridge chambers 124 C, 124 M, 124 Y, 124 K, and which is in contact with the surface of the roller, thereby causing the toner to adhere to the surface, and rotates about the central axis to transport the toner on the surface to the photosensitive drum 121 .
The motor driver 124 md rotates the cartridge rotor 124 rt , and controls the rotation. Specifically, the motor driver 124 md receives information designating one of the four developing rollers 124 dc , 124 dm , 124 dy , 124 dk , from the CPU 139 through the interface 137 , and then rotates the cartridge rotor 124 rt via a motor and gear mechanism which are not shown, while monitoring the position the cartridge rotor 124 rt by a position sensor which is not shown, whereby the designated developing roller is located at a position in the vicinity of the photosensitive drum 121 .
Although not shown, the thus configured rotary developing unit 124 comprises a replacement port through which the toner cartridges 21 are removed from or inserted into the cartridge chambers 124 C, 124 M, 124 Y, 124 K. The replacement port which is not shown has a size which allows one toner cartridge 21 to be inserted into the chamber. In order to access each of the four cartridge chambers 124 C, 124 M, 124 Y, 124 K, an operation of locating the cartridge chamber at the position of the replacement port which is not shown must be conducted. The motor driver 124 md which receives instructions from the CPU 139 rotates the cartridge rotor 124 rt at a 90 degrees increment, thereby conducting this operation.
The printing apparatus 10 which is configured as described above operates in one of printing modes including a color mode, a 4-cartridge monochrome mode, and a 1-cartridge monochrome mode. The color mode is a printing mode where color printing is performed with using toners of color components of CMYK, and the 4-cartridge monochrome mode and the 1-cartridge monochrome mode are printing modes where black and white or monochrome printing is performed with using toners of a color component of K.
The printing mode in which the printing apparatus 10 operates depends on the color combination of toners of the toner cartridges 21 which are loaded respectively in the four cartridge chambers 124 C, 124 M, 124 Y, 124 K of the rotary developing unit 124 .
Specifically, when four toner cartridges 21 respectively having toners of CMYK are loaded in the four cartridge chambers 124 C, 124 M, 124 Y, 124 K, the CPU 139 of the printing apparatus 10 determines that the printing mode is switched to the color mode, sets the printing apparatus 10 to a state where the printing apparatus can operate in the color mode, and initializes information which is recorded in the EEPROM 138 as information relating to use results.
When four toner cartridges 21 having toners of K are loaded respectively in the four cartridge chambers 124 C, 124 M, 124 Y, 124 K, the CPU 139 determines that the printing mode is switched to the 4-cartridge monochrome mode, sets the printing apparatus 10 to a state where the printing apparatus can operate in the 4-cartridge monochrome mode, and initializes information which is recorded in the EEPROM 138 as information relating to use results.
When one toner cartridge 21 having a toner of K remains to be loaded in the cartridge chamber 124 K for K and the other toner cartridges 21 are removed from the cartridge chambers 124 C, 124 M, 124 Y, the CPU 139 determines that the printing mode is switched to the 1-cartridge monochrome mode, sets the printing apparatus 10 to a state where the printing apparatus can operate in the 1-cartridge monochrome mode, and initializes information which is recorded in the EEPROM 138 as information relating to use results.
The ROM 135 stores correspondence information which, for each of the printing modes, defines correspondences between toner color(s) used in the printing mode and the cartridge chambers. On the bases of the correspondence information, the CPU 139 determines whether toner cartridges 21 of adequate colors are loaded in the cartridge chambers 124 K, 124 C, 124 M, 124 Y or not, and switches the printing mode when adequate toner cartridges 21 are loaded.
In the case where the printing mode is changed to the color mode as a result of the printing mode switching process, upon receiving a print request, the CPU 139 controls the print engine 12 so as to conduct the operation of primary-transferring the toner image from the photosensitive drum 121 to the transfer belt, four times for each image of one page as described above. Namely, the CPU 139 controls the cartridge rotor 124 rt so as to make one rotation for one printing sheet.
In the case where the printing mode is changed to the 1-cartridge monochrome mode, upon receiving a print request, the CPU 139 controls the print engine 12 so as to use only the cartridge chamber 124 K for K. In the 1 cartridge monochrome mode, the cartridge chambers 124 C, 124 M, 124 Y which are not for K are not used.
In the case where the printing mode is changed to the 4-cartridge monochrome mode, upon receiving a print request, the CPU 139 controls the print engine 12 so as to use one of the four cartridge chambers 124 K, 124 C, 124 M, 124 Y.
Specifically, in accordance with a predetermined program in the ROM 135 , the CPU 139 controls the print engine 12 so as to switch the cartridge chamber used in printing (the cartridge chamber placed in the vicinity of the photosensitive drum 121 ) to another one, every time when printing is performed on 15 sheets.
After printing is performed on 15 sheets, the CPU 139 performs a process of rotating the cartridge rotor 124 rt by 90 degrees to switch the cartridge chamber to the next one. At this time, the CPU 139 judges whether the cartridge chamber to be switched as the next used one is in an enabled state or not, on the basis of flag information which is recorded in the EEPROM 138 as information of the cartridge chamber itself.
When the flag information defines that the cartridge chamber is in the enabled state, the CPU 139 causes the cartridge chamber to remain to be placed in front of the photosensitive drum 121 . By contrast, when the flag information defines that the cartridge chamber is in a disabled state, the cartridge rotor 124 rt is again rotated by 90 degrees, thereby further performing the process of switching the cartridge chamber to the next one.
When the process is performed repeatedly as required, the cartridge chamber which is defined to be in the enabled state by the flag information is placed in the vicinity of the photosensitive drum 121 , and the CPU 139 is then prepared for the next print request.
Next, the contents displayed in the LCD 111 of the control panel 11 will be described.
The CPU 139 outputs information to be displayed on the LCD 111 of the control panel 11 to the control panel 11 through the interface 137 . The board (not shown) in the control panel 11 produces screen data on the basis of the information supplied from the CPU 139 , and causes the LCD 111 to always display the screen based on the screen data.
FIG. 4 shows an example of the display screen of the LCD 111 in the color mode. The display screen of the LCD 111 of the control panel 11 is partitioned into upper and lower two areas. The upper area is a status display area where the operation status of the printing apparatus 10 is shown by a letter string. On the other hand, the lower area is an accessory status information display area where the residual toner amounts of the toner cartridges 21 , and the size and residual amount of sheets of a sheet cassette are shown.
In the accessory status information display area, four vertical bar graphs are displayed in parallel, and letters “K”, “C”, “M”, and “Y” are displayed above the four bar graphs, respectively.
The bar graph below the letter “K” indicates the residual toner amount of the toner cartridge 21 for K which is set in the rotary developing unit 124 . The letter “K” serves as color identifying information for identifying the color component of the toner the residual amount of which is indicated by the bar graph, and also as position identifying information for identifying the cartridge chamber 124 K for K in which the toner cartridge 21 for K is set.
Similarly, the bar graphs below the letters “C”, “M”, and “Y” indicate the residual toner amounts of the toner cartridges 21 for C, M, and Y which are set in the rotary developing unit 124 , respectively. Each of the letters “C”, “M”, and “Y” serves as color identifying information for identifying the color component of the toner the residual amount of which is indicated by the corresponding bar graph, and also as position identifying information for identifying the cartridge chamber 124 C, 124 M, or 124 Y In which the toner cartridge 21 for C, M, or Y is set.
In this way, the four bar graphs which are displayed on the screen correspondingly with the letters “K”, “C”, “M”, and “Y” enable the operator to easily determine which one of the toner cartridges 21 is to be replaced with a new one.
The letters “K”, “C”, “M”, and “Y” are displayed on the basis of the information read by the CSIC reader 124 rd , and the bar graphs are displayed on the basis of the residual amount information read by the sensors disposed in the cartridge chambers 124 C, 124 M, 124 Y, 124 K.
Every time when a printing process is performed on one printing sheet, the CPU 139 measures the residual toner amounts in the toner cartridges 21 by the sensors, and updates the sizes of the bar graphs on the screen displayed in the LCD 111 of the control panel 11 . Namely, the residual toner amounts indicated by the bar graphs are immediately updated.
Furthermore, the CPU 139 monitors switching of the printing mode in accordance with a predetermined program in the ROM 135 . When it is detected that the printing mode is switched from the color mode or the 1-cartridge monochrome mode to the 4-cartridge monochrome mode, the CPU 139 instructs the control panel 11 to change the color identifying information and position identifying information which are displayed on the screen in the LCD 111 of the control panel 11 .
FIG. 5 shows an example of the display screen of the LCD 111 in the 4-cartridge monochrome mode. In the same manner as the color mode, four vertical bar graphs are displayed in the accessory status information display area in the screen displayed in the LCD 111 of the control panel 11 . However, the letter “K” is indicated above each of the four bar graphs, and the letters “K”, “C”, “M”, and “Y” are indicated between the letters “K” and the bar graphs.
The bar graph designated by “K” and “K” indicates the residual toner amount of the toner cartridge 21 for K which is set in the cartridge chamber 124 K for K of the rotary developing unit 124 . The upper letter “K” serves as color identifying information for identifying the color component of the toner the residual amount of which is indicated by the bar graph, and the lower letter “K” serves as position identifying information for identifying the cartridge chamber 124 K for K in which the toner cartridge 21 for K is set.
The bar graph designated by “K” and “C” indicates the residual toner amount of the toner cartridge 21 for K which is set in the cartridge chamber 124 C for C of the rotary developing unit 124 . The upper letter “K” serves as color identifying information for identifying the color component of the toner the residual amount of which is indicated by the bar graph, and the lower letter “C” serves as position identifying information for identifying the cartridge chamber 124 C for C in which the toner cartridge 21 for K is set.
Similarly, the bar graph designated by “K” and “M” and that designated by “K” and “Y” indicate the residual toner amounts of the toner cartridges 21 for K which are set in the cartridge chambers 124 M, 124 Y for M and Y of the rotary developing unit 124 , respectively. The upper letters “K” serve as color identifying information for identifying the color component of the toners the residual amounts of which are indicated by the bar graphs, and the lower letters “M” and “Y” serve as position identifying information for identifying the cartridge chambers 124 M, 124 Y for M and Y in which the toner cartridges 21 for K are set.
In this way, the four bar graphs which are displayed on the screen correspondingly with the letters “KK”, “KC”, “KM”, and “KY” enable the operator to easily determine which one of the toner cartridges 21 is to be replaced with a new one.
In the 4-cartridge monochrome mode, a further one bar graph is displayed adjacent to the four bar graphs in the accessory status information display area. The bar graph indicates the average of the residual toner amounts of the four toner cartridges 21 , so that it is possible to know the whole residual toner amount of the four toner cartridges 21 . Letters “A” and “V” are displayed above the bar graph indicating the average of the residual toner amounts, and “AV” shows that the bar graph indicates the average of the residual toner amounts.
When it is detected that the printing mode is switched from the color mode or the 4-cartridge monochrome mode to the 1-cartridge monochrome mode, the CPU 139 instructs the control panel 11 to change the color identifying information and position identifying information which are displayed on the screen in the LCD 111 of the control panel 11 .
FIG. 6 shows an example of the display screen of the LCD 111 in the 1-cartridge monochrome mode. Unlike in the color mode and the 4-cartridge monochrome mode, only one vertical bar graph is displayed in the accessory status information display area in the screen displayed in the LCD 111 of the control panel 11 . The letter “K” is indicated above the bar graph.
The one bar graph indicates the residual toner amount of the toner cartridge 21 for K which is set in the rotary developing unit 124 . The letter “K” serves as color identifying information for identifying the color component of the toner the residual amount of which is indicated by the bar graph, and also as position identifying information for identifying the cartridge chamber 124 K for K in which the toner cartridge 21 for K is set.
In this way, the one bar graph which is displayed on the screen correspondingly with the letter “K” enables the operator to easily determine whether the toner cartridges 21 is to be replaced with a new one.
As described above, according to the printing apparatus 10 of the embodiment, even when the combination of toners charged in the toner cartridges 21 which are set in the rotary developing unit 124 is changed, respective residual toner amounts of the toner cartridges 21 used in the printing mode are displayed in the form of bar graphs on the LCD 111 of the control panel 11 . Moreover, an alphabetical letter shows the residual toner amount of the color which is indicated by each of the bar graphs, and the cartridge chamber to which the toner cartridge 21 the residual toner amount of which is indicated is set. Therefore, the operator is not confused.
In the above-described embodiment, the alphabetical characters “K”, “C”, “M”, and “Y” are used as the color identifying information and the position identifying information which are to be displayed on the LCD 111 . However, symbols indicating such colors may be used. Alternatively, the bar graphs themselves are colored in KCMY, respectively, so that the color identifying information and the position identifying information are indicated by the colors of the bar graphs.
Next, a second embodiment of the invention will be described. Similar components to those in the first embodiment will be designated by the same reference numerals and repetitive explanations for those will be omitted.
In the embodiment, the cartridge chambers 124 K, 124 C, 124 M, 124 Y are not provided with a sensor which directly detects the residual toner amount in the corresponding toner cartridge 21 .
As described above in connection with the first embodiment, as information relating to use results, the EEPROM 138 stores: an average of ratios of the number of dots which are actually printed to the total dot number of one page; an average of the number of dots which are required in consumption of 1% of the toner amount; and the residual toner amounts in the toner cartridges 21 which are set in the rotary developing unit 124 . These sets of information are calculated by the CPU 139 in accordance with a predetermined program in the ROM 135 , every time when a printing process is performed on one printing sheet. Particularly, the information related to the residual toner amounts in the toner cartridges 21 is obtained on the basis of the toner use amount calculated from the number of dots which are actually printed, and is not obtained by direct detection of the actual residual toner amounts in the toner cartridges 21 by a sensor or the like.
In accordance with another program in the ROM 135 different form the above-mentioned program, the CPU 139 monitors the residual toner amounts obtained from the actually printed dot number. When the residual toner amount of one of the toner cartridges 21 falls below a predetermined threshold, the CPU starts the process described below.
From the ROM 135 which stores image data respectively corresponding to the cartridge chambers 124 K, 124 C, 124 M, 124 Y, the CPU 139 reads the image data into the RAM 133 . Thereafter, the CPU causes the cartridge chamber 124 K for K to be placed in front of the photosensitive drum 121 , and the image data corresponding to the cartridge chamber 124 K for K to be supplied from the RAM 133 to the video signal generator 134 . When the toner cartridge 21 is loaded in the cartridge chamber 124 K for K at this time, a toner image is formed on the photosensitive drum, and the toner image is primary-transferred to the transfer belt.
Then, the CPU 139 causes the cartridge chamber 124 C for C to be placed in front of the photosensitive drum 121 , and the image data corresponding to the cartridge chamber 124 C for C to be supplied from the RAM 133 to the video signal generator 134 . When the toner cartridge 21 is loaded in the cartridge chamber 124 C for C at this time, a toner image is formed on the photosensitive drum, and the toner image is primary-transferred to the transfer belt.
Furthermore, the CPU 139 executes a process similar to the above on the cartridge chamber 124 M for M and the cartridge chamber 124 Y for Y.
In the print engine 12 , the toner images transferred to the transfer belt are secondary-transferred to a printing sheet by the secondary transferring unit 126 , and then fusion-bonded to the printing sheet by the fusing unit 127 . As a result, the printing sheet on which the test pattern image is printed is discharged from the printing apparatus 10 .
FIG. 7 shows an example of the test pattern image which is printed on a printing sheet by the print engine 12 in the color mode or the 4-cartridge monochrome mode. It is assumed that the vertical direction of this figure coincides with that of the test pattern image. In each of the vicinity of the left edge, the middle portion, and the vicinity of the right edge of the test pattern image, a combination of four linear reference images and letters “K”, “C”, “M”, and “Y” is placed.
Among the four linear reference images, the first reference image is an image colored only by the same color as the toner of the toner cartridge 21 loaded in the cartridge chamber 124 K Above the reference image, letter “K” is placed as identifying information for identifying the cartridge chamber 124 K in which the toner cartridge 21 is loaded. The letter “K” and the reference image corresponding to the letter are reproduced on the basis of the image data which are recorded in the ROM 135 as data corresponding to the cartridge chamber 124 K for K.
The second reference image is an image colored only by the same color as the toner of the toner cartridge 21 loaded in the cartridge chamber 124 C. Above the reference image, letter “C” is placed as identifying information for identifying the cartridge chamber 124 C in which the toner cartridge 21 is loaded. The letter “C” and the reference image corresponding to the letter are reproduced on the basis of the image data which are recorded in the ROM 135 as data corresponding to the cartridge chamber 124 C for C.
Similarly, each of the third and fourth reference images is an image colored only by the same color as the toner of the toner cartridge 21 loaded in the cartridge chamber 124 M or 124 Y Letters “M” and “Y” are placed above the reference images, respectively. The letter “M” and the reference image corresponding to the letter are reproduced on the basis of the image data which are recorded in the ROM 135 as data corresponding to the cartridge chamber 124 M for M. The letter “Y” and the reference image corresponding to the letter are reproduced on the basis of the image data which are recorded in the ROM 135 as data corresponding to the cartridge chamber 124 Y for Y.
Since the test pattern image is configured in this way, each of the four linear reference images is printed with using toner of the toner cartridge 21 loaded in the corresponding cartridge chamber. When the printing mode is the color mode, therefore, four lines respectively colored in KCMY are drawn in each of the vicinity of the left edge, the middle portion, and the vicinity of the right edge of the printing sheet. When the printing mode is the 4-cartridge monochrome mode, four lines colored in K are drawn in each of the vicinity of the left edge, the middle portion, and the vicinity of the right edge of the printing sheet.
For example, the case where the residual toner amount of the toner cartridge 21 loaded in the cartridge chamber 124 C for C is actually reduced in the 4-cartridge monochrome mode will be considered. As shown in FIG. 8 , on the printing sheet on which the test pattern image is printed, only the density of the reference image corresponding to letter “C” is lowered, and the reference images corresponding to letters “K”, “M”, and “Y” remain to have the normal density.
On the other hand, even in the case where the residual toner amounts recorded in the EEPROM 138 fall below the above-mentioned predetermined threshold, when the actual residual toner amounts are large, all the reference images in the test pattern image printed on the printing sheet remain to have the normal density.
The printing apparatus 10 of the embodiment serves as described above. Therefore, the user can refer the test pattern image on the printing sheet which is automatically printed out by the printing apparatus 10 when the residual toner amount falls below the predetermined threshold, whereby the user is enabled to easily determine the presence or absence of a toner cartridge 21 in which the residual toner amount is actually reduced, and the cartridge chamber in the rotary developing unit 124 in which the residual toner amount-reduced toner cartridge 21 is loaded.
Namely, when the user finds a reference image in which the density is lowered in the test pattern image on the printing sheet, the user can know that the toner amount of the toner cartridge 21 in the cartridge chamber indicated by the letter corresponding to the reference image in which the density is lowered is reduced.
Although it is not specifically shown in the accompanying drawings, in the 1-cartridge monochrome mode, three linear reference images colored in K are printed in the vicinity of the left edge, the middle portion, and the vicinity of the right edge of a printing sheet, respectively. This is produced because of the following reason. Since the toner cartridges 21 are not loaded in the cartridge chambers 124 C, 124 , 124 Y for C, M, and Y, the reference images and chamber identifying information based on the image data corresponding to the cartridge chambers 124 C, 124 M, 124 Y are not visualized. Also in the 1-cartridge monochrome mode, when a part or whole of the reference images on the printing sheet is blurred or discolored, the user can know that the toner amount of the toner cartridge 21 in the cartridge chamber 124 K for K is reduced.
In this embodiment, when, in the residual toner amounts recorded in the EEPROM 138 , the residual toner amount of one of the toner cartridges 21 falls below the predetermined threshold, the test pattern image is printed. This is because the toner is wastefully used if the test pattern image is printed while a sufficient amount of toner remains.
In the embodiment, when one of the residual toner amounts recorded in the EEPROM 138 falls below the predetermined threshold, the test pattern image is printed. However, a sensor for detecting the residual toner amount in the toner cartridge 21 may be attached to each of the cartridge chambers 124 K, 124 C, 124 M, 124 Y, and the test pattern image may be printed when one of the residual toner amounts detected by the sensors falls below a predetermined threshold. In this case, even when the accuracies of the residual toner amount detectors are somewhat poor, the user can easily determine whether the toner cartridge 21 in which the amount of toner is actually reduced, based on the test pattern image on a printing sheet.
In the embodiment, as shown in FIGS. 7 and 8 , the combination of reference images and letters is printed in each of the three places or the vicinity of the left edge, the middle portion, and the vicinity of the right edge of the printing sheet, because it can be determined whether the distribution of toner in the toner cartridge 21 is even or not. Namely, when the density of the reference image(s) of the same cartridge chamber in one or two of the three places is lowered and that of the reference image(s) of the other place(s) remains unchanged, the user can determine that the distribution of toner in the toner cartridge 21 which is loaded in the cartridge chamber is uneven.
In the embodiment, alphabetical letters “K”, “C”, “M”, and “Y” are correspondent to the reference images as the chamber identifying information for identifying the cartridge chambers 124 K, 124 C, 124 M, 124 Y. However, these letters are not necessary because of the following reasons. In the color mode, the colors themselves which color the reference images function as the chamber identifying information for identifying the cartridge chambers, In the 4-cartridge monochrome mode, when the arrangement order of the reference images and the order of the cartridge chambers are once defined, the arrangement order of the reference images functions as the chamber identifying information for identifying the cartridge chambers.
The user recognizes the cartridge chamber where the toner cartridge 21 in which the residual toner amount is actually reduced is loaded, as a result of the printing of the test pattern image. In order to prevent the toner cartridge 21 in the cartridge chamber from being used in printing, thereafter, the user sets the cartridge chamber to be disabled from being used.
Specifically, in the example of FIG. 8 , the user operates the control panel 11 to change the flag information of the cartridge chamber 1240 for C from the enabled state to the disabled state. The changing operation causes the flag information which is recorded in the EEPROM 138 as information of the cartridge chamber 124 C for C, to be overwritten from “1” indicative of the enabled state to “0” indicative of the disabled state.
As a result, in the 4-cartridge monochrome mode, the group of cartridge chambers which can be switched every time when printing is performed on 15 sheets is configured by the three cartridge chambers 124 K, 124 M, 124 Y for K, M, and Y. The cartridge chamber 124 C for C is eliminated from the group of cartridge chambers.
In this embodiment, three cartridge chambers can be set at the maximum to the disabled state. When three cartridge chambers are set to the disabled state, only the toner cartridge 21 loaded in the remaining single cartridge chamber supplies toner of K In this case, namely, the embodiment operates in the same manner as in the 1-cartridge monochrome mode.
As described above, according to the printing apparatus 10 of the embodiment, in the 4-cartridge monochrome mode in which toner of the same color is loaded in the cartridge chambers 124 K, 124 C, 124 M, 124 Y, the enabled cartridge chamber(s) and the disabled cartridge chamber(s) are defined by the flag information in the EEPROM 138 , and the flag information can be changed by the user. Therefore, the user can cause the test pattern image to be printed, check a cartridge chamber where a toner cartridge in which the residual toner amount is reduced is loaded, and thereafter set the cartridge chamber to the disabled state. Even when a residual toner amount detector is not installed, therefore, toner in only a toner cartridge in which toner remains can be used in printing.
The above-described printing apparatus may be configured so that, when replacement of the toner cartridge 21 is conducted on the cartridge chamber which is defined to be in the disabled state by the flag information in the EEPROM 138 , the contents of the flag information corresponding to the cartridge chamber is reset to the enabled state.
Specifically, with using a sensor (not shown) for detecting opening and closing of an outer cover which covers the replacement port (not shown), and the CSIC reader 124 rd , the CPU 139 of the printing apparatus 10 monitors whether replacement of the toner cartridge 21 is performed on one of the cartridge chambers. When replacement of the toner cartridge 21 is performed on one of the cartridge chambers, the CPU determines whether the flag information which is recorded in the EEPROM 138 as information corresponding to the cartridge chamber defines the disabled state or not. If the flag information defines the disabled state, the CPU 139 resets the flag information by overwriting the contents to those indicative of the enabled state.
With this configuration, when the toner cartridge 21 is replaced because the residual toner amount is reduced, it is possible to save the trouble of manually (on the control panel 11 ) resetting to the enabled state the contents of the flag information relating to the cartridge chamber on which the replacement of the toner cartridge 21 is performed.
In the above embodiments, the developing sections are incorporated in a rotor so that one of the developing sections is selectively confronted with the photosensitive drum. However, the printing apparatus of the invention may be configured such that a plurality of developing sections may be arranged around a single photosensitive drum so that developed toner images are superposed on the photosensitive drum. Alternatively, the printing apparatus may be configured such that a plurality of developing sections are disposed on respectively corresponding photosensitive drums to configure a so-called tandem print engine.
Although the present invention has been shown and described with reference to specific preferred embodiments, various changes and modifications will be apparent to those skilled in the art from the teachings herein. Such changes and modifications as are obvious are deemed to come within the spirit, scope and contemplation of the invention as defined in the appended claims. | A plurality of chambers are adapted to accommodate a plurality of cartridges each containing toner to be used for printing. A mode changer is operable to change an operation mode of the printing apparatus in accordance with a combination of respective colors of toner in the cartridges accommodated in the chambers. A first detector is operable to detect a residual amount of toner in each of the cartridges. A second detector is operable to detect the respective colors of toner in the cartridges when the operation mode is changed. A controller is operable to generate an image data including a plurality of first identifiers each indicative of the residual amount of toner in one of the cartridges and a plurality of second identifiers each indicative of one of the colors of toner and associated with one of the first identifiers. A display is adapted to display the image data. | 6 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a hatch latching system, and, more particularly, to a hatch latching system for a slideable hatch.
2. Description of the Related Art
Bulk cargo carrying railroad cars often have openings along the top that are opened for the loading of materials and closed for transportation. Many bulk cargo railroad cars are utilized without any cover system. It is desirous to protect the materials carried in the interior of the railroad car from damage, which may be caused by weather or other environmental sources, such as particulate or biological material contained in the air. It is also desirous to prevent the bulk material from being dissipated by transportation due to the movement of air over the bulk material while it is in transit.
During the filling of the railcar, it is desirable to have the top of the railcar open so as to provide an easy way of loading the bulk material cargo from a delivering device, such as an overhead hopper. It is known to have railroad car hatches that are hinged and which are opened by releasing the latches on one side and pivoting the covers to the other side, thereby exposing a portion of the top of the railroad car so that the bulk cargo material may be loaded therein. It is also known to utilize latch systems that require the connection of the hatch to the framework or other structural elements surrounding the hatch. This is typically accomplished by having some portion extend from the framework to the hatch or from the hatch to the framework to engage in an interference type connection, thereby latching the hatch in place.
What is needed in the art is a hatch latching system that holds the hatch in position yet is easily released for opening or closing of the hatch.
SUMMARY OF THE INVENTION
The present invention is directed to a hatch latching system for a sliding hatch and, particularly, for a hatch system associated with a railcar system.
The invention consists, in one form thereof, of a railcar hatch cover latching system including a sliding mechanism and a latching apparatus. The sliding mechanism is attached to a moveable portion of the hatch cover. The latching apparatus is associated with the hatch cover. The latching apparatus includes a biased assembly, a bar, and at least one profiled stop. The bar extends through the biased assembly. The biased assembly is configured to allow the bar to pass through the biased assembly with a first force requirement. The at least one profiled stop is positioned on the bar to encounter the biased assembly and to thereby require a second force requirement to move the bar past the at least one profiled stop. The second force is greater than the first force.
An advantage of the present invention is that the latching system is primarily connected to the moveable hatch for easy assembly/disassembly.
Another advantage of the present invention is that movements of the slideable hatch in directions other than the latching direction do not substantially effect the latching force applied by the biasing assembly.
Another advantage of the present invention is that an automated opening and closing process of a passive nature can be utilized to overcome the latching force to thereby slide the hatch cover to either an open or a closed position.
BRIEF DESCRIPTION OF THE DRAWINGS
The above-mentioned and other features and advantages of this invention, and the manner of attaining them, will become more apparent and the invention will be better understood by reference to the following description of embodiment of the invention taken in conjunction with the accompanying drawings, wherein:
FIG. 1 is a perspective view of a railcar having an embodiment of the hatch latching system of the present invention with a closing device suspended thereover;
FIG. 2 is a partial cross section of the latching system of FIG. 1 taken along lines 2 - 2 of FIG. 1 ;
FIG. 3 is the latching system of FIG. 2 with the hatch cover shown in an open position;
FIG. 4 is another partial cross section showing details of the latching system of FIGS. 1-3 ;
FIG. 5 is another partial cross section of the latching system of FIG. 4 with the latching system being opened past a profiled stop;
FIG. 6 is a partially exploded view of the biasing mechanism of the hatch latching system of FIGS. 1-5 showing it in conjunction with a bracket that is connected to the lower portion of the hatch cover; and
FIG. 7 is a view of a distal end of the hatch cover latching system of FIGS. 1-6 .
Corresponding reference characters indicate corresponding parts throughout the several views. The exemplifications set out herein illustrates one embodiment of the invention and such exemplifications are not to be construed as limiting the scope of the invention in any manner.
DETAILED DESCRIPTION OF THE INVENTION
Referring now to the drawings, and more particularly to FIG. 1 , there is shown a railcar system 10 , including a railcar 12 , moving by a closing system 14 in direction 16 . Cover 18 is being closed as railcar 12 moves in direction 16 by the interaction of elements of the railcar cover and closing system 14 . Cover 18 includes sliding hatch covers 20 with protrusions 22 , which may be in the form of rollers 22 , which encounter structural portions of closing system 14 , thereby moving covers 20 toward each other as railcar 12 moves in direction 16 .
Now, additionally referring to FIGS. 2-7 , there is illustrated latching system 24 that is connected primarily to sliding hatch covers 20 with a bracket 28 connected to cover lower portion 26 . Bracket 28 receives a portion of latching system 24 therein, allowing vertical movement in a sliding manner of latching system 24 therein, but restraining lateral movement of the portion of the latching system contained therein.
Latching system 24 additionally includes a biased assembly 30 , a bar assembly 32 , and an alignment assembly 34 . Alignment assembly 34 includes a male portion 36 and a female portion 38 that interact with each other as covers 20 close. In the embodiment illustrated, there are two latching systems 24 for each rail cover 20 , one having a male portion 36 and the other having a female portion 38 . As can be seen in the figures this allows each railcar 20 to be identically configured and, since one is rotated at 180° relative to the other, the interaction of portions 36 and 38 allow for the engagement of covers 20 in a self-aligning manner as covers 20 are closed. The male portion 36 has a tapered feature allowing engagement with the female portion 38 to thereby assure alignment between covers 20 .
Bar assembly 32 additionally includes a bar 40 having profiled stops 42 connected thereto. Profiled stops 32 are illustrated as having a rounded, triangular profile. However, other profiles are other contemplated and, although symmetrically shown and is utilized as such in the main embodiment, non-symmetrical shapes, such as other triangular configurations and curvilinear shapes are also contemplated. The shape of profiled stops 42 interact with bias assembly 30 to cause the force required to move bar 40 through bias assembly 30 to vary depending upon the interaction of the biasing mechanism, the surface encountering profiled stops 42 , as well as the shape of profiled stops 42 . Profiled stops 42 are illustrated as being on the topside of bar 40 , although other configurations are also contemplated. Generally, profiled stops 42 will have to be oriented in order to properly interact with the biasing features of bias assembly 30 .
Biased assembly 30 includes a biased cassette 44 having a lower bearing surface 46 , an upper bearing surface 48 , springs 50 , and an adjustment mechanism 52 . Biased cassette 44 is slid into bracket 28 , which allows cassette 44 to move up and down in bracket 28 as various vibrations and movements of railcar 12 occurs without significantly altering the latching force provided by cassette 44 . Additionally, bar 40 is narrower than the opening in cassette 44 , allowing latitude for bar 40 to move side-to-side, again, without altering the latching force provided by the interaction between biased cassette 44 and the combination of bar 40 and profiled stops 42 . Bearings 46 and 48 may be rollers having bearings connected to portions of cassette 44 , or bearings 46 and 48 may themselves be a rolling sleeve, or bearing surfaces 46 and 48 may be fixed, having inherent sliding features of their own.
Springs 50 bias upper bearing 48 toward lower bearing 46 and may be stopped having a minimum distance therebetween. Bar 40 has a force required to slide it in a longitudinal direction through cassette 44 by way of the force from springs 50 as it is conveyed to bar 40 . As cover 20 is moved, profiled stop 42 encounters upper bearing 48 , which is part of the biasing features of bias cassette 44 , causing a greater force to be required to move bar 40 as profiled stop 42 interacts with the biased nature of bearings 46 and 48 so that a deliberate greater force is required to move cover 20 past stop 42 .
As can be seen in FIG. 2 , cover 20 is in a closed position with alignment assembly 34 being shown engaged with the opposing reciprocal male and female portions 36 and 38 . In FIG. 3 , cover 20 has been slid to an open position with alignment portions 36 and 38 being separated with the left set of portions 36 and 38 being shown separated from the complementary portions on the right. Additionally, biased cassette 44 has interacted with the other stop 42 to thereby hold cover 20 in an open position. As shown in FIG. 1 , the operation of a mechanism overhead interacts with protrusions 22 to apply force that is translated into linear, or at least quasi-linear, force to open or close hatch covers 20 . Linear bearing arrangements 54 may be arranged along each cover 20 to provide stability in the movement of hatch covers 20 , allowing latching systems 24 to function as latching systems and not bearing systems. Although these features are separate, it is also contemplated that these features could be combined within the scope of the inventive nature of the present invention. It is also contemplated that although bars 40 are shown as being linear other shapes are also contemplated, such as curved and curvilinear.
As seen in FIG. 4 , profiled stop 42 has encountered bearing 48 and the interaction between bearing 46 and 48 hold hatch cover 20 in a closed position relative to lower cover 26 . Adjusting mechanism 52 can be utilized to alter the biasing force of springs 50 , although it is also contemplated to produce a bias cassette 44 without an adjustment feature 52 . It is also contemplated that springs 50 may be non-linear in function, having different compression force requirements based upon the compressed length of spring 50 . As bar 40 is pushed to the right, as shown in FIG. 5 , with increased force being needed to separate bearings 48 and 46 by the interaction of stop 42 , cover 20 is then being moved, if to the right, then to open cover 20 , or if being moved to the left, to thereby close cover 20 .
As can be seen in FIG. 6 , biased cassette 44 is simply slid into bracket 28 . This allows the latching assembly connected to cover 20 to be easily removed without the removal of any fasteners or restraints. This also allows biased cassette 44 to move in a vertical manner to compensate for vibrations and movements as railcar 12 moves from place to place. Additionally, as already mentioned, bar 40 has a width that is substantially narrower than the width of cassette 44 , thereby allowing bar 40 to slide in the direction parallel with the longitudinal axis of railcar 12 . Bar 40 has a longitudinal axis and profiled stops 42 have a stop axis perpendicular therewith that can be understood to be in the direction in which bearing 48 must move as it overcomes stop 42 . This allows cassette 44 to move in bracket 28 in a direction parallel to the stop direction, yet the bracket prevents movement of the cassette in a longitudinal axis direction of bar 40 . Bar 40 can move in the direction substantially normal to the stop direction within biased cassette 44 .
Applicant's invention provides for sliding a bar through the biasing assembly 30 with a first force until encountering the profiled stop 42 connected to bar 40 . Continued sliding of bar 40 past stop 42 requires a second force, the second force being greater than the first force. Although it is understood that it is profiled step 42 that passes between biased cassette 44 's bearings 46 and 48 that the force is reduced once it reaches the top of profiled stop 42 .
Now, referring to FIG. 7 , there is shown distal ends of bars 40 with aligning assembly 34 in an engaged position with portions 36 and 38 showing the alignment of covers 20 in a closed position. No latching between covers 20 occurs with the actual latching occurring within each cover and alignment assembly 34 is used for final alignment of covers 20 as they approach each other.
While this invention has been described with respect to at least one embodiment, the present invention can be further modified within the spirit and scope of this disclosure. This application is therefore intended to cover any variations, uses, or adaptations of the invention using its general principles. Further, this application is intended to cover such departures from the present disclosure as come within known or customary practice in the art to which this invention pertains and which fall within the limits of the appended claims. | A railcar hatch cover latching system including a sliding mechanism attached to a movable portion of the hatch cover and a latching apparatus associated with the hatch cover. The latching apparatus has a biased assembly, a bar and at least one profiled stop. The bar extends through the biased assembly. The biased assembly is configured to allow the bar to pass through the biased assembly with a first force requirement. The at least one profiled stop is positioned on the bar to encounter the biased assembly and having a second force requirement to move the bar past the at least one profiled stop, the second force being greater than the first force. | 1 |
CROSS-REFERENCE TO RELATED APPLICATION(S)
[0001] This application relates to subject-matter more fully explained in my co-pending application Ser. No. 12/______, entitled HEALTH AND SAFETY SYSTEM FOR A TABLE SAW (Attorney Docket 873-013-101), filed the same day as the present application, the disclosure of which is hereby incorporated by reference.
FIELD OF THE INVENTION
[0002] The present invention relates generally to systems for power saws, providing improved health and safety during operation.
BACKGROUND AND SUMMARY OF THE INVENTION
[0003] Table saws are power tools used to cut work pieces of wood, plastic and other materials. Such saws are among the most widely used power tools in woodworking and materials processing shops, carpentry and building work sites. Four general classes of table saws are in common use including bench top table saws, contractor table saws, cabinet table saws and hybrid table saws.
[0004] A table saw includes a flat surface, or table, with a circular saw blade extending vertically up through a slot in the table. The saw blade is mounted on an arbor which is driven by an electric motor (either directly, by belt, or by gears).
[0000] The saw operator slides a workpiece on the table against and past the blade while the circular blade revolves at a high rate of speed (typically about 4,000 rpm) and cuts through the workpiece.
The thickness of the workpiece that can be sawed completely through, or the depth of the cut into the workpiece, is controlled by moving a saw motor trunnion or carriage, holding the motor, saw arbor and saw blade, up or down, relative to the saw table top. The higher the blade protrudes above the table, the deeper the cut that is made in the workpiece. Commonly, the cut into the workpiece is made perpendicular to the saw table, but most table saws also can be adjusted to make cuts at angle of up to 45 degrees from the perpendicular. Such angle or bevel cuts are made by rotating the saw motor carriage from the perpendicular such that the angle of the motor, saw motor, motor arbor and blade are adjusted to provide the desired cutting angle. Table saws are generally designed to allow rotation of the carriage, motor, arbor and blade either to the left or to the right (but not both).
[0005] Table saws typically are provided with various pieces of auxiliary equipment including a rip fence to guide a work piece make rip cuts, that is to cut work pieces generally with the grain, and a miter gauge to cut work pieces perpendicular to or generally at an angle to the grain. A splitter, a vertical projection located behind the saw blade, typically either a pin or a fin shaped piece of metal, is also typically provided as a standard or optional attachment for table saws. The splitter is typically slightly narrower in width than the blade and is aligned directly in line with the blade kerf. Saws also typically are provided with an anti-kickback device that attaches to the splitter, as well as a hinged blade cover also attached to the splitter. Saws usually have an easily replaceable insert around the blade in the table top. This allows the use of special-purpose cutters and inserts as may be required for various cutting operations.
[0006] All species of saw dust have recently been classified as carcinogenic and the finer particles are considered the most harmful. Fine saw dust, such as that generated by a table saw, has been determined to be a human carcinogen and is believed to be implicated in many other respiratory ailments as well. The carcinogenicity of saw dust has been recognized by, among others, the American Conference of Government and Industrial Hygienists (ACGIH), the National Institute of Occupational Safety and Health (NIOSH) and the International Agency for Research on Cancer (IARC). Chronic exposure to saw dust has been implicated as a cause of fibrosis, emphysema, bronchitis, asthma, respiratory allergies and dermatitis. Additionally, substantial research also indicates that many of the chemicals including various glues, adhesives and preservatives used in processed wood products are highly toxic when inhaled as a component of saw dust. Recent research suggests that chronic exposure to saw dust may prove to be an even greater danger to saw operators than the perhaps more immediately obvious risk of serious trauma injury.
[0007] Partial blade enclosures intended for collection of saw dust expelled below the table surface are within the known prior art such as U.S. Pat. No. 6,925,919 issued to LIAO et al., U.S. Pat. No. 4,255,995 issued to J. FRANKLIN CONNOR, U.S. Pat. No. 4,063,478 issued to HANS STUY, and U.S. Pat. No. 4,721,023 issued to BARTLETT et. al. These and similar prior art below-table enclosures intended for dust containment and extraction suffer from shortcomings related to inadequate seal thereby allowing significant amounts of sawdust to escape the enclosure where the seals are inadequate, particularly around the rotating saw arbor and the top of the enclosure at the table insert. Since most of dust generated normally is ejected from the saw below the table it is important to maintain adequate sealing to insure maximum effectiveness of the dust containment and extraction device.
[0008] The most common and oldest prior-art dust collection method for the cabinet type or hybrid table saw allows the sawdust to simply accumulate inside the table saw base and extract it from the base using ducting to a powerful central dust collector system. More recent prior-art has introduced various designs for attaching cloth bags under the base to capture saw dust. Both of these methods fall far short of their intended goal and provide inadequate capture of dust considering the several recently discovered health hazards associated with saw dust exposure. The present invention more effectively captures and extracts saw dust from very close to the saw blade or cutter head and thus protects the saw operator from inhaling said dust. Many woodworkers as well as industrial safety officials have recently come to view, as imperative, increased control and removal of saw dust as close to the source of generation as possible, thereby minimizing environmental exposure of saw operators to these hazards. Although the problem of saw dust control has long been known, it is widely recognized that prior art dust removal efforts have failed to adequately solve this problem. Thus, there exists a need for a table saw with improved dust containment and collection system that significantly reduces exposure of table saw operators to the long term risks of exposure to carcinogenic saw dust. The below-table blade enclosure or guard of the present invention provides a significantly improved dust containment and collection enclosure that may be retrofitted to many existing table saws and, alternatively, may be incorporated into many new table saw designs.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] FIG. 1 is a perspective view of a blade enclosure for saw dust control in accordance with one embodiment of the present invention.
[0010] FIG. 2 is a perspective view of a mounting bracket for a blade enclosure unit for a table saw in accordance with one embodiment of the present invention.
[0011] FIG. 3 is a front view of a blade enclosure for saw dust control in accordance with one embodiment of the present invention.
[0012] FIG. 4 is a rear view of a blade enclosure for saw dust control in accordance with one embodiment of the present invention.
[0013] FIG. 5 is a detailed side elevation, in a partially exploded view, of a preferred embodiment of a blade enclosure, for a table saw in accordance with the present invention.
[0014] FIG. 6 is a perspective view of a secondary insert gasket for use with a blade enclosure for a table saw in accordance with one embodiment of the present invention.
[0015] FIG. 7 is a perspective view of a secondary insert gasket, showing the position of the saw blade, for use with a blade enclosure for a table saw in accordance with one embodiment of the present invention.
[0016] FIG. 8 is a detailed top elevation, in a partially exploded view, of a preferred embodiment of a secondary insert gasket, in accordance with the present invention; AND
[0017] FIG. 9 is a perspective view of a connection to a dust collection and containment system for a table saw blade enclosure in accordance with one embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0018] An exemplary embodiment of a blade enclosure for dust collection and containment in accordance with the present invention is illustrated schematically in FIGS. 1 and 3 . The table saw to which such blade enclosure is adapted may be any type, model or configuration of table saw suitable for cutting wood, plastic or other suitable material that incorporates one or more of the various aspects of the present invention. The present invention includes complete saws as well as systems, parts, pieces or kits of parts which may be mounted on existing table saws to adapt or retrofit them in accordance with one or more of the various aspects of the present invention.
[0019] One aspect of the present invention is a blade enclosure for saw dust containment and collection, as shown in FIGS. 1 through 5 , for a table saw which may be used with a dust containment and collection system for a table saw. Blade enclosures according to the present invention contribute to safe saw operation, not only by containing and collecting hazardous saw dust but also by preventing exposure of the saw operator to the handling of said hazardous saw dust. Blade enclosures of the present invention are mounted below the saw table 62 ( FIG. 1 ), generally on the tiltable portion of the saw and motor frame carriage 61 , such that blade enclosure surrounds the blade, except at the upper edge of the saw blade where the blade passes vertically through the saw table 62 in order to cut the workpiece.
[0020] Blade enclosures of the present invention incorporate one or more of several aspects of the present invention disclosed in detail herein, and shown including: a blade enclosure 50 ( FIG. 3 ), a removable blade cover 51 , a blade enclosure vacuum seal 52 ( FIG. 5 ), a seal 56 between the blade enclosure and the front cover, a front cover arbor vacuum seal 83 ( FIG. 3 ), a blade enclosure mounting bracket 39 ( FIGS. 1 and 2 ), which replaces the manufacturer's supplied splitter mounting bracket and splitter mounting bolt in this exemplary embodiment of the invention. Also incorporated in this invention are blade enclosure bracket mounting bolts 58 FIG. 2 , a blade enclosure mounting screw 87 ( FIG. 2 ), a secondary saw table insert which functions as a gasket 54 (FIGS. 6 , 7 ), and flexible hose connector 86 ( FIG. 9 ) to a dust containment and collection system. A blade enclosure of the present invention, when designed to be retrofitted to an existing table saw, must be designed to fit the below the table structure and design of that particular saw. The exemplary blade enclosure, of FIGS. 1 through 5 , is designed and adapted to be mounted on many models of existing Delta UNISAW® table saws which have been widely used throughout the world for over fifty years. It will be readily appreciated that one of ordinary skill, provided the disclosures herein, would readily be able to design and manufacture a suitable blade enclosure for many other models of table saws.
[0021] Table saws are designed to permit the saw blade, saw arbor 60 and saw motor carriage 61 ( FIG. 1 ), to be adjustably titled at angles of up to 45 degrees relative to the normal upright or vertical saw blade position. This permits the saw operator to make bevel cuts of up to 45 degrees. The blade enclosure 50 ( FIG. 1 ) must, therefore, be shaped and mounted to accommodate such adjustable tilting of the saw blade, saw arbor 60 and to permit saw motor carriage 61 to be adjustably titled at angles of up to 45 degrees without interference or obstruction between blade enclosure 50 or blade cover 51 and the underside of saw table 62 or the underside of saw table insert 57 .
[0022] It will be appreciated that one of ordinary skill in the design, manufacture or operation of table saws would, if given the disclosures herein, understand that there are many ways in which blade enclosure 50 and front cover 51 could be so shaped and mounted. One of ordinary skill in the design, manufacture or operation of table saws, provided the disclosures herein, would readily be able to design and manufacture a suitable mount for a blade enclosure for any model of table saw. Exemplary rear mounting bracket 39 is mounted to saw motor carriage 61 using bolts 58 , as shown in FIG. 2 .
[0000] Blade enclosure 50 is then mounted to rear mounting bracket 39 , which is threaded, using bolt 87 FIG. 2 . Blade enclosure 50 is also mounted to that portion of saw motor carriage 61 adjacent to the front of the saw using bolt 59 FIG. 5 . Bolt 59 fits, and is bolted into, an existing threaded bolt hole in saw motor carriage 61 . Said threaded bolt hole is used in many models of table saw, including many models of Delta UNISAW® table saws, to support a saw dust chip deflector, which saw dust chip deflector is entirely replaced by blade enclosure 50 in the present invention. When the saw motor is tilted, to permit bevel cutting, the blade enclosure will thus also be equally tilted.
[0023] The blade cover 51 ( FIG. 3 ) must be carefully designed to permit the enclosed saw blade to be tilted through the full range permitted by design of the saw, without being impeded by, or interfering with, any part or feature of the saw interior when the secondary table insert gasket is removed. This can be accomplished by careful attention to design of the geometry, shape and dimensions of the blade cover 51 . As previously indicated, the exemplary blade cover 51 is designed to retrofit a blade enclosure of the present invention on a Delta UNISAW® table saw. Blade cover 51 is mounted to rear blade enclosure 50 with thumbscrews 81 ( FIGS. 3 and 5 ) that may be hand tightened and easily removed for changing saw blades. It will be appreciated that one of ordinary skill in the design, manufacture or operation of table saws, if given the disclosures herein, would readily be able to design and manufacture a suitable mount for a blade enclosure for any model of table saw. For complete table saw of the present invention, the blade enclosure cover and the saw interior can be designed together as a system, to permit tilting of the saw blade.
[0024] The blade enclosure 50 and blade cover 51 may be made of any suitable material. Preferably, the enclosure should be primarily fabricated of a durable yet economical material such as steel, fiberglass, graphite, fiber composite or thermoplastic.
[0025] Table saws must permit the saw blade and saw arbor 60 ( FIG. 1 ) to be adjusted vertically, relative to the saw motor carriage 61 , and also to the saw table 62 , to permit the saw to cut work pieces of different thicknesses. The blade enclosure 50 must therefore permit the saw arbor to pass through the blade enclosure at all vertical positions from the centerline of the blade enclosure at the lowest blade position to its uppermost margin. It will be appreciated that one of ordinary skill in the design, manufacture or operation of table saws would, if given the disclosures herein, understand that there are a number of methods in which the blade enclosure 50 , and arbor seals, 52 ( FIG. 4 ) could permit such vertical movement of the saw arbor. An exemplary blade enclosure according to the present invention accommodates vertical adjustment of the arbor by means of a curved slot 84 ( FIG. 5 ), sealed with one or more replaceable strip brush seals 52 , mounted to the body of the blade enclosure 50 by mounting channels 82 as shown in FIGS. 4 and 5 .
[0026] The dust control and collection features of blade enclosures of the present invention are achieved by connection of the blade enclosure 50 to a vacuum dust control and collection system with a 2.00″-2.25″ (50 mm-57 mm) inner diameter (ID) flexible hose and capable of maintaining an nominal air velocity of 1500-2000 feet per minute (760-1014 centimeters per second) at the table insert throat plate 57 ( FIG. 8 ), level with the table surface. Exemplary blade enclosure 50 is thus provided with an exhaust port 55 ( FIGS. 3 , 4 , 5 ). Preferably, one chooses a ratio, between a cross-sectional area of the longitudinal slot in table insert 57 , and a cross-sectional area of outlet port 55 which is suitable to facilitate a desirably high airflow rate for entraining the saw dust particles and particulates.
[0000] It will be readily appreciated that one of ordinary skill, if given the disclosures herein, would readily be able to design and manufacture a suitable dust collection system connection port. Effective functioning of the dust containment and collection aspects of the blade enclosure requires that the blade enclosure 50 and blade cover 51 be carefully designed and constructed, so as to form a system capable of being sufficiently sealed from air leakage and to maintain sufficient vacuum integrity, in order to substantially prevent saw dust leakage into the saw interior or into the air surrounding the saw. The external vacuum or negative air flow employed must be sufficient to contain substantially all the dust produced by the saw within the blade enclosure, and to move such dust out of the blade enclosure and to the dust collection system at approximately the same rate at which dust is produced by the sawing blade. It will be appreciated that one of ordinary skill in the design, manufacture or operation of table saws, if given the disclosures herein, would readily be able to design and manufacture suitable seals for the blade enclosure to maintain a vacuum sufficient to accomplish effective dust containment and removal. The exemplary blade enclosure 50 and cover 51 are provided with a gasket seal 56 ( FIG. 5 ), attached to the blade enclosure 50 that provides a seal between the blade cover 51 and blade enclosure. This gasket seal 56 may be made of any suitable material including rubber, cork, felt, synthetic fabric, polymers or composites.
[0027] The exemplary preferred blade enclosure 50 is provided with a replaceable brush seal 83 ( FIG. 3 ), attached to the blade enclosure 50 to provide a seal over the arbor cutout 85 ( FIG. 5 ) and provides a seal between the blade enclosure 50 and the saw blade arbor 60 ( FIG. 1 ). As the height of the saw blade is adjusted upward, the rapidly rotating and vertically adjustable saw arbor 60 ( FIG. 1 ) will partially project through the front cover cutout 85 ( FIG. 5 ) at the upper range of blade height adjustment.
[0000] Replaceable brush seal 83 ( FIG. 3 ) is intended to help maintain the strength of vacuum air flow within the enclosure 50 , and to minimize saw dust leakage through cutout 85 when the saw is operating in the upper range of blade height adjustment, causing the saw blade arbor to project slightly through the front cover cutout 85 ( FIG. 5 ).
[0028] It will be appreciated that one of ordinary skill in the design, manufacture or operation of table saws, if given the disclosures herein, would readily be able to design and manufacture suitable seals for the blade enclosure/saw arbor interface, of many configurations and designs and to manufacture such seals from many suitable materials or combinations of materials.
[0000] Replaceable seals 83 ( FIG. 3) and 52 ( FIGS. 4-5 ) may be made of any suitable material, including one or more fiber brushes, expanded foam, rubber, cork, felt, synthetic fabric, polymers or composites that will both provide an adequate seal and that will accommodate rotating saw arbor and that will further accommodate vertical adjustment of the saw arbor 60 (FIG.), relative to the saw motor carriage 61 . Brush seals 83 ( FIG. 3) and 52 ( FIGS. 4-5 ) provide the required seal while accommodating saw arbor 60 ( FIG. 1 ) rotational and height adjustment movement, in the exemplary embodiment shown.
[0029] Vacuum integrity within the blade enclosure, and thus effectiveness of the dust control and collection system, can be further improved in table saws of the present invention by provision of a secondary insert gasket 54 ( FIGS. 6-7 ), which provides a seal between saw table 62 ( FIG. 7 ) and the upper edge of blade enclosure 50 and of blade cover 51 , as shown in FIG. 8 . Table saws are typically provided with a port, in the saw table 62 , that is substantially larger than needed to accommodate the saw blade. In addition, table saws are typically provided with a replaceable table insert 57 ( FIG. 8 ) which closely fits into the table port and which closely surrounds different sized blades or cutters, as they project up through the top of the saw table 62 . When these standard inserts are in place, there remains a considerable space between the bottom surface of the insert and the upper edge of blade enclosure 50 and blade cover 51 . A secondary table insert 54 (FIGS. 6 , 7 , 8 ) is employed in the present invention to fill the space between the upper edge of blade enclosure 50 and blade cover 51 and the bottom surface of standard saw table insert 57 which provides an improved vacuum seal for the blade enclosure 50 and blade cover 51 .
[0030] Standard table inserts such as 57 ( FIG. 8 ), are provided with four leveling set screws 40 ( FIG. 8 ), which normally bear against the four insert support tabs 88 ( FIG. 7 ), which are cast into the saw table top 62 ( FIGS. 7-8 ), and are used to precisely adjust the top surface level of the table insert to match the surface level of the saw table. In the present embodiment, to compress table insert gasket 54 ( FIG. 8 ), against the blade enclosure 50 ( FIG. 3 ), and the blade enclosure cover 51 ( FIG. 3 ), the four insert support tabs have been threaded to accommodate longer set screws intended to hold the table insert 57 level and firmly in place, and to compress the table insert gasket 54 against the blade enclosure.
[0031] Saw table insert gasket 54 , may be made of any suitable compressible gasket material including foam board, PVC foam board, polypropylene, plastic, foam rubber, foam core, or any functionally suitable and cost effective material. Saw table insert 54 should be constructed of a material that will be easily and safely cut by the saw blade, such that no hazard will be posed to the saw operator, in the event of any accidental contact between the table insert gasket 54 , with the saw blade. It will be appreciated that one of ordinary skill in the design, manufacture or operation of table saws, if given the disclosures herein, would readily be able to design and manufacture suitable table saw insert gaskets of many configurations and designs, and to manufacture such seals from many suitable materials or combinations of materials.
[0032] A flexible hose, connecting the blade enclosure to a vacuum or dust collection system, may be connected to blade enclosure port 55 and may exit the table saw at any convenient location. In a preferred embodiment, a convenient flexible hose fitting 86 ( FIG. 9 ) is provided and attached to the base of the table saw. A length of flexible hose is connected to blade enclosure port 55 , is run through the base cabinet of the table saw, and is connected to flexible hose fitting 86 inside the saw cabinet. The external side of flexible hose fitting 86 may then be connected by a length of flexible hose to a dust collector or a suitable source of vacuum. It will be appreciated that one of ordinary skill in the design, manufacture or operation of table saws would, if given the disclosures herein, understand that there are many ways in which the below-table blade enclosure of the present invention could be connected to a dust collection and containment system. | A below-table blade enclosure for a table saw protects the health and safety of the person operating the saw, by enclosing the saw blade, and thereby protecting the operator from exposure to hazardous and potentially carcinogenic saw dust. The blade enclosure contains and collects the saw dust, which is removed from the blade enclosure by an external dust collecting system, for example via a vacuum hose. | 8 |
RELATED APPLICATIONS
[0001] This application claims priority and benefit from Swedish patent applications Nos. 0601229 8, filed May 31, 2006, 06017131-3, filed Aug. 16, 2006, and 0601809-7, filed Aug. 24, 2006, the entire teachings of which are incorporated herein by reference.
TECHNICAL FIELD
[0002] The present, invention is concerned with brakes, in particular holding brakes for servo motors.
BACKGROUND
[0003] Servo motors are often used in applications where it is important that they will not move during power off or when there is reason to assume that the control system of the servo motor is not behaving properly, for example when an emergency stop button has been pressed.
SUMMARY
[0004] It is an object of the invention to provide a brake or clutch that that at least in some embodiments can have a compact shape.
[0005] It is another object of the invention to provide a brake or clutch that at least in some embodiments can be produced in a cost-efficient way.
[0006] An electrically controlled brake that can also be used or designed as a clutch includes as conventional a rotatable first mechanical system having one or more friction parts/surfaces and a second mechanical system that has one or more friction parts/surfaces. The friction surfaces can made to come in contact with each other, providing a braking or coupling effect, and be withdrawn from each other releasing the brake or clutch. The second mechanical system is stationary for the case of a brake and is rotatable for the clutch case. Electric windings are provided, e.g. wound around two soft magnetic parts, and are arranged so that electric current flowing in the windings affects magnetic fluxes through the soft magnetic parts to move at least one thereof. The movement is in a direction that affects the effective length of one or more air gaps in the closed main magnetic path created by the current and the soft magnetic parts. In particular the electric current gives attraction forces over the air gap or gaps which forces tend to move one of or both the soft magnetic parts to reduce the length of the air gap. One or more springs create forces acting in a direction substantially opposing the attraction forces. In the movement the friction part of the first mechanical system comes in frictional engagement or frictional disengagement with the friction part of the second mechanical system. Frictional disengagement here means that a frictional engagement between the two mechanical system is released.
[0007] The soft magnetic parts are arranged so that the main magnetic flux path passes along a closed loop that passes about the rotational axis of the first mechanical system, this making it possible to e.g. give the brake or clutch a compact design.
[0008] The soft magnetic parts can together have a toroidal shape having e.g. substantially the same axis as the rotational axis.
[0009] Additional objects and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objects and advantages of the invention may be realized and obtained by means of the methods, processes, instrumentalities and combinations particularly pointed out in the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] While the novel features of the invention are set forth with particularly in the appended claims, a complete understanding of the invention, both as to organization and content, and of the above and other features thereof may be gained from and the invention will be better appreciated from a consideration of the following detailed description of non-limiting embodiments presented hereinbelow with reference to the accompanying drawings, in which:
[0011] FIG. 1 is a front view of a normally active, asymmetrical, angular movement brake in its braking state,
[0012] FIG. 2 is similar to FIG. 1 but shows the brake in its non-braking state,
[0013] FIG. 3 is a front view of the magnetically permeable parts of the brake of FIGS. 1 and 2 ,
[0014] FIG. 4 is a front view of a flat spring arrangement for the brake of FIGS. 1 and 2 ,
[0015] FIG. 5 is front view similar to FIG. 1 of the brake including flat springs as shown in FIG. 4 ,
[0016] FIG. 6 is a cross-sectional view in an axial plane of the brake of FIGS. 1 and 2 assembled inside the rotor of an electric motor,
[0017] FIG. 7 is a front view of a normally active, symmetrical, angular movement brake in its braking state,
[0018] FIG. 8 is a front view of the magnetically permeable parts of a parallel movement brake,
[0019] FIG. 9 is a front view of a flat spring suitable for the brake parts of FIG. 8
[0020] FIG. 10 is a cross-sectional view in radial plane of a parallel movement brake having internal linear guides,
[0021] FIG. 11 is a front view of the brake of FIG. 10 including windings,
[0022] FIG. 12 is a cross-sectional view in a radial plane of a parallel movement brake including air gap mounted springs,
[0023] FIG. 13 is a perspective view of the brake of FIG. 12 , and
[0024] FIG. 14 is similar to FIG. 12 showing a brake that is active (braking) when a control current is active.
DETAILED DESCRIPTION
[0025] FIG. 1 is a front view of a normally active brake in the braking state thereof. The brake consists of two groups of components. The first group is connected to a rotating device, for example the rotor of a motor. In the case shown, there are only two components in this group including the hollow circular cylinder or drum, 101 and the central shaft 108 . The other group is normally connected to a non-rotating or stationary part such as a motor frame. There are two main components in this group, the half-arcs 102 and 103 , each of which has the shape of the half of cylindrical ring, i.e. a cylindrical ring segment corresponding to an angle of substantially 180°. These two parts can rotate within a very limited angle around magnetically permeable shafts 104 and 105 , respectively, the shafts located at axially opposite positions near one of the flat axial surfaces of the half-arc. FIG. 1 shows the two half-arcs where each thereof has been rotated in the clockwise direction around its shaft to take its maximum clockwise position. The movement of the first half-arc 102 is limited to the position where the brake lining pad 106 of high friction material on the envelope surface of the half-arc comes in contact with the interior envelope curved surface of the hollow cylinder 101 . The movement of the second half-arc 103 is limited in the same way. As a consequence of these two movements, there are two air gaps like 107 between the two half-arcs. The force required to move the two half-arcs 102 , 103 clockwise around their respective shafts 104 , 105 can be arranged by springs configured e.g. as that shown in FIG. 5 .
[0026] FIG. 2 shows the two half-arcs 102 , 103 where each half-arc has been rotated around its shaft in the counter-clockwise direction to take its maximum counter-clockwise position. The movement of the first half-arc 102 is limited to the position where it is pressed against the second half-arc 103 . The movement of the second half-arc 103 is limited in the same way. As a consequence of these two movements, there is practically no gap 107 between the two half-arcs in this state. Consequently, there will appear a gap 201 between the brake lining 106 and the interior cylindrical surface of the brake drum 201 . The force required to move the two half-arcs counter-clockwise around their respective shafts 104 , 105 can be arranged by an electric current flowing in coils, not show, located in winding slots like 202 provided in the half-arcs, the electric current creating a magnetic field in the magnetically permeable parts shown in FIG. 3 . The winding slots and the wire turns of the coils therein are located in axial planes, i.e. planes passing through the axis of the brake.
[0027] FIG. 3 shows the magnetically permeable parts of the second (non-rotating) group. They include the two half arcs 102 and 103 , their magnetically permeable shafts 104 and two pins 303 used to permit a path for the braking spring force. In FIGS. 1 and 2 , the magnetically permeable parts are covered by other parts containing the winding slots like 202 .
[0028] In the closed state shown, the two half arcs are in a position corresponding to a non-active brake caused by current flowing in the coils in the winding slots like 202 .
[0029] FIG. 4 shows a flat spring suitable to provide the force required to create sufficient force between the friction lining 106 and the interior of the hollow cylinder 101 .
[0030] FIG. 5 shows springs like 401 assembled in the brake of FIG. 2 .
[0031] FIG. 6 shows a brake like that of FIGS. 1-5 assembled in an electric motor, e.g. a servo motor. The right end of the shaft 104 extending through the soft iron half-arc 301 is rigidly secured in the rear shield 602 . The plastic coil support is visible as 601 . The rotor shaft corresponds to the central shaft 108 of FIG. 1 , and the motor rotor magnet holding cylinder corresponds to the hollow cylinder 101 . The spring 401 is shown in suitable positions.
[0032] The force available over a magnetic air gap like 107 between the two half-arcs is very dependent on the length of the air gap (parallel with the flux lines). Spring loaded magnetically actuated brakes should have small air gaps to permit a large force from a small current. On the other hand, the air gap must be large enough to ensure that the friction surfaces used when the brake is active will be engaged when the brake is active and disengaged when the brake is passive. The required length of the air gap is therefore dependent of the mechanical tolerances in the parts in the brake force path. To overcome the mechanical tolerances of the parts in the force path, the air gap must be longer than the sum of the mechanical tolerances of these parts.
[0033] An advantage of the azimuthal or circumferential force path of the brake of FIGS. 1-6 is that the cost to get tight tolerances of cylindrical parts is comparatively low. The inside of a hollow cylinder like 101 with a diameter of 52.5 can easily be made with a tolerance class 6 corresponding to a diameter variation of 19 micrometers, i.e. is a radial uncertainty of 9.5 micrometers. Using similar rotation production technologies for the adjustment of the friction lining 106 on a set of two half-arcs with no air gap in position 107 can give a total uncertainty of for example 19 micrometers measured at the air gap 201 of the brake lining. This would require some 25 micrometer air gap in position 107 of FIG. 1 to cover the uncertainty of the mechanical dimensions of the parts used (the difference between 19 and 25 micrometers is caused by the distances from the shafts 104 and 105 ). Even after that margins have been added to handle other uncertainties, an air gap 107 of 70 micrometers instead of the 200 micrometers that are normal in spring actuated brakes permit an excitation current of some 35% of the conventional one and a power loss of some 10% of the power loss for the same device using a conventional air gap.
[0034] From this discussion it is obvious that the brake as described herein can be made have its mechanically critical dimension tolerances in the radial direction, utilising the fact that it is less expensive to manufacture radial dimensions with a high precision than axial dimensions. This can make the brake cost-efficient. Also, since short air gaps can be produced at a reasonable cost, the brake can be made to have a high torque to power loss ratio for the braking/releasing operation.
[0035] FIG. 7 shows a slightly different brake. The two parts may rotate slightly around the shafts 701 and 702 . The required spring force is applied between pins 703 and 704 .
[0036] The brake lining 707 will give a higher brake torque for a counter-clockwise movement of the brake drum 708 than for a clock-wise movement of the drum, as the friction force will cause an increase of the force perpendicular to the drum surface, causing a positive feedback. In the brake of FIG. 7 , this is compensated by the fact that the brake torque from the other lining 711 will give lower brake torque for a counter-clockwise movement of the brake drum 708 than for a clockwise movement of the drum, thus giving a torque that is independent of the rotation direction. The brake shown in FIG. 1 will have a torque dependent on the rotation direction and may hence be suitable for e.g. robot parts moving against gravity.
[0037] The angle shown as 709 in FIG. 7 will affect the brake torque obtained for a given spring force. For a given magnetic air gap, there will be a corresponding possible spring force. If the angle 709 is reduced by another design of the position of the brake lining, the friction force and therefore the torque caused by a constant spring force will change. A given magnetic air gap will give different gaps between the brake lining like 711 and the brake drum depending on the angle 709 .
[0038] Large values of the angle 709 combined with high friction coefficients for the lining—drum materials will result in a self-locking brake with a brake torque that is limited only by the breakdown of the weakest components.
[0039] FIG. 8 shows the magnetically active parts of a toroidal brake that has a parallel movement of the two parts. While such a brake can have two moving parts, the embodiment of FIG. 8 has one arc part 801 fixed to the chassis by screws in holes 803 , 804 , 805 and aligned by pins in holes like 806 . The other arc part 802 moves vertically. With no electric current flowing in the coils described under item 903 and 1101 below, the two parts are separated by a spring force, and the lining 807 is pressed by the spring force against the interior surface of a drum.
[0040] FIG. 9 shows a flat spring 902 intended to be connected to the two parts 801 - 802 shown in FIG. 8 . There are four winding slots like 903 which can be wound using toroidal winding machines.
[0041] FIG. 10 is a radial axial sectional view of a brake that has internal linear bearings and springs. The springs like 1004 are centered around pins like 1003 that are pressed into the moving arc part 1002 but can move smoothly inside bearings like 1005 , that can be PTFE covered steel tubes.
[0042] FIG. 11 shows the winding 1101 of the brake of FIG. 10 . The brake is shown in its no current, braking state in FIG. 10 and in its current carrying, not braking state in FIG. 11 .
[0043] FIG. 12 is a radial axial sectional view of a parallel movement brake having the springs in the magnetic air gap. The brake is shown in its active (braking) state. It contains two half toroids 1202 and 1203 . The half toroids are permitted to move inside a narrow space. Radially the half toroid 1202 is restricted against movements upward as seen in the drawing by the friction block 106 and the brake drum 1208 . In the direction left, downwards and right it is limited by the stationary bars like 1204 . These bars are preferably made of a material having a very low magnetic permeability such as some stainless steels.
[0044] FIG. 12 shows the brake after the drum 1208 has turned in the clockwise direction, thus moving the two half toroids in the clockwise direction. This has caused the half toroids to make a small clockwise rotation, causing a small gap indicated by arrow 1206 between the lower side of the stationary bar 1204 and the half toroid 1203 and a direct contact between the half toroid 1202 and the stationary bar 1204 . Should there appear a counter-clockwise movement of the drum 1208 , the two half toroids would move counter-clockwise and a gap would instead appear on the upper side of the stationary bar 1204 .
[0045] The brake is shown with a hollow shaft 1207 .
[0046] The springs are located in the gap 1205 but are not visible in any detail in FIG. 12 .
[0047] FIG. 13 shows the brake of FIG. 12 in another view. The stationary bar 1204 shown only in a section in FIG. 12 is here shown complete. On its end there is a top part 1301 that restricts the movement of the half toroids in the axial direction. The springs 1302 act to separate the two half toroids. If there is no electric current flowing in the coils, the springs will separate the two half toroids until the friction blocks 106 are pressed against the drum 1208 . In this state, there might be a total air gap between the two half toroids of some 0.4 mm. The springs are preferably made of steel having a high magnetic permeability, and the thickness of the spring material is not included in the air gap. When the coils are connected to a suitable DC voltage, the two half toroids are attracted by a force larger than the separating force from the springs, and the half toroids are then pressing against the stationary parts like 1204 , leaving only a minor air gap in the order of 0-0.1 mm. It might be preferable to make sure that both half toroids press against the stationary parts like 1208 by intentionally designing the system so that a small air gap remains when the half toroids press against the bar 1204 ; this will fix the position of the half toroids so that they cannot vibrate freely.
[0048] FIG. 14 is a front view of a brake that is substantially similar to that of FIG. 12 except that it acts on the centre shaft 1401 through two friction blocks like 1402 . This brake is active, i.e. is braking, when the controlling current in the coils is active. To limit the movement of the half toroids, blocking bars like 1403 are provided.
[0049] As is obvious for those skilled in the art, the invention shown can be varied in many ways. All embodiments shown have the friction blocks or pads 106 mounted to the outside of the half toroids or half-arcs pressing against the inside surface of a drum when there is no current in the windings. Obviously, if the friction blocks are moved to the inside of the half toroids and then pressing against a central shaft, the braking effect would appear when there is electric current flowing in the windings. Also, the embodiments shown have one drum part rotating while the half toroids and their associate hardware are stationary, thus giving a brake. Obviously, the half toroids and their associated hardware can be assembled on a rotating part, thus creating a clutch.
[0050] While specific embodiments of the invention have been illustrated and described herein, it is realized that numerous other embodiments may be envisaged and that numerous additional advantages, modifications and changes will readily occur to those skilled in the art without departing from the spirit and scope of the invention. Therefore, the invention in its broader aspects is not limited to the specific details, representative devices and illustrated examples shown and described herein. Accordingly, various modifications may be made without departing from the spirit or scope of the general inventive concept as defined by the appended claims and their equivalents. It is therefore to be understood that the appended claims are intended to cover all such modifications and changes as fall within a true spirit and scope of the invention. Numerous other embodiments may be envisaged without departing from the spirit and scope of the invention. | An electrically controlled brake or clutch includes a rotatable first mechanical system ( 101, 108 ) and a second mechanical system that is stationary for the case of a brake but rotatable for the clutch case. In the second system windings are wound around two soft magnetic parts ( 102, 103 ) so that electric current flowing in the windings affects magnetic fluxes through the soft magnetic parts to move them in a direction that affects the effective length of an air gap in the closed main magnetic path. A spring ( 401 ) creates a force acting in a direction opposite that of the attraction force. The soft magnetic parts are arranged so that the main magnetic flux path passes along a closed loop about the rotational axis of the first mechanical system, this giving a compact design of the brake or clutch. | 7 |
[0001] This is a continuation in part of PCT Application No. PCT/JP2004/009330, filed on Jul. 1, 2004, which claims the benefit of Japanese Patent Application No. 2003-190501, filed on Jul. 2, 2003, all of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] The present invention relates to a forming method of a low dielectric constant insulating film of a semiconductor device, a semiconductor device, and a low dielectric constant insulating film forming apparatus, and more particularly, to a method and an apparatus which generate plasma by using a microwave, thereby curing a low dielectric constant coating film used as an interlayer insulation film of a semiconductor device while maintaining a low dielectric constant.
DESCRIPTION OF THE RELATED ART
[0003] In accordance with an increase in integration degree of a semiconductor integrated circuit, an increase in wiring delay time ascribable to an increase in inter-wiring capacitance, which is a parasitic capacitance between metal wirings, comes to be a hindrance to achieving a higher performance of the semiconductor integrated circuit. The wiring delay time is proportional to a product of a resistance of the metal wiring and the wiring capacitance. In order to lower the resistance of the metal wiring for achieving a shorter wiring delay time, highly conductive copper (Cu) is used instead of conventionally used aluminum (Al).
[0004] Further, a possible way of reducing the wiring capacitance is to lower a dielectric constant (k) of an interlayer insulating film formed between the metal wirings. As a low dielectric constant interlayer insulating film, used is an insulating film which is lower in dielectric constant than conventional oxide silicon (SiO 2 ). Such a low dielectric constant insulating film is formed on a wafer by, for example, a SOD (Spin-on-Dielectric) system. Specifically, the SOD system coats the wafer with a high-molecular forming material in liquid form and applies curing such as heating thereto, thereby forming an insulating film. The dielectric constant of the coating film, at the stage where it is formed by the SOD system, keeps a low value.
[0005] However, the insulating film, if left as it is after being formed, is low in mechanical strength and low in adhesiveness to a base substrate. Therefore, the insulating film is thermally cured while keeping its low dielectric constant. The insulating film increases in strength by a chemical bonding force when molecules thereof are bonded into a polymer by this thermal curing, so that the peeling of the films at the time of chemical mechanical polishing (CMP) is prevented.
[0006] Conventionally, for curing the insulating film, for example, 30 to 60 minute heating is applied by using a furnace. However, this method not only requires a long time for the processing but also cannot attain predetermined mechanical hardness, and the long heating may possibly increase the dielectric constant.
[0007] Another curing method is to use an electron beam, but this method, though only taking 2 to 6 minutes for curing, can only achieve insufficient hardness. Therefore, a method of curing the insulating film in a short time while further lowering the dielectric constant is being demanded.
[0008] Further, Japanese Patent Application Laid-open No. Hei 8-236520 describes a method of curing an insulating film by generating plasma in a parallel-plate plasma reactor.
[0009] A first object of the method of curing the insulating film by generating the plasma in the parallel-plate plasma reactor described in the above Japanese Patent Application Laid-open No. Hei 8-236520 is to cure a SOG film without producing any residues or the like. A second object of this method is to prevent property deterioration of current/voltage due to moisture generation when a photosensitive film is removed after a subsequent masking process.
[0010] The above-described method reduces a defect in the SOG film such as —OH and —CH 3 causing leakage current by curing the insulating film at a temperature of 200° C. to 450° C. for 60 minutes. However, in order to maintain the low dielectric constant, CH 3 is indispensable, and exposing the SOG film to the plasma atmosphere for no less than 60 minutes has a problem that CH 3 disappears to make the dielectric constant higher.
SUMMARY OF THE INVENTION
[0011] It is a major object of the present invention to provide a forming method of an insulating film of a semiconductor device capable of curing the insulating film of the semiconductor device in a short time while maintaining a low dielectric constant, and to provide a semiconductor device having an insulating film formed by, for example, this method, and a low dielectric constant insulating film forming apparatus.
[0012] A forming method of a low dielectric constant insulating film of a semiconductor device of the present invention includes the step of placing in a vacuum vessel a substrate on which a coating film is formed and applying, to the coating film, high-density plasma processing at a low electron temperature, thereby curing the coating film while keeping a low dielectric constant.
[0013] Accordingly, it is possible to cure the coating film in a short time while keeping the low dielectric constant.
[0014] Preferably, the curing step includes curing the coating film in a processing time of five minutes or less. This can increase the number of the substrates processable per hour, resulting in an improved throughput in semiconductor processing steps.
[0015] Preferably, the curing step includes generating plasma with a low electron temperature of 0.5 eV to 1.5 eV and an electron density of 10 11 to 10 13 electrons/cm 3 . Thus curing the coating film at the low electron temperature makes it possible to reduce energy of an electron absorbed in the coating film, so that a damage given to the coating film when the electron collides with the coating film can be alleviated.
[0016] Preferably, the curing step includes causing an intermolecular dehydration-condensation reaction by hydroxyls in a molecule and another molecule included in the coating film.
[0017] According to another aspect, a semiconductor device of another invention of the present invention includes: a substrate; and a low dielectric constant insulating film applied on the substrate and cured by high-density plasma processing at a low electron temperature.
[0018] An example of a molecular structure of the insulating film cured by the high-density plasma processing is one including a Si—O—Si bond.
[0019] According to still another aspect, a low dielectric constant insulating film forming apparatus of the present invention includes: a curing means for curing a coating film while keeping a low dielectric constant, by placing in a vacuum vessel a substrate on which a coating film is formed and applying, to the coating film, high-density plasma processing at a low electron temperature based on microwave excitation.
[0020] An example of the curing means is one generating plasma with a low electron temperature of 0.5 eV to 1.5 eV and an electron density of 10 11 to 13 13 electrons/cm 3 .
[0021] According to this invention, the substrate on which the low dielectric constant coating film is formed is placed in the vacuum vessel and the high-density plasma processing is applied to the coating film at the low electron temperature based on the microwave excitation, whereby it is possible to cure the coating film in a short time while keeping the low dielectric constant and in addition, to bring the coating film in close contact with the base substrate.
[0022] Further, setting a processing time of the curing to five minutes or less makes it possible to increase the number of the substrates processable per hour, so that the throughput in the semiconductor processing processes can be improved.
[0023] In addition, generating the plasma with the low electron temperature of 0.5 eV to 1.5 eV and the electron density of 10 11 to 13 13 electrons/cm 3 makes it possible to reduce electron energy absorbed by the coating film, so that the damage given thereto when the electron collides with the coating film can be alleviated.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] FIG. 1 is a cross-sectional view showing a plasma substrate processing apparatus used for forming a low dielectric constant insulating film of the present invention;
[0025] FIG. 2 is a perspective view partly in section of a slot plate shown in FIG. 1 ;
[0026] FIG. 3A to FIG. 3C are cross-sectional views of an insulating film, showing processes for forming the low dielectric constant insulation film according to one embodiment of the present invention, FIG. 3A showing a substrate before being processed, FIG. 3B showing a state in which a coating film is formed on the substrate, and FIG. 3C showing a state in which the insulating film is formed by curing the coating film;
[0027] FIG. 4A is a view showing a molecular structure of the insulating film before being cured and FIG. 4B is a view showing a molecular structure of the insulating film cured by the plasma substrate processing apparatus;
[0028] FIG. 5 is a chart showing the correlation between curing time and dielectric constant in curing in the embodiment of the present invention and in conventional curing using an electron beam;
[0029] FIG. 6 is a chart showing the correlation between curing time and modulus of elasticity in the curing in the embodiment of the present invention and in the conventional curing using the electron beam;
[0030] FIG. 7A is a table showing, for comparison, concrete experiment results of curing in another embodiment of the present invention and in conventional curing using a furnace, FIG. 7B is a table showing, for comparison, concrete experiment results of the curing in the other embodiment of the present invention and the curing using the electron beam, and FIG. 7C is a table showing, for comparison, concrete experiment results of the curing in the other embodiment of the present invention and the curing using the electron beam;
[0031] FIG. 8 is a chart showing changes in dielectric constant and modulus of elasticity when a mixture ratio of hydrogen gas is varied in the embodiment of the present invention;
[0032] FIG. 9 is a chart showing a change in methyl residual ratio when the mixture ratio of the hydrogen gas is varied in the embodiment of the present invention;
[0033] FIG. 10 is a chart showing changes in dielectric constant and modulus of elasticity when process pressure is varied in the embodiment of the present invention; and
[0034] FIG. 11 is a chart showing a change in methyl residual ratio when the process pressure is varied in the embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0035] Hereinafter, embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view of a plasma substrate processing apparatus used for forming an insulating film of the present invention. FIG. 2 is a perspective view partly in section of a slot plate shown in FIG. 1 .
[0036] As shown in FIG. 1 , the plasma substrate processing apparatus 100 has a plasma processing chamber 101 in a cylindrical shape as a whole, with a sidewall 101 a and a bottom portion 101 b thereof, for example, being made of conductors such as aluminum, and an inner part of the plasma processing chamber 101 is formed as an airtight processing space S. The plasma processing chamber 101 may be formed in a box shape.
[0037] This plasma processing chamber 101 houses a mounting table 102 for placing a processing target (for example, a semiconductor wafer W) on an upper surface thereof. The mounting table 102 is made of, for example, anodized aluminum or the like and formed in a substantially columnar shape. The mounting table 102 has therein a heater H for heating the wafer W when necessary. The mounting table 102 further provides lift pins 103 for lifting the wafer W.
[0038] On the upper surface of the mounting table 102 , an electrostatic chuck or a clamping mechanism (not shown) for keeping the wafer W supported on the upper surface is provided. Further, the mounting table 102 is connected to a matching box (not shown) and a high-frequency power source for bias (for example, for 13.56 MHz; not shown) via a feeder (not shown). Note that in a case of CVD processing or the like, that is, when the bias is not applied, this high-frequency power source for bias need not be provided.
[0039] A ceiling portion of the plasma processing chamber 101 has an opening, in which an insulating plate 104 (for example, about 20 mm in thickness) made of a ceramic dielectric such as, for example, quartz or Al 2 O 3 and transmissive for a microwave is airtightly provided via a sealing member (not shown) such as an O-ring.
[0040] On an upper surface of the insulating plate 104 , a slot plate 105 functioning as an antenna is provided. The slot plate 105 has a circular conductor plate 105 a made of, for example, a disk-shaped thin copper plate, and a large number of slots 105 b are formed in the circular conductor plate 105 a , as shown in FIG. 2 . Owing to these slots 105 b , uniform electric field distribution is formed for a space in the processing space S.
[0041] The circular conductor plate 105 a is constituted of a thin disk made of a conductive material, for example, silver- or gold-plated copper or aluminum. The circular conductor plate 105 a may be in a square shape or a polygonal shape, not limited to the disk shape. In this embodiment, as the slot plate 105 , used is a RLSA (Radial Line Slot Antenna) having a plurality of pairs of slots, the slots in each pair making a T shape or perpendicularly facing each other, and these pairs being arranged for example, concentrically, circularly, or spirally.
[0042] On an upper surface of the slot plate 105 , a retardation plate 106 made of a highly dielectric material, for example, quartz, Al 2 O 3 , AlN, or the like is provided to cover the slot plate 105 . The retardation plate 106 , which is sometimes called a wavelength shortening plate, lowers the propagation speed of a microwave to shorten the wavelength thereof, thereby improving propagation efficiency of the microwave emitted from the slot plate 105 .
[0043] The microwave is propagated from the waveguide 107 to the slot plate 105 . The frequency of the microwave is not limited to 2.45 GHz but other frequency, for example, 8.35 GHz may be used. The microwave is generated by, for example, a microwave generator 108 . The waveguide 107 has a rectangular waveguide 114 and a coaxial waveguide 115 , and the coaxial waveguide 115 is composed of an outer conductor 115 a and an inner conductor 115 b . The microwave generated by the microwave generator 108 is uniformly propagated to the slot plate 105 via the rectangular waveguide 114 and the coaxial waveguide 115 and is further supplied uniformly from the slot plate 105 via the insulating plate 104 .
[0044] A conductive shield cover is disposed on the retardation plate 106 to cover the slot plate 105 , the retardation plate 106 , and so on. A cooling plate 112 for cooling the slot plate 105 , the retardation plate 106 , the insulating plate 104 , and so on is disposed on the shield cover, and refrigerant paths 113 for cooling these members are provided inside the cooling plate 112 and the sidewall 101 a . The cooling plate 112 has an effect of preventing thermal deformation and breakage of the slot plate 105 , the retardation plate 106 , and the insulating plate 104 for stable plasma generation.
[0045] In the sidewall 101 a of the aforesaid plasma processing chamber 101 , gas supply nozzles 120 as gas supply ports for introducing rare gas such as Ar and Kr, and oxidizing gas such as O 2 , nitriding gas such as N 2 , or vapor-containing gas into the processing space S are provided at equal intervals. In the plasma substrate processing apparatus 100 , for the purpose of uniform exhaust of the atmosphere in the processing space S, a gas baffle plate 121 is disposed to be substantially perpendicular to the sidewall 101 a . The gas baffle plate 121 is supported by a supporting member 122 . Further, on inner sides (sides facing the processing space S) of the sidewall 101 a and the gas baffle plate 121 , liners 123 made of, for example, quartz glass are disposed for preventing the occurrence of particles such as metal contamination generated from the walls due to the sputtering by ions.
[0046] Gas in the atmosphere in the plasma processing chamber 101 is uniformly exhausted by an exhaust device 125 via exhaust ports 124 A, 124 B.
[0047] As gas supply sources to the aforesaid gas supply nozzles 120 being the gas supply ports, an inert gas supply source 131 , a process gas supply source 132 , and a process gas supply source 133 are prepared, and these gas supply sources are connected to the gas supply nozzles 120 via inner opening/closing valves 131 a , 132 a , 133 a , massflow controllers 131 b , 132 b , 133 b , and outer opening/closing valves 131 c , 132 c , 133 c , respectively. Flow rates of the gases supplied from the gas supply nozzles 120 are controlled by the massflow controllers 131 b , 132 b , 133 b.
[0048] A controller 140 controls ON-OFF and output control of the aforesaid microwave generator 108 , the flow rate adjustment by the massflow controllers 131 b , 132 b , 133 b , adjustment of an exhaust amount of the exhaust device 125 , the heater H of the mounting table 102 , and so on so as to allow the plasma substrate processing apparatus 100 to perform the optimum processing.
[0049] This invention uses the plasma substrate processing apparatus 100 shown in FIG. 1 to apply plasma processing to be described below, thereby curing an insulating film in a short time while keeping a low dielectric constant.
[0050] FIG. 3A to FIG. 3C are cross-sectional views of an insulating film, showing processes for forming the insulating film according to one embodiment of the present invention. FIG. 4A and FIG. 4B are views showing a molecular structure of the insulating film before being cured and a molecular structure of the insulating film plasma-processed by the plasma substrate processing apparatus 100 .
[0051] First, a substrate 1 shown in FIG. 3A is prepared, the substrate 1 is coated with a low dielectric constant insulating film material by, for example, a generally-known SOD system, so that a coating film 2 is formed, as shown in FIG. 3B . Here, the applied insulative material is a low dielectric constant insulating film such as, for example, porous MSQ (Methyl Silsesqueoxane) whose dielectric constant is, for example, 2.4 or lower. As shown in FIG. 4A , the porous film MSQ has a structure such that one molecule is terminated with a hydroxyl bonded to Si of O—Si—O and the other molecule is terminated with a hydroxyl bonded to Si of O—Si—O, and it also includes a structure such that one molecule and the other molecule are dissociated.
[0052] Next, the substrate 1 on which the coating film 2 is formed is carried into the processing space of the plasma substrate processing apparatus 100 shown in FIG. 1 by a not-shown carrier. Then, non-mixed gas of argon (Ar), hydrogen (H 2 ), or helium (He) or mixed gas made of the combination of these is introduced into the processing space of the plasma substrate processing apparatus 100 , and at the same time, the 2.45 GHz microwave is supplied to the coaxial waveguide 115 , whereby plasma with a low electron temperature of 0.5 eV to 1.5 eV and an electron density of 10 11 to 10 13 electrons/cm 3 is generated in the processing space at a temperature of about 250° C. to about 400° C. By this high-density plasma, plasma processing is applied for curing the coating film 2 , with a processing time of, for example, five minutes or less, more preferably, one minute to two minutes, so that the coating film 2 turns to a cured insulating film 3 , as shown in FIG. 3C .
[0053] Note that the aforesaid low electron temperature was measured by a Langmuir probe in a space between the gas nozzles 120 of raw material gas and the silicon wafer W under the same condition in advance. Further, the electron temperature was also confirmed by Langmuir probe measurement.
[0054] By this plasma processing, one and the other molecules adjacent to each other are bonded together as shown in FIG. 4A and FIG. 4B . That is, hydrogen of the hydroxyl of one molecule shown in FIG. 4A is dissociated and the bond of the hydroxyl and Si of the other molecule is dissociated. Then, the dissociated hydrogen and hydroxyl are bonded into water, and this water is removed, so that intermolecular dehydration-condensation reaction takes place. By such intermolecular dehydration-condensation reaction, the Si—O—Si bond takes place as shown in FIG. 4B . By such Si—O—Si bond, the insulating film 3 cures.
[0055] FIG. 5 is a view showing the correlation between curing time and dielectric constant in curing in the embodiment of the present invention and in conventional curing using an electron beam, and FIG. 6 is a view showing the correlation between curing time and modulus of elasticity in the curing in the embodiment of the present invention and in the conventional curing using the electron beam. In these drawings, circular marks represent the results of the conventional curing using the electron beam, and triangular marks represent the results of the plasma processing in the embodiment using the plasma substrate processing apparatus 100 .
[0056] As shown in FIG. 5 , in the curing by the electron beam, the dielectric constant is about 2.25 when the processing time is 120 seconds, and the dielectric constant becomes higher to about 2.3 when the processing time is set longer to 360 seconds. On the other hand, in this embodiment using the plasma substrate processing apparatus 100 , the dielectric constant is about 2.2 when the plasma processing time is 60 seconds, and when the plasma processing time is set longer to 300 seconds, the dielectric constant only slightly exceeds the value of 2.2 and thus no significant change is seen in the dielectric constant. When the plasma processing time is between 60 seconds and 300 seconds, the dielectric constant also keeps the value of about 2.2. The processing time is preferably 1000 seconds or less, more preferably, 600 seconds or less.
[0057] That is, it is seen from FIG. 5 that the plasma processing using the plasma substrate processing apparatus 100 can achieve a lower dielectric constant than the curing by the electron beam. Further, it is seen that the use of the plasma substrate processing apparatus 100 can keep the dielectric constant substantially the same even when the plasma processing time becomes longer, while the use of the electron beam tends to increase the dielectric constant as the curing time becomes longer.
[0058] As is apparent from the correlation between modulus of elasticity and processing time shown in FIG. 6 , in the case of using the electron beam, when the curing time is 120 seconds, modulus of elasticity is about 6 GPa, and when the curing time is 300 seconds, modulus of elasticity increases to about 8 GPa. On the other hand, in the case of using the plasma substrate processing apparatus 100 , when the plasma processing time is 60 seconds, modulus of elasticity is about 6.5 GPa, and when the plasma processing time is 360 seconds, modulus of elasticity increases to about 8.2 GPa. When the plasma processing time falls within the range from 60 seconds to 300 seconds, the value of modulus of elasticity falls within the range from 6.5 GPa to 8.2 GPa. Thus, modulus of elasticity presents an increasing tendency as the processing time becomes longer both in the case of using the electron beam and in the case of using the plasma substrate processing apparatus 100 . The processing time is preferably 60 seconds to 1000 seconds, more preferably, 60 seconds to 600 seconds.
[0059] Therefore, it is confirmed from the results shown in FIG. 5 and FIG. 6 that the curing using the electron beam can increase modulus of elasticity but also increases the dielectric constant when the processing time is set longer. On the other hand, the plasma processing using the plasma substrate processing apparatus 100 can not only increase modulus of elasticity and but also keep the dielectric constant at the same value when the processing time is set longer. In this case, the processing time is preferably 60 seconds to 1000 seconds, more preferably, 60 seconds to 600 seconds.
[0060] FIG. 7A to FIG. 7C are tables showing, for comparison, concrete experiment results of curing in another embodiment using the plasma substrate processing apparatus 100 and concrete experiment results of conventional curing using a furnace and conventional curing using the electron beam. Note that a MSQ1 film is used in FIG. 7A , while a MSQ2 film is used in FIG. 7B and FIG. 7C .
[0061] As shown in FIG. 7A , as a result of the curing by the furnace under the conditions that the temperature was 420° C. and the processing time was 60 minutes, the following film quality was obtained: dielectric constant 2.16, modulus of elasticity 5.4 GPa, hardness 0.5 GPa, and methyl residual ratio (Si—Me/SiO) 0.025. On the other hand, as a result of the plasma processing using the plasma substrate processing apparatus 100 under the condition that the temperature was 350° C. and the processing time was one minute, the following film quality was obtained: dielectric constant 2.39, modulus of elasticity 6.9 GPa, hardness 0.6 Gpa, and methyl residual ratio 0.011.
[0062] It is apparent from these results that the plasma processing in the embodiment using the plasma substrate processing apparatus 100 can extremely shorten the time taken for the curing, and as for the film quality, can increase modulus of elasticity and hardness, though slightly increasing a dielectric constant, compared with the conventional curing by the furnace.
[0063] Further, as shown in FIG. 7B , as a result of the curing by the electron beam under the condition that the temperature was 350° C. and the processing time was two minutes, the following film quality was obtained: dielectric constant 2.24, modulus of elasticity 5.9 GPa, and hardness 0.52 GPa. At this time, the residual ratio of a methyl group could not be confirmed. On the other hand, as a result of the plasma processing by the plasma substrate processing apparatus 100 under the condition that the temperature was 350° C. and the processing time was one minute, the following film quality was obtained: dielectric constant 2.21, modulus of elasticity 7.6 GPa, hardness 0.7 GPa, and methyl residual ratio 0.026. It is seen from these results that the dielectric constant can be made lower while the methyl group is allowed to exist.
[0064] Moreover, as shown in FIG. 7C , as a result of the curing by the electron beam under the condition that the temperature was 350° C. and the processing time was six minutes, the following film quality was obtained; dielectric constant 2.31, modulus of elasticity 8.2 GPa, and hardness 0.75 GPa. At this time, the residual ratio of the methyl group could not be confirmed. On the other hand, as a result of the plasma processing by the plasma substrate processing apparatus 100 under the condition that the temperature was 350° C. and the processing time was five minutes, the following film quality was obtained: dielectric constant 2.21, modulus of elasticity 8.6 GPa, hardness 0.8 GPa, and methyl residual ratio 0.021.
[0065] It is seen from these results that the value of the dielectric constant in the conventional curing by the electron beam is substantially the same as the value of the dielectric constant in the plasma processing by the plasma substrate processing apparatus 100 , but the processing by the plasma substrate processing apparatus 100 can more increase modulus of elasticity and hardness while allowing the methyl group to remain.
[0066] Next, FIG. 8 shows changes in modulus of elasticity (GPa) and dielectric constant to. a hydrogen gas ratio when the MSQ2 film is cured by the plasma processing by the plasma substrate processing apparatus 100 while a flow rate ratio of argon gas/hydrogen gas in the process gas is varied. At this time, the temperature for processing the substrate 1 is 350°, the process pressure is 0.5 Torr, and the processing time is 60 seconds. It is seen from the results that modulus of elasticity increases from 6.0 to 7.1 GPa, while the dielectric constant keeps a low value of 2.2 even when the hydrogen gas ratio is increased up to 50 percent. Further, as for the methyl residual ratio when the processing is applied under the same conditions, the methyl residual ratio gets lower as the hydrogen gas ratio increases, and when the hydrogen gas ratio is 50%, the methyl residual ratio is 0.019, as shown in FIG. 9 .
[0067] As is seen from the above, when the curing is applied by the plasma processing by the plasma substrate processing apparatus 100 , increasing the hydrogen gas mixture ratio makes it possible to increase modulus of elasticity as film quality while keeping the low dielectric constant. More preferably, the hydrogen gas mixture ratio is 50% or lower. This is because the increase in the H 2 ratio lowers a ratio of high-energy Ar+, so that the decomposition of Si—Me is inhibited, resulting in increased hardness.
[0068] For reference, FIG. 8 and FIG. 9 also show results obtained when non-mixed gas of helium is used as the process gas used in the plasma processing. It has been found out from these results that it is possible to obtain a still higher value for modulus of elasticity while the dielectric constant keeps the same low value as in the case of using argon gas/hydrogen gas.
[0069] Next, pressure dependency was studied. Specifically, as a process gas condition, a flow rate ratio of hydrogen gas in argon gas/hydrogen gas was fixed to 10% (argon gas/hydrogen gas=1000/100 SCCM), the temperature of the substrate was set to 350°, and the processing time was set to 60 seconds. Changes in modulus of elasticity (Gpa) and dielectric constant under these conditions with the process pressure being varied from 0.1 Torr to 2.0 Torr are shown in FIG. 10 , and a change in methyl residual ratio in the same case is shown in FIG. 11 .
[0070] From these results, it has been found out that even the processing under the increased process pressure causes no change in dielectric constant, but causes an increase in modulus of elasticity from 6.5 to 7.1 GPa. Further, as for the methyl residual ratio, it has been found out that the increase in the process pressure causes a decrease in the methyl residual ratio, but even under the process pressure of 2.0 Torr, the methyl residual ratio keeps 0.018. Therefore, the processing under the increased process pressure makes it possible to increase modulus of elasticity as film quality while keeping the low dielectric constant. The process pressure is preferably 2.0 Torr or lower. Such processing under the high pressure contributes to hardness increase of the film since the plasma mainly composed of radicals inhibits the decomposition of Si—Me in the film.
[0071] Incidentally, FIG. 10 and FIG. 11 also show results when non-mixed gas of helium is used as the process gas in the plasma processing. It has been found out from these results that the dielectric constant is the same as in the case of hydrogen gas, but a still higher value is obtained for modulus of elasticity.
[0072] Further, in this embodiment, since the use of the plasma substrate processing apparatus 100 using the microwave can produce the atmosphere at a low electron temperature, damage to the insulating film can be alleviated. Specifically, high electron temperature increases sheath bias voltage, which increases energy when electrons in the plasma are directed to the insulating film, so that the insulating film is damaged when the electrons collide with the insulating film. On the other hand, when the electron temperature is low, the energy when the electrons are directed to the insulating film gets small, which can alleviate the damage to the insulating film when the electrons collides with the insulating film and can lower the dielectric constant without lowering the methyl group residual ratio.
[0073] Further, setting the curing time to five minutes or less, more preferably, one minute to two minutes makes it possible to process 20 to 30 wafers per hour, even if the transfer time of the wafers is taken into consideration, which enables improved throughput in semiconductor processing processes.
[0074] In the above-described example, the plasma is generated by the microwave, but a plasma generating means (plasma source) in the present invention is not limited to any specific one. That is, besides the microwave, plasma sources such as, for example, ICP (inductively coupled plasma), ECR, a surface reflected wave, magnetron, and the like are also usable.
[0075] Hitherto, the embodiment of the present invention has been described with reference to the drawings. However, the present invention is not limited to the shown embodiment. Various kinds of changes can be made to the shown embodiment within the same range as or an equivalent range to that of the present invention.
[0076] The present invention is useful for forming a low dielectric constant insulating film in manufacturing processes of various kinds of semiconductor devices. | It is an object of the present invention to cure an insulating film of a semiconductor device in a short time while keeping a low dielectric constant. In the present invention, a coating film made of porous MSQ is formed on a substrate, the substrate on which the porous MSQ is formed is placed in a vacuum vessel, and high-density plasma processing at a low electron temperature based on microwave excitation is applied to the coating film by using a plasma substrate processing apparatus, thereby causing an intermolecular dehydration-condensation reaction of hydroxyls in a molecule and another molecule included in the porous MSQ to bond the molecules together, so that a cured insulating film is generated while a low dielectric constant is maintained. | 7 |
BACKGROUND
[0001] People often carry electronic devices into remote locations while camping, backpacking, performing research, or for military action. Often times these electronic devices require the use of batteries, which are heavy and may not last very long. If the batteries are rechargeable, the user may be able to carry a solar panel, fuel cell, or some other energy storage device into the field to recharge the batteries. However, a solar panel is often not a reliable source of energy due to cloud cover, the angle of the sun, shadows, and nightfall. Other energy storage devices like fuel cells often run on a single fuel source like methanol, have a short lifespan, and can be complex and expensive for the average user. These systems typically have mechanical and/or electrical feedback control systems in place to regulate fuel and temperature. However, the feedback control components often add significant weight and complexity to the system. Another option to recharging batteries in the field is to harvest energy from a heat source such as a camping stove by using a thermoelectric module. The current invention intends to provide a lightweight source of reliable energy in the field by harvesting energy from a heat source using a thermoelectric module coupled to a camping pot. The current invention improves upon prior art by maximizing power output and efficiency, increasing energy density and power density, reducing the risk of damaging the thermoelectric module, and providing communication to the electronic device being charged.
PROBLEM
[0002] Prior art depicts using a thermoelectric module harvesting energy from a stove and using a pot of water to cool one side of the module. Although this depiction is similar to the present invention, several problems are evident. The electrical current that is produced by the thermoelectric module must flow through several inches of wire to a Direct Current to Direct Current converter (DC to DC converter) that sits several inches away from the pot and heat source. Because the current is large, significant power losses may be experienced. These wires may also become exposed to the heat source and could be at risk of catching on fire or melting the insulation on the conductor and causing a short circuit. Prior art depicts using a DC to DC converter to output power from the thermoelectric module. However, using a DC to DC converter may not provide the maximum power or maximum efficiency of the thermoelectric module unless specific measures are taken. Another problem is that the prior art simply bolts a metal plate to the pot in order to sandwich the thermoelectric module. However, this does not optimize the thermal conductivity between the heat source and the thermoelectric module, and thus, this decreases the overall efficiency of the system. The reduced efficiency of the system from heat source to electrical output results in lower energy and power density which increases the weight needed to be carried in the field. Mother problem is that the prior art does not inform the user when there are potentially harmful conditions for the thermoelectric device. The thermoelectric module may withstand temperatures upward of 250 Celsius, but temperatures above this will shorten the lifespan of the module. If a heat source is left unchecked or if the pot is left empty, the temperature of the thermoelectric module may start to rise and degrade the module permanently. Lastly, the prior art does not depict the ability to communicate with the devices it is powering. This means the prior art acts as a “dumb” charger or power source. Devices that could benefit from communicating will not be able to do so.
DETAILED DESCRIPTION OF THE INVENTION
[0003] The following detailed description is of the contemplated modes of carrying out exemplary embodiments of the invention. The description is not to be taken in a limiting sense, but is made merely for the purpose of illustrating the general principles of the invention, since the scope of the invention is best defined by the appended claims. Broadly, an embodiment of the present invention generally provides a multi-use camping pot that produces power from heat.
[0004] An embodiment of the present invention may use a solid-state thermoelectric module that generates electrical power while the user is heating the contents of the pot using an external heat source or fuel. The device may conserve weight by excluding an automated feedback control system and because it is used both as a cooking utensil and a power generator. Since there are no moving parts, the lifespan of the invention may be long. Due to the low complexity, the cost may be low as well. The present invention solves many problems present in the prior art. The present invention integrates the DC to DC converter into the detachable handle of the pot. This reduces the length of high current-carrying wires which increases the overall efficiency of the system, reduces the risk of fire, and reduces the risk of tripping. The handle may be detachable from the pot using an attachment mechanism. The handle may also house electrical connectors which couple the thermoelectric module to the DC to DC converter input and electrical connectors that couple the DC to DC converter output to an external electronic device. The present invention also solves the problem of maximizing the available power output or efficiency of the thermoelectric module. By operating the DC to DC converter in a voltage limit control and/or current limit control and limiting the output current to the maximum power point of the thermoelectric module, the converter can optimize the power or efficiency of the thermoelectric device. Power point tracking is another method that is commonly used by converters on solar panels and could be implemented by the converter of the present invention to improve output power or efficiency of the thermoelectric module. The present invention also improves upon the prior art by using heat fins on the heat sink in order to increase the thermal conductivity between the heat source and the thermoelectric device. The overall increase in efficiency results in higher energy and power density, which reduces the weight needed to be carried in the field. The present invention also reduces the risk of overheating the thermoelectric device by using a thermocouple to measure the temperature near the thermoelectric module and using logic circuits in the user interface to inform the user when adverse conditions arise. The user interface may also display other important information such as when the electrical power is available or information received by an external electrical device. The present invention also improves upon the prior art by using a communication signal to enable the transfer of information to and from an external electrical device. The communication protocol may be SMBus, PMBus, USB, or some other type of protocol.
[0005] As depicted in the figures, an embodiment of a thermoelectric module 1 may include material that converts heat to electricity. The material may include but is not limited to bismuth, telluride, polymers, ceramics, or kapton tape. While there might be no limit to the efficiency, voltage, current, or power of the thermoelectric module, the module may be between 1% and 25% efficient, output 1-15V, output 1-50 A, and output between 1 and 500 W. Other embodiments of a module may be 4-10% efficient, output 0.1-12 volts, 0.001-35 A, 1-50 W. While there might be no limit to the number of thermoelectric modules, the device may have 1-5 modules connected electrically in series, parallel, or a combination of series and parallel connections. Other embodiments may have a single module. The modules may be between 1 inches square and 10 inches square. A thermocouple 2 may include two dissimilar metals that produce a voltage that changes with temperature. An embodiment may include a combination of metals, including but not limited to chromel, alumel, constantan, iron, nicrosil, nisil, platinum, rhodium, copper, tungsten, rhenium, nickel, molybdenum, cobalt, or gold. The direct current-to-direct current (DC to DC) converter 3 may include circuit elements that regulate the input or output voltage and/or current. The DC to DC converter may include any of the known converter topologies including but not limited to buck, boost, buck-boost, flyback, push-pull, single ended primary inductor converter (SEPIC), Cuk, forward, half-bridge, full-bridge, or resonant converters. The converter may be between 0% and 99.9% efficient. The DC to DC converter may be controlled by either analog or digital circuitry including but not limited to analog or mixed signal integrated circuits (ICs), microcontrollers, or field-programmable gate arrays (FPGAs). The connectors 4 may include a body that contains metal contacts used for conducting electricity. The connectors may take a form for conducting electricity and mating with counterpart connectors. The user interface (UI) 5 may include circuits for processing and displaying information to the user and/or a mechanism for the user to enter commands to the electrical system. The UI may include but is not limited to electronic displays, a speaker, logic circuits, microcontrollers, and processors. The UI may display information regarding the operation of the invention and present command options for the user to enter or accept. The UI may also include button(s) that allow the user to enter commands to the electrical system for use in operation of the system. The vessel 6 may include a cup made out of metal that holds material such as liquids, solids, or a combination of the two. The vessel may include metal, such as aluminum, stainless steal, titanium or other alloys. The vessel may take on a number of shapes and sizes but may be between 2 and 12 inches in diameter and between 2 and 12 inches tall. The vessel also may include a handle 8 made of metal or plastic. The handle may have a cavity for the circuitry of the invention and for housing wires and connectors. The handle 8 may be detachable from the vessel. The plate 7 comprises a thin sheet of metal that compresses the thermoelectric module between the plate and the vessel 6 . The plate may be comprised of any type of metal but is preferably made of aluminum, stainless steal, titanium or other alloys. The plate may take on a number of shapes and sizes but is preferably round with a diameter between 2 and 12 inches. The plate is preferably between 0.001 inches and 1 inch in thickness. The plate may have holes, slots, threaded holes, threaded studs, dips or other attachment mechanisms for attaching it to the vessel 6 . The plate may have heat fins on the bottom for collecting heat. The plate may be attached to the vessel 6 using bolts, nuts, studs, collars, clamps, screws, dips, or any other method for attachment.
[0006] An embodiment may include the vessel 6 , the thermoelectric module 1 , the plate 7 , the DC to DC converter 3 , and the wiring and connectors 4 . Alternate embodiments may include elements that provide additional benefits and features as described above. For example, an embodiment may include a mechanical connection for connecting with a camping stove. This connection may use bolts, nuts, studs, collars, clamps, screws, dips, or any other method for attachment. An embodiment may also include insulative articles that increase the thermal performance such as a rubber or plastic lid, a neoprene cozy around the outside of the vessel 6 , or aerogel or ceramic insulation placed between the thermoelectric module 1 and the vessel 6 and plate 7 . In an embodiment, the bottom flat part of the vessel 6 may be attached to the plate 7 with the thermoelectric module 1 in between the two. The thermoelectric module 1 may be electrically insulated from the vessel 6 and the plate 7 either by anodizing the vessel 6 and plate 7 or by using anodized metal plates or ceramic plates placed on either side of the thermoelectric module 1 . Thermal grease may also be used when attaching each of these components to aid in the conduction of heat. The vessel 6 may be attached to the plate 7 using bolts, nuts, studs, collars, clamps, screws, dips, or any other method for attachment. The thermoelectric module 1 may be connected the DC to DC converter 3 via wire conductors. The DC to DC converter 3 may be connected to the UI 5 and its circuit components via wire. The DC to DC converter 3 and/or UI 5 may be enclosed in the handle 8 of the vessel 6 and connected to the thermoelectric module 1 via a wire and connector. The thermocouple 2 may be situated near the thermoelectric module 1 either on top, on bottom, or to the side of the thermoelectric module 1 . The thermocouple 2 may be connected to the circuitry of the UI 5 and alert the user to operating conditions via a display or speaker. The DC to DC converter 3 and the UI 5 may be a part of the same circuit and/or circuit board. The circuits may be arranged next to each other, far apart, or via connectors. The connectors 4 may be used to connect the thermoelectric module 1 to the DC to DC converter 3 , the thermoelectric module 1 to the UI 5 , the DC to DC converter 3 to the external electrical load, and/or the thermocouple 2 to the UI circuitry 5 . An embodiment of the vessel 6 may be filled with material such as water in order to provide a heat sink and a way of regulating the temperature of one side of the thermoelectric module. The bottom of plate 7 may employ heat fins and be placed near a heat source to absorb heat. The heat will travel through the plate 7 , through the thermoelectric module 1 , and through the vessel 6 to the material in the vessel. The thermoelectric module 1 may convert a certain percentage of the heat into electricity while the rest of the heat energy will be used to heat up the material in the vessel 6 . The electrical power may be converted using the DC to DC converter 3 to a regulated output voltage and/or current. The output power may flow through the connector 4 and wiring to the load. The thermocouple 2 may sense the temperature near the thermoelectric module 1 and provide a voltage reading to the logic circuitry of the UI 5 . The thermoelectric module 1 may also provide a voltage signal to be used by the UI 5 . The UI may use this information to determine if the temperature of the thermoelectric module 1 is too high. If the temperature is too high, the UI may relay the information to the user through either the speaker, the electronic display, or both. The UI may also command the DC to DC converter to shut down or otherwise alter its operation via a communications signal.
[0007] To make an embodiment, one could provide the vessel 6 and anodize the bottom flat surface, place thermal grease on the surface, and place the thermoelectric module 1 against the surface. One could then anodize the plate 7 and place thermal grease on the plate. If the plate were stainless steal, one could place an additional anodized plate or ceramic plate against the plate 7 and apply thermal grease to this surface. The plate 7 could then be connected to the vessel 6 via bolts, nuts, studs, collars, clamps, screws, dips, or any other method for attachment. The thermoelectric module 1 could connect to the DC to DC converter 3 and/or the UI circuitry 5 via wiring and/or electrical connectors. The DC to DC converter 3 and UI 5 could be made by building a circuit board or boards and populating the board(s) with the circuit components. The components and wiring could be soldered to the board(s). The connectors could be soldered to the circuit board(s) and/or wiring. The connectors 4 could be attached to the handle 8 of the vessel or placed in line with the wire. The circuit board(s) could be placed in the handle 8 enclosure and attached via bolts, nuts, studs, collars, clamps, screws, dips, or any other method for attachment. The handle 8 could be provided and attached to the vessel 6 via weld, bolts, nuts, studs, collars, clamps, screws, dips, or any other method for attachment. In an embodiment, the thermoelectric module 1 , plate 7 , circuitry 3 and 5 , and connector 4 could all be detachable.
[0008] To use an embodiment, a person could first fill the vessel 6 with a material such as water and place it over a source of heat such as a camp fire or camping stove. As the device heats up, electrical power may be available via the output connector 4 . Additionally, the material in the vessel, such as water, may heat up. The user could connect his electronic device to the invention via a cable plugged into the connector on the handle 8 . When the person handles the invention he/she could place liquid in the vessel and place the invention over a stove or other heat source. The user would then plug in an electrical device to the output of the DC to DC converter via the connectors 4 . When the person is done powering his/her electronic equipment or heating the contents of the vessel 6 , he/she could move the device off the heat source using the handle. An embodiment could include a mechanism for thermally attaching the plate 7 to a source of heat such as an exhaust pipe, radiator, or engine component in an industrial or automotive application. Embodiments may include a mechanism for compressing and attaching the thermoelectric module to the vessel in order to increase efficiency. It should be understood, of course, that the foregoing relates to exemplary embodiments of the invention and that modifications may be made without departing from the spirit and scope of the invention as set forth in the following claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] FIG. 1 depicts an isometric view of embodiment of the present invention;
[0010] FIG. 2 depicts an exploded view of part of embodiment of the present invention;
[0011] FIG. 3 depicts an exploded view of embodiment of FIG. 1 partly assembled;
[0012] FIG. 4 depicts a detailed isometric view of part of embodiment of FIG. 3 ; and
[0013] FIG. 5 depicts an electrical block diagram of embodiment. | People often need to recharge batteries for portable electronics in remote locations where there is no electrical grid. One way to recharge these batteries is to harvest energy from a source of heat such as a camping stove using a thermoelectric module. Prior art depicts using a thermoelectric module harvesting energy from a stove and using a pot of water to cool one side of the module. The current invention improves upon prior art by maximizing power output and efficiency, increasing energy and power density, reducing the risk of damaging the thermoelectric module, and providing communication to the electronic device being charged. | 0 |
CLAIM OF PRIORITY UNDER 35 U.S.C. §119
[0001] The present application is a continuation and claims priority to U.S. application Ser. No. 11/454,419, filed Jun. 16, 2006, entitled “NEGOTIATED CHANNEL INFORMATION REPORTING IN A WIRELESS COMMUNICATION SYSTEM” and to Provisional Application No. 60/691,704, filed Jun. 16, 2005, entitled “NEGOTIATED CHANNEL INFORMATION REPORTING IN A WIRELESS COMMUNICATION SYSTEM”, and assigned to the assignee hereof and hereby expressly incorporated by reference herein.
BACKGROUND
[0002] 1. Field
[0003] The present description relates generally to wireless communication and more specifically to feedback of channel quality information (CQI) in a wireless communication system.
[0004] 2. Background
[0005] An orthogonal frequency division multiple access (OFDMA) system utilizes orthogonal frequency division multiplexing (OFDM). OFDM is a multi-carrier modulation technique that partitions the overall system bandwidth into multiple (N) orthogonal frequency subcarriers. These subcarriers may also be called tones, bins, and frequency channels. Each subcarrier is associated with a respective sub carrier that may be modulated with data. Up to N modulation symbols may be sent on the N total subcarriers in each OFDM symbol period. These modulation symbols are converted to the time-domain with an N-point inverse fast Fourier transform (IFFT) to generate a transformed symbol that contains N time-domain chips or samples.
[0006] In a frequency hopping communication system, data is transmitted on different frequency subcarriers during different time intervals, which may be referred to as “hop periods.” These frequency subcarriers may be provided by orthogonal frequency division multiplexing, other multi-carrier modulation techniques, or some other constructs. With frequency hopping, the data transmission hops from subcarrier to subcarrier in a pseudo-random manner. This hopping provides frequency diversity and allows the data transmission to better withstand deleterious path effects such as narrow-band interference, jamming, fading, and so on.
[0007] Feedback of Channel Quality Indicator (CQI), e.g. channel information in a MIMO system is generally more challenging than CQI feedback for SISO systems. For SISO users, the CQI is computed at the access terminal (AT), using pilots sent over a dedicated control or signaling channel (FL-CTRL) or a data channel (FL-data). The CQI is fedback using a dedicated resource of a reverse link signaling or control channel (RL-CTRL).
[0008] Existing CQI feedback schemes assume a CQI table with a deterministic mapping scheme between the quantized CQI values and the packet-formats that can be supported by the AT. However, future wireless systems will support ATs with different capabilities (laptops, low-cost cell-phones, PCs, PDAs etc). This provides a great range of CQI quantization possibilities and thus increases the complexity of the feedback required. Furthermore, the deployments of next-generation wireless systems can vary hot-spots, partially loaded systems, fully loaded systems etc. Further, the different access points may vary from being configured for SISO to MIMO operation. Each of the scenarios generally requires different gradations of CQI quantization, and this further increases the complexity of the CQI feedback.
[0009] Thus, there exists a need in the art for a system and/or a methodology to optimize CQI feedback for different scenarios while at the same time maintaining the possibility of supporting the different scenarios.
SUMMARY
[0010] The following presents a simplified overview or summary of one or more embodiments in order to provide a basic understanding of such embodiments. This summary is not intended to be an extensive overview of all contemplated embodiments, and it is not intended to identify key or critical elements of all embodiments nor is it intended to delineate the scope of any or all embodiments. Its sole purpose is to present some concepts of one or more embodiments in a simplified form as a prelude to the more detailed description that is presented later.
[0011] In accordance with one or more embodiments and corresponding disclosure thereof, various aspects are described in connection with enhancing performance in a wireless communication system by optimizing CQI feedback for different scenarios while at the same time maintaining the possibility of supporting the different scenarios. According to one aspect, a method for determining and providing feedback information, can comprise receiving an indicator identifying at least one feedback table to use, where a feedback table is used for quantizing channel information, selecting a feedback table, from at least one feedback table, where selecting is determined at least in part by the received indicator, and transmitting the information associated with the feedback table.
[0012] According to another aspect the method can also comprise broadcasting a type of one or more of the at least one feedback table, wherein the received indicator may be determined by the type of feedback table broadcast. In addition, the method can be used for providing a range of signal-to-noise ratios, wherein each of the at least one feedback tables comprises a range of signal-to-noise ratios each range corresponding to a feedback value. The method can also be used for providing information regarding a forward link channel quality, wherein each of the at least one feedback tables includes information indicative of a forward link channel quality as well as providing information regarding a data transmission format, wherein each of the at least one feedback tables includes information that may be utilized to determine a packet format appropriate for data transmission. The method may also include transmitting a feedback table indicator, wherein the feedback table indicator comprises at least one bit, and a feedback table comprising a smaller number of entries contains less quantizing channel information compared to a feedback table comprising a larger number of entries. In yet another aspect the method can comprise determining a system loading, wherein the selection of the feedback table is further a function of system loading, determining the capability of an access terminal, wherein the selection of the feedback table is further a function the capability of an access terminal transmitting the indicator. The method may also comprise determining a reverse link capacity, wherein the selection of the feedback table is further a function of the reverse link capacity, and determining the reverse link capacity utilizing a reverse link control channel capacity metric. In the methods discussed the feedback table can be a CQI table.
[0013] According to another aspect, when the determination indicates that the at least one feedback table identified by the at least one second received indicator is not one of the at least one feedback table identified by the at least one first transmitted indicator the method may include transmitting at least one first indicator identifying at least one feedback table from a plurality of feedback tables for quantizing channel information, receiving at least one second indicator identifying at least one feedback table, determining based at least upon whether the at least one feedback table identified by the at least one second indicator is one of the at least one feedback table identified by the at least one first indicator, electing a feedback table from the plurality of feedback tables based on the determination, and transmitting information associated with the selected feedback table. The method may also comprise transmitting at least one additional indicator identifying at least one feedback table from a plurality of feedback tables for quantizing channel information, receiving at least one additional indicator identifying at least one feedback table, determining whether the at least one feedback table identified by the at least one additional received indicator is one of the at least one feedback table identified by the at least one additional transmitted indicator, and selecting a feedback table from the plurality of the feedback tables based on the determination associated with the additional transmitted and received indicators. The method may include determining a decoding complexity of an access point wherein the selection of the feedback table is further a function of the access point decoding complexity.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] The features, nature, and advantages of the present embodiments may become more apparent from the detailed description set forth below when taken in conjunction with the drawings in which like reference characters identify correspondingly throughout and wherein:
[0015] FIG. 1 illustrates aspects of a multiple access wireless communication system according to an embodiment;
[0016] FIG. 2 illustrates aspects of a transmitter and receiver in a multiple access wireless communication system;
[0017] FIG. 3 illustrates a CQI table.
[0018] FIG. 4 illustrates a methodology for selecting a CQI table.
[0019] FIG. 5 illustrates another methodology for selecting a CQI table.
[0020] FIG. 6 illustrates a functional block diagram for selecting a CQI table.
[0021] FIG. 7 illustrates a functional block diagram for selecting a CQI table.
DETAILED DESCRIPTION
[0022] Various embodiments are now described with reference to the drawings, wherein like reference numerals are used to refer to like elements throughout. In the following description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of one or more embodiments. It may be evident, however, that such embodiment(s) may be practiced without these specific details. In other instances, well-known structures and devices are shown in block diagram form in order to facilitate describing one or more embodiments.
[0023] As used in this application, the terms “component,” “system,” and the like are intended to refer to a computer-related entity, either hardware, a combination of hardware and software, software, or software in execution. For example, a component may be, but is not limited to being, a process running on a processor, a processor, an object, an executable, a thread of execution, a program, and/or a computer. One or more components may reside within a process and/or thread of execution and a component may be localized on one computer and/or distributed between two or more computers. Also, these components can execute from various computer readable media having various data structures stored thereon. The components may communicate by way of local and/or remote processes such as in accordance with a signal having one or more data packets (e.g., data from one component interacting with another component in a local system, distributed system, and/or across a network such as the Internet with other systems by way of the signal).
[0024] Furthermore, various embodiments are described herein in connection with a user device. A user device can also be called a system, a subscriber unit, subscriber station, mobile station, mobile device, remote station, access point, base station, remote terminal, access terminal, user terminal, terminal, user agent, or user equipment. A user device can be a cellular telephone, a cordless telephone, a Session Initiation Protocol (SIP) phone, a wireless local loop (WLL) station, a PDA, a handheld device having wireless connection capability, or other processing device connected to a wireless modem.
[0025] Moreover, various aspects or features described herein may be implemented as a method, apparatus, or article of manufacture using standard programming and/or engineering techniques. The term “article of manufacture” as used herein is intended to encompass a computer program accessible from any computer-readable device, carrier, or media. For example, computer readable media can include but are not limited to magnetic storage devices (e.g., hard disk, floppy disk, magnetic strips . . . ), optical disks (e.g., compact disk (CD), digital versatile disk (DVD) . . . ), smart cards, and flash memory devices (e.g., card, stick, key drive . . . ).
[0026] Referring to FIG. 1 , a multiple access wireless communication system according to one embodiment is illustrated. A multiple access wireless communication system 100 includes multiple cells, e.g. cells 102 , 104 , and 106 . In the embodiment of FIG. 1 , each cell 102 , 104 , and 106 may include an access point 150 that includes multiple sectors. The multiple sectors may be formed by groups of antennas each responsible for communication with access terminals in a portion of the cell. In cell 102 , antenna groups 112 , 114 , and 116 each correspond to a different sector. In cell 104 , antenna groups 118 , 120 , and 122 each correspond to a different sector. In cell 106 , antenna groups 124 , 126 , and 128 each correspond to a different sector.
[0027] Each cell includes several access terminals which may be in communication with one or more sectors of each access point. For example, access terminals 130 and 132 are in communication base station 142 , access terminals 134 and 136 are in communication with access point 144 , and access terminals 138 and 140 are in communication with access point 146 .
[0028] It can be seen from FIG. 1 that each access terminal 130 , 132 , 134 , 136 , 138 , and 140 is located in a different portion of it respective cell relative to each other access terminal in the same cell. Further, each access terminal may be a different distance from the corresponding antenna groups with which it is communicating. Both of these factors provide situations, due to environmental and other conditions in the cell, which cause different channel conditions to be present between each access terminal and the corresponding antenna group with which it is communicating.
[0029] In certain aspects, each access terminal 130 , 132 , 134 , 136 , 138 , and 140 may negotiate a feedback scheme, e.g. a CQI table that it will utilize to provide feedback for providing channel state information to the access point. In some aspects, this may be by selecting one or more feedback tables, or equivalents thereto, received via an over the air message from the access point. In other aspects, it may be a communication session between the access point and the access terminal after registration with the access point.
[0030] As used herein, a CQI table may encompass any set of information that may be used to associate an indicator to sets of values indicative of channel conditions.
[0031] As used herein, an access point may be a fixed station used for communicating with the terminals and may also be referred to as, and include some or all the functionality of a base station. An access terminal may also be referred to as, and include some or all the functionality of, a user equipment (UE), a wireless communication device, a terminal, a mobile station or some other terminology.
[0032] Referring to FIG. 2 , one embodiment of a transmitter and receiver in a multiple access wireless communication system is illustrated. At transmitter system 210 , traffic data for a number of data streams is provided from a data source 212 to a transmit (TX) data processor 214 . In an embodiment, each data stream is transmitted over a respective transmit antenna. TX data processor 214 formats, codes, and interleaves the traffic data for each data stream based on a particular coding scheme selected for that data stream to provide coded data. In some embodiments, TX data processor 214 applies precoding weights to the symbols of the data streams based upon the user and the antenna from which the symbols are being transmitted. In some embodiments, the precoding weights may be generated based upon an index to a codebook generated at the receiver 202 and provided as feedback to the transmitter 200 which has knowledge of the codebook and its indices. Further, in those cases of scheduled transmissions, the TX data processor 214 can select the packet format based upon rank information that is transmitted from the user.
[0033] The coded data for each data stream may be multiplexed with pilot data using OFDM techniques. The pilot data is typically a known data pattern that is processed in a known manner and may be used at the receiver system to estimate the channel response. The multiplexed pilot and coded data for each data stream is then modulated (i.e., symbol mapped) based on a particular modulation scheme (e.g., BPSK, QSPK, M-PSK, or M-QAM) selected for that data stream to provide modulation symbols. The data rate, coding, and modulation for each data stream may be determined by instructions performed by processor 230 . As discussed above, in some embodiments, the packet format for one or more streams may be varied according to the rank information that is transmitted from the user.
[0034] The modulation symbols for all data streams are then provided to a TX MIMO processor 220 , which may further process the modulation symbols (e.g., for OFDM). TX MIMO processor 220 then provides N T modulation symbol streams to N T transmitters (TMTR) 222 a through 222 t . In certain embodiments, TX MIMO processor 220 applies precoding weights to the symbols of the data streams based upon the user to which the symbols are being transmitted to and the antenna from which the symbol is being transmitted from that user channel response information.
[0035] Each transmitter 222 receives and processes a respective symbol stream to provide one or more analog signals, and further conditions (e.g., amplifies, filters, and upconverts) the analog signals to provide a modulated signal suitable for transmission over the MIMO channel. N T modulated signals from transmitters 222 a through 222 t are then transmitted from N T antennas 224 a through 224 t , respectively.
[0036] At receiver system 250 , the transmitted modulated signals are received by N R antennas 252 a through 252 r and the received signal from each antenna 252 is provided to a respective receiver (RCVR) 254 . Each receiver 254 conditions (e.g., filters, amplifies, and downconverts) a respective received signal, digitizes the conditioned signal to provide samples, and further processes the samples to provide a corresponding “received” symbol stream.
[0037] An RX data processor 260 then receives and processes the N R received symbol streams from N R receivers 254 based on a particular receiver processing technique to provide N T “detected” symbol streams. The processing by RX data processor 260 is described in further detail below. Each detected symbol stream includes symbols that are estimates of the modulation symbols transmitted for the corresponding data stream. RX data processor 260 then demodulates, deinterleaves, and decodes each detected symbol stream to recover the traffic data for the data stream. The processing by RX data processor 260 is complementary to that performed by TX MIMO processor 220 and TX data processor 214 at transmitter system 210 .
[0038] The channel response estimate generated by RX processor 260 may be used to perform space, space/time processing at the receiver, adjust power levels, change modulation rates or schemes, or other actions. RX processor 260 may further estimate the signal-to-noise-and-interference ratios (SNRs) of the detected symbol streams, and possibly other channel characteristics, and provides these quantities to a processor 270 . RX data processor 260 or processor 270 may further derive an estimate of the “operating” SNR for the system. Processor 270 then provides estimated (CSI), which may comprise various types of information regarding the communication link and/or the received data stream. For example, the CSI may comprise only the operating SNR. The CSI is then processed by a TX data processor 238 , which also receives traffic data for a number of data streams from a data source 276 , modulated by a modulator 280 , conditioned by transmitters 254 a through 254 r , and transmitted back to transmitter system 210 .
[0039] In addition, processor 270 may select the index(ces) or entry(ies) that correspond to the matrix(ces) or vector(s) that provide indications of some desired channel conditions, e.g. SNR, for the receiver 202 based upon the signals received by the receiver. Processor 270 can quantize the index or entry according to a feedback table, e.g. a CQI table, which is known at transmitter 200 . In some embodiments, five-bit codes may be utilized allowing a wide range of channel conditions. The codebook size and entries can vary per device, per sector, per cell, or per system and may be updated over time based upon communication conditions, system updates, or the like. As discussed with respect to FIG. 1 , the feedback table that is utilized may be obtained by negotiation or selected from a broadcast message.
[0040] At transmitter system 210 , the modulated signals from receiver system 250 are received by antennas 224 , conditioned by receivers 222 , demodulated by a demodulator 240 , and processed by a RX data processor 242 to recover the CSI reported by the receiver system. The reported quantized information e.g. CQI is then provided to processor 230 and used to (1) determine the data rates and coding and modulation schemes to be used for the data streams and (2) to generate various controls for TX data processor 214 and TX MIMO processor 220 .
[0041] At the receiver, various processing techniques may be used to process the N R received signals to detect the N T transmitted symbol streams. These receiver processing techniques may be grouped into two primary categories (i) spatial and space-time receiver processing techniques (which are also referred to as equalization techniques); and (ii) “successive nulling/equalization and interference cancellation” receiver processing technique (which is also referred to as “successive interference cancellation” or “successive cancellation” receiver processing technique).
[0042] A MIMO channel formed by the N T transmit and N R receive antennas may be decomposed into N S independent channels, with N S ≦min {N T , N R }. Each of the N S independent channels may also be referred to as a spatial subchannel (or a transmission channel) of the MIMO channel and corresponds to a dimension.
[0043] For a full-rank MIMO channel, where N S =N T ≦N R , an independent data stream may be transmitted from each of the N T transmit antennas. The transmitted data streams may experience different channel conditions (e.g., different fading and multipath effects) and may achieve different signal-to-noise-and-interference ratios (SNRs) for a given amount of transmit power. Moreover, in those cases that successive interference cancellation processing is used at the receiver to recover the transmitted data streams, and then different SNRs may be achieved for the data streams depending on the specific order in which the data streams are recovered. Consequently, different data rates may be supported by different data streams, depending on their achieved SNRs. Since the channel conditions typically vary with time, the data rate supported by each data stream also varies with time.
[0044] In some aspects, the CQI may be transmitted on a Code Division Multiplexed (CDM) channel and as a result the number of CQIs which can be sent is limited by the number of available codes. Thus, when a system is partially loaded, there are codes available to be used as a CQI, and when the system is fully loaded there are may be no codes which may be used as a CQI available. Thus, by using the codes available on a partially loaded system a precoding gain is achievable by dividing the available bandwidth, performing frequency hopping on the divided portions, reporting a channel quality index for each divided portion, and using the CQI in such a manner as to improve the precoding and also reduce the overhead required for precoding.
[0045] CQI reporting may be done for each spatial subchannel, may be combined over multiple spatial subchannels, per frequency subcarrier, or combined for groups of frequency subcarries.
[0046] Referring to FIG. 3 , the table illustrates CQI mapping to the Forward Link (FL) Packet Format and Number of Forward Link Physical Frames. FIG. 3 illustrates the use of a 4-bit CQI value and use of a 5-bit CQI value. In an aspect, 4-bit CQI values are used for Single-Input-Multiple-Output (SIMO), and 5-bit CQI values are used with Multiple-Input-Multiple-Output (MIMO). An AT measures the Forward Link (FL) channel quality and determines a signal to noise ratio, e.g. E s /N o value. The AT then does a lookup to quantize the CQI value which represents the signal to noise ratio. The AT transmits the CQI value to the Access Point (AP), and the AP does a table lookup to get the E s /N o value. Now the AP knows the FL channel quality, and based on the FL channel quality the AP knows which packet formats are supported for the next transmission or transmissions.
[0047] In one embodiment, an AP may maintain 10 CQI tables, and an AT may negotiate with an AP as to which CQI table to use. For example, in the case of an AT which supports 4 packet formats, it may be most efficient to use a 2-bit CQI value. In this scenario, an AT that can use a 2-bit CQI value, the coding and decoding complexity is decreased and Reverse Link (RL) capacity is improved. In an embodiment, a RL control channel capacity metric may be used to indicate the RL capacity. Also, in an embodiment, an AP decode complexity metric may be used to indicate the coding and decoding complexity of an AP. On the other hand, an AT which supports 64 packet formats may request a higher resolution CQI value, for example a 6-bit CQI value. The higher packet formats supports high data rates, and benefits from users using less resources such as time frequency resources.
[0048] Referring to FIG. 4 , in an embodiment, an AP may maintain a plurality of CQI tables, and an AT may maintain one or more CQI tables based on the AT's capabilities. The AT may advertise, through the Reverse Link (RL), to the AP the CQI tables the AT supports, 402 . The AP then selects a CQI table to use based on the CQI tables supported by the AT, 404 . The AP may inform the AT of the CQI table selected or the selection may be implicit, 406 . The AP and the AT begin transmitting data using a packet format appropriate for the FL channel, 408 . The AP may select a CQI table solely on the AT's capability. Also, for example, in the case of an AT that supports more than one CQI table, other factors such as system loading where system loading is determined by how much of the systems resources are being utilized. By using other factors along with the CQI tables supported by the AT, the network can optimize the performance of the AT's served by the AP.
[0049] Referring to FIG. 5 , in another embodiment the selection of a CQI table may be deployment specific. In such an embodiment this may occur when an AP that serves a hot-spot or supports high packet format applications and services. The AP may advertise one preferred CQI table or several preferred CQI tables, 502 . In some cases and the AP may advertise several preferred CQI tables in order of preference or based on the application to be used by the AT. If the AT supports a CQI table preferred by the AP, the AT will notify the AP of one or more preferred CQI table it supports, 504 . If the AT does not support one or more CQI tables advertised by the AP, 505 , the AP may select its next preferred CQI table or tables, 508 . The AP would then advertise its next preferred CQI table, 502 . If the AT does support the CQI table, 505 , the AP selects the preferred CQI table, 506 , notifies the AT which CQI table to use, 510 , and the AP and AT may begin transmitting data with the appropriate packet format 512 . Alternatively, the AP may direct the AT of the CQI table to use, 510 . All AT(s) that support a high packet format may use a CQI table as desired by the AP to optimize the performance between the AP(s) and AT(s).
[0050] In yet another embodiment, the AP(s) may use the AT capability, system conditions, such as system loading, and type of deployment to advertise and/or decide which CQI table to use. Using these factors, the AP(s) may dynamically select which CQI table(s) to use to optimize performance between the AP(s) and AT(s). In another embodiment, the AP may simply send a high or low command to instruct the AT to use a high packet format or a low packet format. This may be useful for a heavily loaded AP.
[0051] Referring to FIG. 6 , a functional block diagram for selecting a feedback table 600 is illustrated. An indicator identifying at least one feedback table to use is received by the means for receiving, 602 . The means for selecting, 604 , selects a feedback table, from at least one feedback table, for quantizing channel information, wherein selecting is determined at least in part by the received indicator. The indicator is then transmitted by the means for transmitting, 606 .
[0052] Referring to FIG. 7 , a functional block diagram for selecting a feedback table 700 is illustrated. At least one first indicator identifying at least one feedback table from a plurality of feedback tables for quantizing channel information is transmitted by the means for transmitting, 702 . At least one second indicator identifying at least one feedback table is received by the means for receiving, 704 . A determination based at least upon whether the at least one feedback table identified by the at least one second indicator is one of the at least one feedback table identified by the at least one first indicator is made by the means for determining, 706 . A selection of a feedback table from the plurality of feedback tables based on the determination is provided by the means for selecting, 708 . The information associated with the selected feedback table is transmitted by the means for transmitting, 710 . The means for transmitting, 710 , may also be the same means for transmitting, 702 .
[0053] The word “exemplary” is used herein to mean “serving as an example, instance, or illustration.” Any embodiment described herein as “exemplary” is not necessarily to be construed as preferred or advantageous over other embodiments.
[0054] Those of skill in the art would understand that information and signals may be represented using any of a variety of different technologies and techniques. For example, data, instructions, commands, information, signals, bits, symbols, and chips that may be referenced throughout the above description may be represented by voltages, currents, electromagnetic waves, magnetic fields or particles, optical fields or particles, or any combination thereof.
[0055] Those of skill would further appreciate that the various illustrative logical blocks, modules, circuits, and algorithm steps described in connection with the embodiments disclosed herein may be implemented as electronic hardware, computer software, or combinations of both. To clearly illustrate this interchangeability of hardware and software, various illustrative components, blocks, modules, circuits, and steps have been described above generally in terms of their functionality. Whether such functionality is implemented as hardware or software depends upon the particular application and design constraints imposed on the overall system. Skilled artisans may implement the described functionality in varying ways for each particular application, but such implementation decisions should not be interpreted as causing a departure from the scope of the present disclosure.
[0056] The various illustrative logical blocks, modules, and circuits described in connection with the embodiments disclosed herein may be implemented or performed with a general purpose processor, a digital signal processor (DSP), an application specific integrated circuit (ASIC), a field programmable gate array (FPGA) or other programmable logic device, discrete gate or transistor logic, discrete hardware components, or any combination thereof designed to perform the functions described herein. A general purpose processor may be a microprocessor, but in the alternative, the processor may be any conventional processor, controller, microcontroller, or state machine. A processor may also be implemented as a combination of computing devices, e.g., a combination of a DSP and a microprocessor, a plurality of microprocessors, one or more microprocessors in conjunction with a DSP core, or any other such configuration.
[0057] The steps of a method or algorithm described in connection with the embodiments disclosed herein may be embodied directly in hardware, in a software module executed by a processor, or in a combination of the two. A software module may reside in RAM memory, flash memory, ROM memory, EPROM memory, EEPROM memory, registers, hard disk, a removable disk, a CD-ROM, or any other form of storage medium known in the art. An exemplary storage medium is coupled to the processor such the processor can read information from, and write information to, the storage medium. In the alternative, the storage medium may be integral to the processor. The processor and the storage medium may reside in an ASIC. The ASIC may reside in a user terminal. In the alternative, the processor and the storage medium may reside as discrete components in a user terminal.
[0058] The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the disclosure. Thus, the present disclosure is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein. | Techniques to enhance the performance in a wireless communication system using CQI feedback optimized to support different scenarios. According to one aspect, an access terminal may select a CQI feedback table based on the access terminals capability. According to another aspect, an access point may select a CQI feedback table based on an access terminals capability, system loading and the type of service provided by the access point. An access point which provides services that require high data rates may select a larger CQI feedback table to support the high data rates for access terminals which support the larger CQI feedback table. The same access point may select a smaller CQI feedback table for access terminals which do not have the capability or need for the high data rate services. | 7 |
FIELD OF THE INVENTION
The present invention relates to a method of optimising the functioning of a submerged arc furnace for producing molten metal.
BACKGROUND OF THE INVENTION
It is known how to use submerged arc furnaces (SAFs) for the production of ferro-alloys (Fe—Mn, Fe—Cr, etc.) and pig irons by the reduction and melting of charges of already partially pre-reduced ore, particularly by using coke as a reducing agent. It is also known how to use these SAFs for the reduction and melting of metallic residuary products, particularly metal powders which are charged in the form of fines, granules or pellets. The reduction and melting methods used in these SAFs are generally distinguished by a considerable production of slag; the mass of slag is often comparable with or even greater than the mass of metal. The bath of metal is consequently covered by a layer of molten slag of considerable depth (about 0.4 m to 1.50 m), which represents a charge of about 1 to 3.75 tonnes of slag per square metre of the bath. The electrodes of the SAF are located in the central zone of the furnace, while the charge is loaded into the peripheral zone, i.e. between the central zone with the electrodes and the furnace wall.
In the SAF, the heat energy required for melting the metallic products is generated by the conduction of the current through the molten slag. Consequently, there is no actual plasma arc (or free arc) set up between the electrodes and the bath of metal. The electrical power developed in an SAF is therefore only from 0.2 to 0.5 MW per m 2 of crucible surface area, which is a very low power compared with one of about 2 MW per m 2 of crucible surface area developed in free arc furnaces. Since the energy requirements for the reduction and melting of ferro-alloys or metallic residuary products are, on the contrary, very high, the result is that the productivity of SAFs currently leaves a lot to be desired.
Problem Underlying the Invention
It is therefore an object of the present invention to increase the productivity of a SAF.
SUMMARY OF THE INVENTION
The method according to the invention makes it possible to optimise the functioning of a submerged arc furnace for the production of molten metal. This electric furnace incorporates at least one electrode and contains a bath of molten metal covered with a thick layer of molten slag having a mass per unit area of at least 1 t/m 2 . According to an important aspect of the invention, the slag is made to foam locally around the electrode so as to create around this electrode a local layer of foaming slag in which the density of the slag is at least 50 per cent lower than in the rest of the furnace. If the furnace has several electrodes, the slag is preferably made to foam locally around all the electrodes in the furnace.
The method according to the invention offers the possibility of optimising the functioning of an electric SAF containing a large amount of molten slag, and particularly of increasing its productivity. In effect, the creation of a local layer of foaming slag changes the way in which the electric energy passes into the bath. Conduction of the electric current through the resistive molten slag is at least partially replaced by a “plasma” arc formed in a gaseous medium, even if this medium also includes a certain proportion of molten slag. It is possible in this way to improve the characteristics of the arc, i.e. the arc voltage and the length of the arc. The electric field in plasma mode immersed in a foaming slag is at least two to four times larger than in the resistive mode (conduction in the molten slag). As a result, there is an appreciable increase in the power of the SAF. Since the power is higher, it is possible to reduce the melting time and hence increase the productivity. Besides, the conditions for the production of molten metal in foaming slag are less severe than in molten slag. That is the reason for the lower consumption of the electrode or electrodes in the local layer of foaming slag.
The electric furnace may contain a bath of molten metal covered with a thick layer of molten slag having a thickness from 0.4 to 1.5 m. Preferably, the local layer of foaming slag surrounding the electrode comprises at least 50 per cent of gas, and optimally at least 80 per cent of gas.
Advantageously, the local layer of foaming slag is formed by the addition of at least one carbon-containing fuel and/or at least one oxidant, in or on said layer of slag and/or said bath of molten metal. The reaction of the carbon-containing fuel with the oxygen contained in the bath of molten metal produces CO, which causes the slag to foam. In addition, the combustion of the carbon-containing fuel provides an input of energy which is then added to the heat energy of electrical origin for the reduction and the melting. By injecting the gas containing oxygen into the top third of the layer of slag, post-combustion of the CO can be achieved, i.e. a reaction which also contributes to the input of heat energy.
According to a preferred mode of execution, the electric furnace comprises at least three electrodes located in the centre of the furnace. A local layer of foaming slag is then created between the three electrodes. In other words, the local layer of foaming slag surrounds each electrode and extends between the electrodes at the centre of the furnace.
Preferably, the raw materials are added mainly at the centre of the electric furnace.
According to a first mode of execution, the raw materials are added in the form of fines injected into the lower part of the layer of slag and/or into the bath of molten metal. It is, for example, possible to use this method to inject fines of pre-reduced iron ore.
According to a second mode of execution, the raw materials are added in the form of pellets or bricks. This makes it possible to introduce into the electric furnace raw materials that cannot be injected, by agglomerating them for example into pellets or bricks with a high enough density to penetrate the layer of slag.
BRIEF DESCRIPTION OF THE DRAWINGS
Other special features and characteristics of the invention will emerge from the detailed description of an advantageous mode of execution given below, as an illustrative example, making reference to the appended drawing. This shows:
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 : a cross-sectional view of a submerged arc furnace in which the method according to the invention is carried out.
FIG. 1 represents a cross-sectional view of an electric furnace 10 of the submerged arc type (SAF: Submerged Arc Furnace). A bath of molten metal 12 is received on to the hearth 14 of the furnace. A thick layer of molten slag 16 lies above the bath of metal. This layer of molten slag may reach heights exceeding 1.5 m. It represents a charge of about 1 to 3.75 tonnes per square metre of the bath of metal. Several electrodes 18 are placed at the centre of the furnace, two of which are visible in FIG. 1 . The bottom end of these electrodes is located well below the normal level of the slag in the hearth 14 .
It should be appreciated that the layer of molten slag 16 around the electrodes 18 is made to foam, so as to create a local layer of foaming slag 20 in which the density of the slag is at least 50 per cent lower than in the rest of the electric furnace. When the furnace has three electrodes, they are generally placed in a triangle at the centre of the furnace. The local layer of foaming slag is then formed so that it extends between the three electrodes and surrounds each of them. The local layer of foaming slag alters the way the electric current passes through the bath and the slag. It should be noted that the electrodes in this case are placed in a triangle, but they could also be in a straight line. In addition, the furnace could have more than three electrodes.
When the electrodes are surrounded by molten slag, the input of electrical energy is achieved by conduction. By creating a local layer of foaming slag around the electrodes, it is possible to form “plasma” arcs in a quasi-gaseous medium, which improves the characteristics of the arc. An electric field that would be 0.1 V/mm in resistive mode (conduction through the molten slag) may be increased to 0.5 V/mm in plasma arc mode in the local layer of foaming slag.
It should be pointed out that the method of the present invention is well suited to the production of molten metal from raw materials generating a lot of slag, for example, iron ore that is pre-reduced to a certain extent and metallic residuary products. Even with layers of molten slag with thicknesses of up to 1.5 m, it is possible to cause the slag to foam locally in the region of the electrodes. In this way, it is possible to take advantage of the conditions in which foaming slag is produced without any risk of overflowing.
In order to create the local layer of foaming slag, carbon and oxygen for example may be added to the bottom layer of the slag and/or to the bath of molten metal. FIG. 1 shows, for example, a lance 22 which is injecting a jet of solid carbon-containing pulverised material into the bottom third of the layer of slag 16 . The flow per unit time of solid carbon-containing pulverised material through the lance 22 is from 10 to 30 kg/min, keeping to a flow rate per unit area from 0.5 to 5 kg/min.m 2 , preferably 1 kg/min.m 2 . It is also possible to inject a primary jet of oxygen using a lance 24 into the bottom third of the layer of slag 16 . The flow rate of the oxygen is preferably proportional to the flow rate of the carbon, at a rate between 1 and 2 m 3 /kg. This primary jet of oxygen is intended to produce CO in accordance with the following reactions:
C (metal bath) +½O 2 →CO
and
Fe (metal bath) +½O 2 →FeO,
followed by
FeO+C (injected) →Fe+CO
A secondary jet of oxygen may be injected into the top third of the slag 16 (not represented), in order to burn the CO:
CO+½O 2 →CO 2
This post-combustion of CO releases a larger amount of energy than the combustion of C to CO.
It should be noted that the amount of oxygen injected is adjusted according to the amount of reducible oxides contained in the raw materials (metallic products to be reduced and melted). If the raw materials contain large amounts of oxides, for example FeO or NiO, the amount of oxygen injected to create the foaming slag can be reduced or even eliminated.
It is clear that the carbon added to create the foaming slag must be injected in addition to that necessary for the reduction of the charge and the decarburising of the metal.
Depending on the amounts of oxygen and carbon introduced into, and contained in, the bath 12 , it is therefore possible to vary the proportion of gas in the layer of foaming slag 20 . Care should be taken to ensure that a layer of foaming slag 20 is formed containing at least 50 per cent of gas, and preferably more than 80 per cent of gas.
The reference numbers 25 and 26 indicate a peripheral and central opening respectively in the roof 28 of the furnace 10 for the introduction of the raw materials.
The raw materials in the form of fines or granules are preferably injected in the bottom layer of the slag and/or at the interface (not represented) between the bath and the slag.
Raw materials incapable of being injected are agglomerated in the form of bricks or pellets and are introduced preferably through the central opening 26 . The bricks and pellets are fabricated so that their mass enables them to penetrate the layer of slag and so that they can break up easily.
In FIG. 1, the arrows 30 indicate the introduction into the furnace 10 of pellets 32 through the peripheral openings 25 and the central opening 26 .
Quantitative Theoretical Example
An existing SAF with a crucible diameter of 3.5 m (surface area of crucible ≈10 m 2 ) develops a power of 3 MW. For the reduction and melting of a charge of 1 tonne, an energy of 1500 kWh is required. When the SAF is operated conventionally (i.e. with a molten slag surrounding the electrodes), the electrical-to-thermal energy efficiency is about 0.7 and the “raw” productivity (excluding casting time and downtime) is
3000(kW)×0.7/1500(kWh/t)≈1.4t/h.
The injection near the electrodes of 10 kg/min of carbon with an energy content of 9 kWh/kg amounts to an input of
10×9×60=5400 kW.
By transferring energy from the carbon with an efficiency of 40 per cent, the productivity increases to
((3000×0.7)+(5400×0.4))/1500≈2.8t/h.
In addition, the release of CO near the electrodes forms a local layer of foaming slag surrounding the electrodes and hence promotes the establishment of a plasma arc. By boosting the electrical supply to the electrodes (change of transformer, with the same maximum current), the arc voltage may be doubled. The electrical power developed thus changes to 6 MW. By assuming that, to a first approximation, the electric-to-thermal energy efficiency is unchanged, the productivity of the furnace is potentially increased to
((6000×0.7)+(5400×0.4))/1500≈4.2t/h.
A calculation of the various consumptions enables some idea of the profitability of the method to be obtained. For the oxygen requirements, a rate of 1.5 m 3 of O 2 per kg of carbon is estimated.
In conventional functioning, the consumption is:
3000/1.4=2143 kWh/t.
By considering the input of energy from the solid carbon-containing pulverised material, the consumption is:
electrical energy: 3000/2.8=1071 kWh
carbon: (10×60)/2.8=214 kg/t
oxygen: 214×1.5=321 m 3 /t.
When functioning with the input of energy from the solid carbon-containing pulverised material and the plasma arc, the consumption is:
electrical energy: 6000/4.2=1428 kWh
carbon: (10×60)/4.2=143 kg/t
oxygen: 143×1.5=214 m 3 /t.
As these calculations show, 1 kg of C and 1.5 m 3 of O 2 are substituted for 5 kWh of electrical energy. This substitution hardly causes any additional running costs. However, the increase in productivity (from 1.4 to 4.2 t/h) is such that the method proves to be very profitable. | A method for producing molten metal by the reduction and melting of raw materials in a submerged arc type electric furnace includes at least one electrode, where substantial amounts of slag are generated so that the electric furnace contains a bath of molten metal covered with a thick layer of molten slag having a mass per unit area of at least 1000 kg/m 2 . The thick layer of molten slag is made to foam locally around the at least one electrode so as to create around the electrode a local layer of foaming slag in which the density of the slag is at least 50 per cent lower than in the rest of the electric furnace. | 8 |
The present invention relates generally to apparatus for controlling the environment in commercial work areas and, more particularly, to an arrangement for exhausting solid, liquid, or gaseous pollutants, especially exhaust gases from an internal combustion engine, from a work area such as a garage or automotive repair facility.
The invention is particularly directed to the type of apparatus wherein a longitudinal stationary duct is provided with an exhaust hose attached thereto by means of a bearing bracket wherein the bearing bracket may engage with areas in the stationary exhaust duct through a suction slot provided with sealing elements, and wherein the sealing elements may be moved by the bearing bracket from a position sealing the suction slot to a position releasing the suction slot and vice versa.
Known devices of the type to which the present invention relates are generally used in vehicle workshops or vehicle depots and consist of suction ducts installed in the region of the ceiling of the workshop and connected with an exhaust ventilator. The suction ducts include a track on their interior at which the suction carts or bearing brackets are movably arranged. The underside of the suction ducts, which permits passage of the suction carts, is constructed as a suction slot sealed by sealing lips such as packing washers located at an angle relative to each other, wherein during movement of the suction carts, the sealing lips are moved apart and are again joined closely together after the suction cart has passed therethrough.
Such arrangements are especially disadvantageous due to the fact that after long use, the sealing lips, which are made of a rubber-like material, will lose their sealing effect because of fatigue. As a result, the exhaust ventilator will draw in more and more outside air and the unit will become ineffective.
Additionally, the sealing lips are usually only heat resistant to a very limited extent and therefore the units are not suitable for high performance test stands or similar equipment. Known units also have the disadvantage that, if the hose carts are arranged with insufficient space between each other, the sealing lips will no longer completely close so that even with intact sealing lips, a high volume of outside air will be drawn in.
The present invention is directed toward the provision of a solution with which a unit may be created by economical means which will be especially suitable for use in dealing with harmful substances having high temperatures where the sealing means of the suction duct will not be subjected to excessive wear and wherein it will be possible for the hose carts to follow each other in close succession.
SUMMARY OF THE INVENTION
Briefly, the present invention may be defined as apparatus for removing pollutants, particularly automotive exhaust gases, from work areas or the like comprising elongate stationary duct means for exhausting pollutants therethrough, exhaust hose means adapted to receive pollutants operatively connected with said duct means, bearing bracket means longitudinally movable along said duct means connecting said exhaust hose means with said duct means, and displaceable sealing means on said duct means adapted to be moved by said bearing bracket means between a position sealing said duct means and a position allowing said hose means to be placed in flow communication with said duct means as said bearing bracket means is moved along said duct means.
In accordance with the present invention, the displaceable sealing means comprise sealing elements which are constructed as link elements of heatproof material. These links are connected to each other and are movable relative to each other and they are preferably slideable in the longitudinal direction or transverse to the direction of movement of the bracket means, with the link elements being guided at the suction duct.
With the link elements according to the invention, very effective sealing of the suction duct is possible in a simple manner wherein simultaneously the opening and closing of the suction slot necessitated by the bearing bracket means can be undertaken in an especially easy and effective manner.
In order to prevent problems which may arise from the use of sealing lips, the invention provides a sealing effect by means of the link elements connected with each other which, depending upon their construction, can be manufactured of suitable material, and which need not have only a mere sealing function, but which may also guarantee the mobility of the entire seal.
In an embodiment in accordance with the invention, it is provided that the link elements are connected with each other so that they can slide in the longitudinal direction wherein it can be provided in another embodiment that a longitudinal end face of the link element is constructed to engage behind the corresponding end face region of the adjoining element. This embodiment makes it possible to cover the suction slot in such a way that it is practically totally prevented from receiving any flow of outside air.
It has proven to be practical for the link elements to be provided each with a roller which may be acted upon by a coulisse surface at the bearing bracket or hose cart, wherein the hose cart is preferably equipped with a guide track for the positive guidance of the rollers at the link elements.
With this embodiment, preferred in accordance with the present invention, i.e., with a control portion at each link element which makes lifting and lowering possible and with a positive guiding function for the control hose at each hose cart, false actuation of the elements is precluded. Moreover, movement of the hose carts or bearing brackets will be especially facilitated when the control portions are constructed as rollers which are positively guided in a control template at the inside of the hose cart of the portions duct.
It is particularly practical if, as is also provided in accordance with an embodiment of the invention, fixation of the link elements at the suction duct involves at least one link element equipped with a guidance. This guidance can be constructed, for instance, as a guide rod engaging into the hollow space of the profiled link element, as is described hereinafter.
Basically, it is possible to arrange the suction slot at any side of the suction duct, for instance at the underside thereof, and to form the sealing elements with two chains of link elements which are moved if appropriate against the spring tension of the hose carts. However, the invention intends to provide an embodiment where the suction slot is arranged at a lateral, essentially vertical wall of the suction duct. This embodiment has the advantage that only one chain of link elements is needed for sealing of the suction duct. The suction cart moves under the chain and lifts the links against the direction of the force of gravity.
Since the series of curves, resulting from lifting of the link elements, usually has a slightly larger bending radius than that of the suction nozzle which effects this movement, openings will result between the suction nozzle and the lower edge of the adjoining link elements through which basically outside air could be drawn in. Therefore, the invention provides that the hose cart or bearing bracket is provided with a sealing disc which can be moved parallel to the suction slot and which covers the opening resulting from the lifting of the link elements wherein the suction nozzle is guided through this sealing disc. Consequently, the sealing disc prevents outside air from flowing in so that the full suction efficiency of the system will be ensured independent of the position of the hose carts.
In accordance with the invention, it may also be provided that the guide profiles for the link elements and the tracks for the hose carts assigned to these elements may be constructed by one upper and one lower profile attached at the suction duct and preferably made of light metal wherein the hose carts are preferably guided on an endless track through the intermediary of the suction duct provided with inlet and outlet sluices.
A further goal of the invention is the creation of a solution wherein a hose cart can be moved independently of the curvature of the track, the slope of the track or the distance of the track, and independently of adjoining hose carts insofar as free mobility is possible.
The invention therefore contemplates that the hose carts be guided at another guide track together with the drive unit and that they are permanently connected with the drive unit in a positive locking manner.
As a result of this capability, each hose cart may be provided with its own drive in such a way that, in addition to being controlled separately and being capable of movement in both directions along a guide track, it is also independent of the radii of curvature of the guide tracks, i.e., extremely small radii of curvature can be driven with the unit according to the invention which leads to a very compact construction of the entire system equipped with this unit. Additionally, it is a special advantage that known systems of conventional construction can be equipped subsequently with a device in accordance with the invention without requiring complicated modifications of the individual hose carts.
The invention provides, in an embodiment thereof, that the driving device be equipped with a driving motor and with an undercarriage, movable in another guide track and carrying a friction drive, wherein it may also be provided that the undercarriage is connected with a hose cart by means of a joint element having a joint axis aligned essentially perpendicularly.
It has been shown that in order to balance especially narrow radii of curvature, it is advantageous to have the undercarriage of the drive and the hose cart with the rollers supported in another guide track whose suspension is constructed to be rotatable with respect to the undercarriage and the hose cart.
In fields other than those related to the present invention, drives movable in tracks which pull other parts of a unit are already known. For example, known apparatus exists having an electromotor friction drive for a supply cable to be pulled. In drives of this type, the friction wheel will run in the interior of a support track constructed as a hollow track with an essentially C-shaped configuration. In structures of this type, disadvantages arise in that total symmetry of construction of all parts of the system is necessary in order to prevent tilting of rollers. Also, a friction wheel running inside requires very large radii of curvature of the track.
However, in the present invention, it is provided that the driving device be formed with a horizontally aligned electric motor and a friction drive running on another guide track wherein, in a special embodiment, it can be provided that the friction wheel to balance out a radius of curvature of another side track has a greater width than the effective area of another guide track in contact with the friction wheel.
These measures in accordance with the invention have the advantage that very small radii of curvature of the guide track are possible.
For the transfer of large frictional forces from the driving motor via the friction wheel to the guide track, it is also provided in accordance with the invention that the profile of the friction wheel at its contact surface be equipped with a center apex arranged approximately symmetrically, a radius of curvature or similar in such a way that the friction wheel can engage with an area that projects slightly from the profile into the motion slot of the guide track.
For exact dosing of the frictional force of the friction wheel at the track, it is provided in accordance with the invention that the rollers of the driving unit be adjustable in their distance from the undercarriage so that, due to change of the distance between the rollers and the undercarriage relative to the guide track, the friction wheel which is stationary with respect to the undercarriage can be stressed against the track.
Another essential feature of the invention consists in that the working planes of the joint, connecting the hose cart and the driving device in positive locking manner be arranged offset in steps with the mass centers of the hose cart on the one hand and the driving device on the other hand being arranged always on different sides of the guide track. Due to these measures, the entire system is balanced with regard to weight to that it can move without special guide elements from the other guide track directly to the tracks at the suction duct with additional guide rollers.
In accordance with a further embodiment of the invention, the stationary duct means may have connected thereto elongate movable duct means with the exhaust hose means being connected through the bearing bracket means and through the displaceable sealing means with the elongate movable duct means. The movable duct means are connected with the stationary duct means by similar bearing bracket means and sealing link elements so that the movable duct means, with the exhaust hose means movably connected thereto, may be, in turn, longitudinally moved in flow communication along said stationary duct means.
In this embodiment of the invention, features of particular advantage arise in that greater mobility of the exhaust hose means results in that all points in a workshop or similar area may be reached with the apparatus. Furthermore, each location where the apparatus may be used can be better controlled and free mobility is provided first in an x/y plane and ultimately in an x/y/z space. This embodiment of the invention has the advantage that, due to the assignment of a stationary suction duct and the effective connection of the movable suction duct with the hose carts of the exhaust hose means, in turn movable at the suction duct, large surfaces can be covered wherein the entire system is especially suitable for automated control.
In accordance with some of the more detailed features of this embodiment of the invention, the stationary and the movable suction ducts may be constructed in an identical form thereby making prefabrication during manufacturing possible, which will provide an especially economical structural arrangement. The hose carts of the movable duct may be connected with the movable duct by means of a flexible hose. It is advantageous to attach the movable suction duct with the stationary suction duct at a longitudinal end of the movable suction duct, which end may have a suction cart rigidly attached thereto.
In order to effect automated control of this embodiment, it is considered especially practical to provide suction carts and/or the additional suction duct and/or the hose carts with their own drive means wherein the drive means may, for instance, be comprised of double-acting pneumatic cylinders without piston rods or other driving means for example endless chains, spindles, electromotive drives or the like. The assignment of effective suction openings at the hose carts for each point in the space can be realized either by lifting and lowering of the suction openings at the hose of the hose carts or by providing a third suction duct.
The various features of novelty which characterize the invention are pointed out with particularity in the claims annexed to and forming a part of this disclosure. For a better understanding of the invention, its operating advantages and specific objects attained by its use, reference should be had to the accompanying drawings and descriptive material in which there are illustrated and described preferred embodiments of the invention.
DESCRIPTION OF THE DRAWINGS
In the drawings:
FIG. 1 is a perspective view of a portion of the exhaust apparatus in accordance with the present invention showing the suction duct with the hose carts arranged thereon to be movable relative thereto;
FIG. 2 is a top view of the link element of the invention shown on an enlarged scale;
FIG. 3 is a side view of the link elements shown schematically as they are being lifted by the hose cart or bracket means;
FIG. 4 is a sectional view taken along the line IV--IV in FIG. 5;
FIG. 5 is a lateral view of an arrangement in accordance with the invention shown with a driving unit;
FIG. 6 is a simplified schematic view showing the system in accordance with the embodiment of FIG. 5; and
FIG. 7 is a simplified lateral view of apparatus in accordance with a further embodiment of the invention which is shown partly in section.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to the drawings, wherein similar reference numerals are used to designate like elements throughout the various figures thereof, apparatus for the exhaust and removal of harmful substances is shown and identified in its entirety by reference numeral 1. The apparatus consists essentially of an elongate stationary suction duct 2 having an essentially rectangular cross section which is installed, for example, in the region of the ceiling of a workshop or automobile repair shop. The suction duct 2 is connected by means of a suction opening 3 with an exhaust ventilator 4.
The suction duct 2 is equipped with a vertical wall 5 having a suction slot 6 which is closed by a plurality of essentially beaver-tail shaped link elements 7 (see FIG. 3) or rectangularly shaped link elements 8 (see FIG. 5).
The link elements 7, 8 are alternately arranged in overlapping relationship and the link elements may be made of plates of metal or asbestos cement or other heatproof materials.
In order to provide guidance for the link elements 7, 8, the vertically extending lateral wall 5 is profiled in a manner depicted in FIGS. 1 and 4. At its bottom part there are formed two short guide bars 10, while in the top region thereof, two long guide bars 11 are provided within which the link elements, as shown especially in FIGS. 3 and 5, can be lifted up to a distance so that below them a suction nozzle 12 or 12' may be moved, as will be further described hereinafter.
In addition to the short guide bars 10, an outwardly and upwardly directed track 13 is formed in one piece in the lower region, with an outwardly and downwardly directed track 14 being formed in the upper region of the wall 5. Rollers 16, 16' arranged in bearing blocks 15 run on the tracks 13 and 14 (FIG. 4). The bearing blocks 15 are fastened to a sealing disc 17 which is slideable in the plane of the vertical wall 5 by means of rollers 16 wherein the suction nozzle 12, 12' is guided through the sealing disc into the interior of the suction duct 2, as is evident from FIG. 4.
As will be seen especially from FIG. 2, the link elements 7 are connected with each other so as to be slideable in the direction of their longitudinal dimension, with the link elements alternately engaging on opposite sides thereof by means of a dovetail-shaped longitudinal slot 28 and on the other side by means of a longitudinal projection 29 engaging in the longitudinal slot. The link elements are made of metal, asbestos cement, or any other heatproof material. The embodiment illustrated relates to hollow aluminum profiles. As can be seen especially in FIG. 2, each link element 7 is provided with a roller 32, if appropriate, running in ball bearings which are directed to the interior of the duct 2. When the hose cart 23 and consequently the guide disc 30 are moved in the interior of the duct, then the rollers 32 engage one after the other with the guide track 31 and effect lifting and lowering of the laterally guided link elements 7, 8 in the direction of the double arrow 33 seen in FIG. 3. The link elements 7 are formed with an angular configuration at the lower ends thereof so that a point contact region 34 is provided.
The link element 7' (FIG. 3) is held at the suction duct by means of guide rod 35 in such a way that it can move in the direction of the double arrow 33. However, movement in the driving direction of the hose cart 23 is prevented.
As an additional seal to prevent outside air from entering the duct 2, there is provided in the embodiment shown at the sealing disc 17 sealing rollers 36 whose width corresponds to the width of the suction slot 6.
In FIGS. 1 and 4, there is depicted an arrangement wherein the entire duct 3 is constructed from individual sections wherein the rear wall section 37, which can be adjusted as to size to specific requirements and may, if appropriate, be made of aluminum sheets, is arranged so it can be fixed by means of clamping sections 38 at the track sections 39 or 40 which are of the same construction in all embodiments.
The suction duct can be equipped with inlet and outlet sluices 41a which make it possible to utilize an endless movement of several hose carts, which is not shown in detail.
In the modified embodiment according to FIGS. 5 and 6, the hose cart 23 is connected in a positive locking manner by means of a joint element 43 with a driving device 42.
The hose cart 23 is, in addition, movably arranged in another guide track 41 by means of rollers 47, and the driving device 42 is also equipped with rollers 48 running in the same guide track 41. The rollers 47 and 48 are mounted to be pivotal about vertical axes 49 and 49', as seen in FIG. 5, at the respective parts of the devices.
The joint element 43 is arranged in such a way that its swivel axis 50 is also essentially vertically aligned. As will be seen from FIG. 5 and in connection with FIG. 6, the joint element 43 is arranged relative to the guide track 41 at the hose cart 23 and the driving device 42 in such a way that the centers of gravity of the two device elements 23 and 42, identified in FIG. 6 with reference numerals 51 and 52, are arranged each on one side of the guide track 41.
The driving device 42 consists essentially of an undercarriage 46, an electric motor 44 arranged at the undercarriage, a gearing 57 and a friction wheel 58. The rollers 48 at the undercarriage 46 of the driving device 42 can be changed with regard to their spacing in such a manner that the friction wheel 58 may be stretched against the under side of the guide track 41 so that contact pressure can be varied. The electric motor 44 is supplied with energy over another contact rail 59, indicated in FIG. 4, but not described in greater detail.
Of course, the embodiments described may be changed in various ways without departing from the basic concepts of the invention. The invention is especially not limited to the selected suspension of the hose cart and the driving device, and it is also not limited to the specific forms of the link elements shown. In addition to the shown vertical position of the suction slot, a horizontal arrangement can also be used for the sealing of the suction duct, for example, with two rows of spring loaded sealing elements. This variation makes it possible to also install the suction duct in the floor area of a workspace.
The invention is also not limited to the dovetail projection 28, 29 of the individual elements 7, 8. It will be apparent that other types of connection may be utilized which will guarantee longitudinal guidance of the link elements.
Additionally, the driving device 42 shown in FIG. 5 may also be installed, for example, in a piggyback arrangement on the suction nozzle 12' wherein a suspension may be selected in such a manner that it may be moved vertically to the conveying direction for radius compensation when extending through a curve, or a friction roller can be used in place of the friction wheel. For compensation during movement through a curve, the undercarriage 46 can be equipped with a double joint.
A further embodiment of the invention is depicted in FIG. 7. The exhaust apparatus shown in FIG. 7 is identified in its entirety by the reference numeral 1" and is formed in the example illustrated with a stationary elongate suction duct 2' which has operatively connected therewith a suction cart 60. The suction cart 60 is arranged to be movable in the longitudinal direction of the stationary duct 2' and another movable elongate suction duct 61 is joined with the stationary duct 2' by means of the suction cart 60 which is joined with the movable duct 61 through a suction nozzle 62. As a result, the entire movable duct 61 may move along the longitudinal direction of the stationary duct 2' in a direction perpendicular to the plane of the drawing of FIG. 7.
The suction ducts 2' and 61 are formed essentially with the same construction. However, they may of course have different dimensions, particularly with regard to their effective cross-sectional areas. The dimensions will depend upon expediency and the required suction capacity. In view of this, only one suction duct is described, the description being intended to apply to both ducts. Additionally, the function and construction of the suction cart 60 and of the hose cart 23, which is connected with the movable duct 61, are basically the same and in one case a suction nozzle 62 which is flanged at the end face of the suction duct 61 is attached at the suction cart 60 and in the other case a suction cart 63 with an open suction funnel 64 is attached at the hose cart 23.
In FIG. 7, the suction cart and the hose cart are shown only schematically in a simplified form. The carts are guided to be movable at the suction duct in guide tracks 13' and 14' with rollers 16' and 16" which are arranged at a sealing plate 17. The suction nozzle 12" is guided with a region 65 into the interior of the suction duct and this region carries a coulisse disc 30' which is equipped with a coulisse track 31' whose function was previously described in detail. In the example illustrated, an arm 66 is welded to the sealing plate 17 and the arm is connected with a driving element 67 of a double-acting hydraulic cylinder 68 so that when the driving means 67 is moved, the suction cart or the hose cart is also moved because the hydraulic cylinder 68 is stationarily connected at the suction duct.
Control circuits parallel to the hydraulic cylinder 68 for the attachment of solenoid-operated switches or similar devices to control the positions of each element are not further shown in FIG. 7. The electrical connections, for instance connections made through cables 69 and 70, are only indicated schematically in FIG. 7, this applying also to sensor switches 71 at the suction funnel 64 which stop the movement of the exhaust apparatus when, for example, an obstacle is encountered. A control panel 72 with, for example, a plurality of positions which may be approached by means of switches 73 is also indicated only schematically in FIG. 7.
The movable suction duct 61 is guided at the end opposite the end thereof connected to the suction cart 60 in a stationary track 74 by means of rollers 75. Driving means may also be provided, for example, in this area, which driving means are not further described. In addition to the suspended construction, the free end of the suction duct 61 may also be guided, for example, by means of sliding elements so as to rest upon a sliding track or the like.
In the operation of the apparatus depicted in FIG. 7, during use of the mechanism in, for example, a brake test stand or efficiency test stand of a specific automotive installation, it is possible because of the types of automobiles in the program, based upon specific exact positions of the rear axle on a roller test stand, to determine exactly in advance the position of each individual exhaust of the different types of vehicles with respect to this roller stand and to feed them to an electric circuit. When driving the vehicle to the roller test stand, a driver may actuate the control panel 72 through the window of the vehicle in accordance with the type of vehicle involved and the suction funnel 64 will be moved by means of an appropriate circuit from a parking position automatically to the exhaust of the vehicle.
If the incorrect type of vehicle is erroneously programmed, then a sensor switch 71 will prevent further movement of the exhaust apparatus 1" if, for example, the vehicle which is actually on the test stand is much longer than the vehicle programmed. The apparatus may then, for example, be moved back into the parking position and subsequently into the correct position. The same circuit may also respond to height (z-axis) which, however, is not shown in FIG. 7.
The apparatus may also be arranged, for example, on the arms of automatic welding machines carrying welding electrodes and it can move with these arms in accordance with the control provided so that harmful substances resulting during welding or cutting may be drawn in directly at the place where they originate because the suction ducts will also be suitable for high temperatures.
Of course, the embodiment described may also be modified in several aspects without neglecting the basic concept of the invention. The invention is especially not limited to a specific type of drive of the individual elements and it is also not limited to the preferred installation in one plane. For example, the apparatus can be equipped to first sweep over a vertical wall of the shop if this should be feasible, depending upon the machine tools or the sources of harmful substances which may be encountered.
While specific embodiments of the invention have been shown and described in detail to illustrate the application of the inventive principles, it will be understood that the invention may be embodied otherwise without departing from such principles. | Apparatus for removing pollutants, particularly automotive exhaust gases, from work areas or the like is formed with an elongate stationary duct for exhausting pollutants therethrough and with a bearing bracket longitudinally movable along the stationary duct for connecting an exhaust hose to the duct adapted to receive pollutants. By movement of the bearing bracket along the duct, the exhaust hose may be moved to any one of a number of desired locations. The stationary duct is formed with displaceable sealing elements which are moved by the bearing bracket between a sealing position and a position allowing the hose to be placed in flow communication with the stationary duct as the bearing bracket is moved along the duct. Alternatively, the exhaust hose may be connected with a second elongate duct which is itself movably connected with the stationary duct through displaceable sealing elements. | 1 |
FIELD OF THE INVENTION
Apparatus for pitting a whole drupe with a pitting knife which removes the pit or stone by forcing it through the body of the drupe. The term "drupe" refers to a fleshy fruit or vegetable such as a peach, plum, date, cherry, avocado or olive, usually having a single hard stone (or "pit") that encloses a seed. More particularly, the invention provides at least one knife having a novel structure designed to provide a method for removing undesirable contaminants from within a generally axial passage left when a drupe is pitted. Such contaminants include the eggs of an insect such as a moth, or larvae of the insect, or the excretions of the larvae left during the period of their development, until the larvae can leave as a moth. These contaminants are not removed from within the passage formed by currently available or known pitting machines.
BACKGROUND OF THE INVENTION
Machines which automatically pit a drupe have laid the foundation for an agribusiness which makes it possible for a person with even less than average income to enjoy fruits and vegetables which would otherwise be consumed only by the wealthy. Such machines are the subject of U.S. Pat. Nos. 2,157,518; 2,219,832; 2,630,205; and 2,688,352 to Ashlock, Jr.; of U.S. Pat. Nos. 3,153,473; and 3,556,281 to Margaroli et al.; and of U.S. Pat. Nos. 4,090,439 and 5,577,439 to Chall et al. and Cimperman et al., inter alia. Such machines have successfully achieved in the U.S. what is still done manually in countries where human labor is relatively inexpensive.
In the aforementioned pitting machines, a pitting knife or an assembly of plural pitting knives in a pitting head, cuts through the skin and flesh of the drupe being pitted, ejects the stone, and is then retracted leaving a substantially central passage in the drupe.
When a moth chooses a drupe to nurture its progeny, it lays its eggs on or near the drupe, typically on its upper surface. The eggs progress to the larva stage. The time it takes an egg to get to the larva stage typically corresponds uncannily to the period during which the drupe ripens. As the drupe ripens, a portion of its skin immediately surrounding its stem, tends to pull away from the stem and at some stage, may do so, leaving a narrow passage through which a larva burrows its way into the flesh of the ripe drupe. The larva feeds on the ripe flesh of the drupe, and as the larva matures, its excretions, referred to as "frass", build up within the now contaminated drupe. When the contaminated drupe is harvested and pitted, the frass, if not the larva itself, is left behind in the passage within the pitted drupe because a pitting knife cannot remove the frass even if it successfully ejects the larva with the pit.
United States Standards for Grades of Dates specifies a defect when an unacceptable percentage of dates are "affected by insect infestation--presence of dead insects, insect parts, or excreta "frass" (no live insects are permitted)."
A typical harvest may include from relatively few, to an economically disastrous percentage of contaminated fruit, and the extent of contamination can only be estimated by inspecting a large number of individual fruits. To date, when contamination is extensive, contaminated fruit has been disposed of as garbage, because there is no economical method of decontaminating the fruit. Worse, since it is currently impractical to sort contaminated fruit from uncontaminated fruit, marketable fruit is discarded along with the contaminated fruit.
When contamination is not extensive, the problem of removing the contaminants from within a pitted drupe has been addressed, unsuccessfully for the most part, by soaking the fruit in water, or passing the pitted fruit under a cascading stream of water, with the faint expectation that some of the water will enter the pit-free passage and flush away the frass. Besides being only marginally effective, both methods result in dissolving or otherwise sacrificing an unacceptably large portion of a fruit, such as a date or a prune, which typically has a relatively high water-soluble sugar content.
A pitting knife is usually made from hard stainless steel. Typically, plural pitting knives are mounted in a knife assembly held within the confines of a pitting head which houses the driving mechanism for timing and thrusting the knives into rows of fruit individually held in chucks, which are in turn, mounted on carriers carried by a conveyor belt. One does not expect to use a pitting knife for any purpose other than its designated purpose. One does not consider boring a pitting knife. Nevertheless, this invention does so; and thereby provides for contacting the S walls of the passage of a pitted drupe with a decontaminating quantity of a decontaminant fluid, thus providing an effective solution to the problem of drupes internally contaminated with contaminants such as "frass".
SUMMARY OF THE INVENTION
It has been discovered that a pitting knife for a drupe may be provided with a longitudinal bore through which a decontaminant or cleansing fluid is discharged in a generally radial direction (relative to the longitudinal axis of the knife) to cleanse a pitted drupe. Use of the fluid during pitting has the added benefit of minimizing build-up of particles and remnant pieces of fruit adhering not only to portions of the pitting head but also to the chucks of fruit holders carried by the conveyor.
It is therefore a general object of this invention to provide an elongated pitting knife having a longitudinal bore and at least one generally radially extending bore in open communication with the axial bore and the knife's outer surface; and means for supplying an effective quantity of decontaminant fluid to the axial bore, the fluid being under sufficient pressure to be ejected generally radially from the knife so as to contact the walls of the pitted passage.
It is a specific object of this invention to provide an assembly of plural knives each having an axial bore; the knife essentially simultaneously pits plural drupes to leave a pitted passage in each, and cleanses the passage; the assembly is connected with a means for supplying a decontaminant fluid to the knives; the fluid flushes each passage with sufficient cleansing fluid to remove contaminants from the passage.
It is also a specific object of this invention to provide (i) an assembly of plural conventional pitting knives which together first pit drupes to leave a pitted passage in each, and, (ii) an assembly of cleansing rods positioned after the assembly of pitting knives, which cleansing rods supply sufficient decontaminant fluid discharged under sufficient pressure to contact the walls of the passage left by the ejected drupe and cleanse them. "Cleansing rods" are longitudinally-bored pitting knives having the primary function of providing cleansing fluid, rather than a cutting function. Cleansing rods are so termed, rather than "cleansing knives", to emphasize the cleansing function, and to distinguish over "pitting and cleansing knives" which also have a cleansing function. Such sequential pitting and cleansing may be accomplished in a single pitting head, or in multiple pitting heads arranged serially along the path of the conveyor for the carriers. Alternatively, in another sequential operation, a first set of plural rows of pitting and cleansing knives may be succeeded by a second set of plural rows of cleansing rods the function of which is to provide a moisture-removing gas ("drying gas") from within pitted and cleansed passages. The cleansing rods thus function as "drying rods". As before, the pitting and cleansing knives, and drying rods, may be mounted in a single assembly in a single pitting head, or for sequential operation, in two assemblies in separate pitting heads.
It is another specific object of this invention to provide a method for decontaminating a drupe which is internally contaminated, comprising, inserting a pitting knife within the drupe, ejecting a pit from within the drupe leaving a passage therewithin, flowing a decontaminant fluid through the pitting knife, and, ejecting the fluid in a generally radial direction, to contact walls of the passage, thereby flushing out contaminants; the fluid may be a liquid, or a gas, or a mixture thereof; the liquid may be water or an aqueous decontaminant, e.g. a solution of hydrogen peroxide; the gas may be ozone.
BRIEF DESCRIPTION OF THE DRAWING
The foregoing and additional objects and advantages of the invention will best be understood by reference to the following detailed description, accompanied with schematic illustrations of preferred embodiments of the invention, in which illustrations like reference numerals refer to like elements, and in which:
FIG. 1 is a side elevation diagrammatically illustrating a pitting mechanism and a portion of a conveyor means carrying rows of carriers.
FIG. 2 is a section taken along the lines 2--2 of FIG. 1 providing a plan view a pitting mechanism and a portion of an endless conveyor carrying a multiplicity of carriers.
FIG. 3 is an end elevation view of an assembly of pitting knives, each knife, one of which is shown in cross-section, having a longitudinal axial bore terminating at its lower end, and plural, generally radially extending bores in open fluid communication with the longitudinal bore.
FIG. 4 is an end elevation view of a single pitting knife for use in a pitting head in which a single pitting knife is mounted, and in which head a connection to a source of fluid at the upper end of the knife is not restricted.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The invention is described herebelow with particular reference to decontaminating dates contaminated with frass, and to pitting knives used in commercially available machines for pitting dates. It will be appreciated that the invention extends to any drupaceous fruit or vegetable prone to contamination in a zone contiguous to the drupe's stone. Frass is introduced by an external source such as an insect, and is deposited in a zone surrounding the stone or pit. No claim is made to the overall machine but only to the pitting and cleansing knife and the assembly of pitting and cleansing knives, and the method for decontaminating the drupe using a cleansing rod which is inserted within a pitted drupe.
A conventional pitting machine holds each drupe in a chuck. To date, a highly favored machine such as the one described in U.S. Pat. No. 3,556,281 uses plural chucks aligned in a carrier or fruit holder, and plural carriers are secured in a chain-driven endless conveyor means. A pitting head, positioned near one end of the conveyor, thrusts an assembly of pitting knives downwardly; each knife is thrust into a fruit held above a pitting rubber in a chuck so that the knives are in one-to-one correspondence with each fruit as it goes through the flesh of each fruit to eject its pit. The pitting head and conveyor are driven by a motor with interconnecting speed reducer and drive sprockets mounted on shafts journalled for rotation in the side members (plates) of the frame. The pitting head or guideway for the pitting mechanism is moved forward in the direction of advance of the carrier, and at the same time, the guideway is advanced downwardly toward the carrier, to allow the pitting mechanism to pit fruit on the carrier. The pitting mechanism thus moves horizontally forward over the carriers and conveyor at a rate such that the pitting mechanism is held directly above a selected carrier. While so held, the mechanism is lowered to engage and pit fruit on the carrier, thereafter being raised out of engagement, whereupon the head is returned to a point of beginning, from which the pitting head is again moved forward above another carrier. This operation is explained in detail in the '832 patent and will be summarized hereunder in relation to the drawing taken from the '832 patent only to provide a clear understanding of the framework within which my invention operates.
Operation with an assembly of pitting and cleansing knives for substantially simultaneous pitting and cleansing:
Referring to FIGS. 1 and 2, a conventional pitting machine such as one described in the '832 and '281 patents, includes an endless chain-drive conveyor 10 carried within a frame 16. Secured on the conveyor are plural fruit carriers or holders 19 each having several chucks 24 within each of which an individual date (not shown) is held, typically with its major axis in a vertical plane. Details of a holder and the spring-actuated chucks are disclosed in the '281 patent. Each knife 26 is elongated having a mounting end and a terminal end which is thrust through a date and against the pit within it. When knives 26 are lowered further, each knife pushes the pit out of the date, and through a passage 25 in a rubber member of the fruit carrier 19.
Oppositely disposed, vertical side members 51 are supported on frame 16 and connected above by member 52. The pitting mechanism is supported by rods 54 through the side members 51 and secured with nuts 53. Between the side plates 51 is a head or guide structure which includes horizontal plates 55 spaced apart by spacers 56. Each plate near opposed sides thereof, carries a V block 58 engaged with V rollers 59 journalled for rotation on stub-shafts 61 secured in each side member 51 in a horizontal plane. The V blocks and V rollers support the head structure provided by plates 55 for a reciprocating movement between the side members, toward and away from the carrier structure.
A vertical shaft 62 slidably held in bearings 63 in plates 55 allows the head structure to be reciprocated due to an eccentric follower 64 carried by the shaft 62. Within the eccentric follower 64 is an eccentric 66 rotated by shaft 39. Shaft 39 is driven by a suitable drive mechanism (not shown) so that upon rotation of shaft 39, eccentric 66 reciprocates the head structure over an angular path.
Each V block 58 has an angular V section 100 which engages an associated supporting V roller. The V block surfaces are positioned so that the head reciprocates toward and away from the carrier.
The pitting head structure includes two plungers 71 journalled in bearings 72 secured to plates 55. Near rod 54 carries fixed arms 74 which extend to provide support for spaced levers 76 between which is mounted cam follower 77. Each spaced lever 76 is slotted near its distal end to provide slots 78 within which rollers 79, carried upon plungers 71, are rotatably engaged. Cam follower 77 is maintained in engagement with cam 81 carried on shaft 39, spring 82 engages pad 80, which joins levers 76, the spring urging levers 76 clockwise in FIG. 1 so that the cam follower engages the cam at all times.
Extending between plungers is a mounting plate 91 which carries an assembly of pitting knives 26 arranged in successive rows, in the direction of travel of the conveyor, the number of knives in each row across plate 91 corresponding to the number of chucks in each carrier. This arrangement ensures that dates held in plural carriers are pitted substantially simultaneously.
As shown, but not necessary for operation, is a cleaning plate 93 yieldably secured to mounting plate 91 by bolt 94, springs 96 urging the plate 93 away from plate 91. The pitting knives advance through apertures in the cleaning plate 93, engaging fruit held in the chucks of the carriers. Extensions 95 on mounting plate 91 engage the carriers and move with them. When the pits are pushed through apertures 25 in the carriers, the knives are cleaned by the plate 93 as they are withdrawn.
Referring to FIG. 3 there is shown an end elevation view, that is, viewed from the discharge end of a conveyor carrying fruit holders, an assembly, referred to generally by reference numeral 200, of pitting and cleansing knives 201 removably securely held in a plate 210 carried by plungers 71 in a pitting machine more fully described in the aforementioned '281 patent. The conveyor is fitted with 4 chucks in a row, equidistantly spaced-apart along a lateral axis (at right angles to the horizontal axis), and the assembly 200 includes 8 pitting and cleansing knives 201 arranged in 2 rows, each row with 4 knives, one to be centered above and thrust through each chuck.
Each knife 201 for pitting dates is preferably a stainless steel cylindrical rod having an outside diameter (o.d.) of about 9 mm, the length being chosen according to the particular dates being pitted. For Deglet dates, the overall length of the knife is about 12.5 cm. For pitting prunes a knife is about 13 mm in diameter and has an overall length of about 12.5 cm. Near the knife's mounting end (upper end) 203 it is threaded, and the knife's fruit-cutting end 204 has a bottom cutting face 205 which is inwardly concave. The radius of the concave face is not narrowly critical being sufficient to provide a periphery which lends itself to being sharpened. Preferably, the periphery of bottom face 205 is sharpened to a knife-edge, to facilitate cutting through each date cleanly. The geometry of the cutting face 205 of the knives' ends is not narrowly critical, and the end could be star-shaped as described in the '832 patent. Each knife is slidably inserted through a vertical passage in plate 201 and removably tightly held by a nut 208. The plate 201 is also provided with two lateral through-passages 211, spaced apart so that the cross-bores 206 in each row of knives are aligned in each passage. At least one of the opposed ends 212 of each passage 211 is threaded to permit connection with a source of decontaminant fluid, and if only one end is threaded, the other end is plugged. Preferably both ends 212 and 213 are threaded so that fluid can be fed from both ends of each passage 211.
Each knife is provided with a longitudinal axial bore 202 the lower end of which terminates above the cutting face 205, the upper end of the bore 202 being plugged in the threaded end 203. It will be appreciated that the function of the longitudinal bore 202 is unrelated to its location being axial, the function being to supply fluid to one or more radially directed bores, but for ease of machining, the bore is axial. Each knife is also provided with a through cross-bore 206 which is aligned within, and in open fluid communication with bore 211 of the plate 210. To assist in registering the cross-bore 206 with the lateral bore 211, the knife is provided with a circumferential shoulder 215 the upper surface of which is abutted against the lower surface of the plate 210.
Near the lower terminal end of bore 202, each knife is provided with at least one, and preferably plural radially extending through passages 207 which are in open fluid communication with the bore 202. Where the end of the knife is star-shaped, a radial bore is provided in, or directly above each radiating member of the star. Preferably 4 such passages 207 are provided, each spaced apart by 90°, so that fluid from the bore 202 can be discharged radially outwards from the surface of the knife. Preferably, the radial bores are angulated, either downwards or upwards, most preferably downwards, from the lateral plane in the range from about 5° to about 65° so that the discharge from each bore contacts the wall of the pitted date at a downward angle.
It will be evident that axial bore 202 does not extend through the bottom cutting face 205 because squirting fluid directly downwards does not serve to cleanse the walls of the passage in a pitted date. However, it may be found that a small quantity of such directly downwardly squirted fluid helps to minimize the build-up of date remnants in passages 25 of the fruit holders. In such an event, if a downward discharge is desirable, it must be kept in mind that the diameter of the bore 202 near the bottom face will preferably be relatively smaller than the diameter of a radial bore 207 so as to permit the radial bore 207 to supply an effective amount of cleansing fluid.
To pit and simultaneously cleanse dates while they are being pitted, the 9 mm (11/32 inch) knives are preferably provided with an axial bore 202 having a diameter of about 3 mm (1/8 inch) and 4 radial bores each 1.6 mm (1/16 inch) diameter. In general, the sum of the areas of the cross-sections of the radial bores is about equivalent to the area of the cross-section of the axial bore.
In the assembly 200 of the '832 and '281 machines, spatial constrictions in the pitting head dictate that fluid be supplied through the plate 210. In an instance where such constriction does not apply, e.g. for knives held in a mount member in a pitting turret such as described in the Cimperman et al '439 patent, fluid may be supplied directly to the knife through a connection to the upper end of the longitudinal bore 202, and no cross-bore is required in the knife.
Referring to FIG. 4 there is illustrated a cross-section view of a single knife 301 to be mounted in a pitting turret in which individual knives 301 pit dates sequentially. As before, preferably each knife 301 is cylindrical and is provided with a longitudinal axial bore 302, but axial bore 302 does not extend through the bottom cutting face 305. Near the lower terminal end of bore 302, each knife is provided with at least one, and preferably plural radially extending through passages 307 which are in open fluid communication with the bore 302. Preferably 4 such passages 307 are provided, each spaced apart by 90°, so that fluid from the bore 302 can be discharged radially outwards from the surface of the knife; preferably, as before, the radial bores are angulated in the aforesaid angular range, and shown angulated upwards in this knife, so that the discharge from each bore contacts the wall of the pitted date at an upward angle. Each knife is preferably provided with a circumferential shoulder 315 the function of which is to help mount the knife in the pitting turret so that the knife is directed in a vertical direction.
In the foregoing operation for simultaneous pitting and cleansing, the pitting head thrusts the knives into and through dates held in the chucks of the fruit holders while fluid is being supplied to the knife assembly. All knives in the assembly are lowered into contact with the dates beneath and travel with them until the pits are ejected and the remaining passages cleaned while the pits are being ejected and upon withdrawal of the knives from the dates. Though water is typically the cleansing liquid used to remove frass, some forms of frass may be amenable to removal with a cleansing gas such as air, or air mixed with ozone. When a cleansing gas is effective, it provides the advantage of not wetting the internal passage left by the ejected pit. One skilled in the art will recognize that the dimensions of a pitting and cleansing knife, or of a cleansing rod, will be chosen depending upon the length of the axis (in the vertical direction) of the particular drupe being pitted, the diameter of the pit, and the pitting machine in which the knife or rod is to be used.
Substantially simultaneous pitting and cleansing with individual knives operating sequentially:
If desired, where individual drupes, e.g. dates or prunes, are to be pitted sequentially in a pitting turret such as is described in U.S. Pat. No. 5,577,439, a single pitting and cleansing knife 201 may be secured in a mount member held in a pitting turret (identified as 2A and 12 respectively in the '439 patent) wherein eighteen identical pitting knives (identified therein by reference numeral 6), each pitting knife mounted in a cylindrical, vertically oriented, channel 2B (shown in FIG. 21 of the '439 patent) through mount member 2A.
Operation with a single assembly of pitting knives and cleansing rods for sequential pitting and cleansing:
For first pitting, then cleansing the pitted dates, conventional pitting (only) knives may be used in a first row of plural knives, preferably in a first set of plural rows, and cleansing rods, or pitting and cleansing knives (which would provide primarily a cleansing function since the fruit is pitted by the preceding pitting knives), are used in the subsequent second row of plural rods, or second set of plural rows of rods, which would be positioned nearer the discharge end of the conveyor than the last row of pitting knives and downstream thereof. In this arrangement, fluid is supplied to the second row (or second set) of cleansing rods only, the mounting plate being bored accordingly. The first set of conventional pitting knives are conventionally mounted in the mounting plate. It is unnecessary to have the bottom faces of the cleansing rods sharpened as these rods primarily provide a cleansing function and essentially no cutting function. Thus, in cross-section, such cleansing rods appear to be identical to a pitting and cleansing knife, except for the concave bottom with its (pitting knife's) sharpened periphery.
Though pitting may be effected with a conventional pitting knife, such as a star-shaped one, it is most preferable to use a cylindrical pitting knife having a concave pitting face on its pitting end, with the periphery of the face sharpened to cleanly cut through the skin and flesh of a drupe to be pitted. The radius of the concave surface is not narrowly critical being chosen approximately to overlap the longitudinal cross-sectional area of the pit in a drupe to be pitted. In a 9 mm diameter pitting knife for a typical date, the length of the pitting knife is about 12.5 mm (4") and the radius of the concave face is in the range from about 9 mm to 30 mm.
Since the function of a cleansing or drying rod is primarily to discharge the desired fluid against the walls of the passage within a pitted drupe, the rod's length is not narrowly critical provided it enters the passage. Preferably the length is long enough to traverse the length of the major axis of the drupe. Its body is provided with a longitudinal, preferably axial, bore and one or more radial bores, as is a pitting and cleansing knife.
Operation with dual assemblies of pitting knives and cleansing rods for sequential pitting and cleansing:
Instead of pitting and cleaning in a single pitting head, it may be desirable to extend the horizontal section of the conveyor so as first, to pit dates in a conventional pitting head and thereafter cleanse the pitted dates in a separate cleansing head which is essentially the same as the first pitting head except that only cleansing rods are used. The operation of the machine would be similar to operation with a single pitting head, except for additional interconnecting chain drives and sprockets which time the operation of the second head in the same manner as the timing of the first head.
Operation with a single assembly of (i) pitting and cleansing knives and (ii) of drying rods, for simultaneous pitting and cleansing and sequential drying:
In some instances, it may be necessary to dry fruit which has been pitted and internally cleansed. Fruit, especially dates, internally cleansed with liquid retains enough moisture within the cleansed passage to slow down the drying of the pitted dates to meet moisture content specifications. Since the difficulty of drying is attributable mainly to liquid held within the cleansed passage, it may be desirable to contact the walls of the passage with a drying gas to accelerate drying of the a pitted dates. To do so, a single assembly of knives may include a first row of plural axially bored and cross-bored pitting and cleansing knives, or a first set of plural rows thereof, followed by a subsequent second row of plural drying rods, or second set of plural rows of drying rods, which (second row or second set) would be positioned nearer the discharge end of the conveyor than the last row, and downstream thereof. In this arrangement, cleansing liquid is supplied to the first row (or first set), and a drying gas is supplied to the second row (or second set). The drying gas is supplied under sufficient pressure to remove enough moisture from within the passage so as not to delay conventional drying of the dates.
Choice of fluid:
The choice of decontaminant fluid depends upon the particular nature of the contaminant to be cleansed and the degree of cleansing desired. Where frass is to be flushed out, clean water is preferred. However, if some degree of bacterial "kill" is desired, the decontaminant fluid may be a bacteriostatic or bactericidal solution of hydrogen peroxide, the concentration of which being chosen in accordance with the degree of "kill" sought. Alternatively, the decontaminant fluid may be a bacteriostatic or bactericidal gas, for example steam or ozone, or a mixture of such a gas and air. Still another alternative is the use of a mixture of liquid and gas, neither of which, or, one or both of which, may be bacteriostatic or bactericidal.
The amount of decontaminant fluid used should be sufficient to flush away frass and/or any other contaminant which adheres to the inner walls of the passage left in the pitted dates. Typically, water is supplied to each 212 and 213 end of the bores in the plate 210 at elevated pressure, preferably in the range from about 170 kPa (10 psig) to 790 kPa (100 psig), sufficient to flush away frass but insufficient to diminish the mass of the fruit significantly.
Where it is desired to dry wetted passages within pitted and cleansed fruit, a second set of plural knives may be used to do so in a manner analogous to sequential pitting and cleansing. Such drying is effected by contacting the walls of the passage with a drying gas under enough pressure and in an amount sufficient to force loosely adherent water from within the passage. For greater efficiency such drying gas may be bone-dry air which has been de-moisturized in a desiccator means.
Having described the longitudinally bored pitting and cleansing knife, an assembly of such knives, and the overall process of using the invention in detail, and having illustrated the invention with specific examples of the best mode of making the knife and using it to pit and cleanse drupes, particularly dates, it will be evident that the invention may be used in a wide choice of combinations depending upon the drupe to be pitted or de-seeded and the contaminant to be removed; and that the invention has provided an effective solution to an old and difficult problem. It is therefore to be understood that no undue restrictions are to be imposed by reason of the specific embodiments illustrated and discussed, and particularly that the invention is not restricted to a slavish adherence to the details set forth herein. | A drupe which is infested with a larva of a moth or larvae of other insects, and is contaminated with related excretions, referred to as a "frass", in a central zone within the drupe, is cleansed with a longitudinally bored pitting knife mounted in the pitting head of a conventional pitting machine. A source of cleansing fluid is connected to the bore within the knife and fluid is discharged through radial passages in the knife, which radial passages communicate with the longitudinal bore. In operation, while the knife pits the drupe, fluid discharged from within the knife contacts the walls of the passage left by the ejected pit, and removes the frass. If desired, the drupe may be first pitted, then decontaminated or washed, and/or dried sequentially, in separate stages. The invention is particularly effective with dates, prunes, olives, cherries, nectarines, peaches and avocados. | 0 |
FIELD OF THE INVENTION
[0001] The present invention relates to an electrochemical cell structure and a method of fabrication. In particular, the present invention relates to a metal oxide particles dispersion liquid used in the formation of a metal oxide layer.
BACKGROUND OF THE INVENTION
[0002] The International Energy Agency's “World Energy Outlook” predicts that global primary energy demand will increase by 1.7% per year from 2000 to 2030. It also predicts that 90% of this demand will be met by fossil fuels. Consequently, there will be a 1.8% per year increase in carbon dioxide from 2000 to 2030, reaching 38 billion tonnes in 2030. Cleaner, renewable energy sources, including solar cells, have long been heralded as counters to this increased pollution trend. While advanced silicon based solar cells are now widely commercially available, their uptake has been slow due to high production costs, a lack of robustness and associated visual pollution resulting from the large surface exposure requirements.
[0003] Dye Sensitised Solar Cells (DSSC) are an alternative to crystalline solar cells that are cheaper than crystalline solar cells to produce. However, DSSC's are less efficient than crystalline solar cells. Therefore, DSSC's require significant area coverage to be effective power generators.
[0004] U.S. Pat. No. 4,927,721 entitled “Photo-Electrochemical Cell”, by M Gratzel et al. discloses a typical DSSC. As illustrated in FIG. 1 , the DSSC 10 comprises a first transparent insulating layer 1 ; a first transparent conductive oxide (TCO) electrode layer 2 ; a transparent metal oxide layer 3 of titanium dioxide (TiO 2 ); a molecular monolayer of sensitiser (dye) 4 ; an electrolyte layer 5 ; a second transparent conductive oxide (TCO) electrode layer 6 ; and a second transparent insulating layer 7 .
[0005] A DSSC generates charge by the direct absorption of visible light. Since most metal oxides absorb light predominantly in the ultra-violet region of the electromagnetic spectrum, a sensitiser (dye) 4 is absorbed onto the surface of metal oxide layer 3 to extend the light absorption range of the solar cell into the visible light region.
[0006] In order to increase the amount of light that the metal oxide layer 3 and the sensitiser (dye) layer 4 can absorb, at least some portion of the metal oxide layer 3 is made porous, increasing the surface area of the metal oxide layer 3 . This increased surface area can support an increased quantity of sensitiser (dye) 4 resulting in increased light absorption and improving the energy conversion efficiency of the DSSC to more than 10%.
[0007] An electrochromic display (ECD) is a new type of display, which has a unique property of bi-stability.
[0008] An electrochromic display (ECD) is a relatively new electrochemical, bi-stable display. While the application is different to the DSSC, these devices share many physical attributes, illustrated in FIG. 1 , exchanging the sensitiser (dye) layer 4 by an electrochromic material layer which undergoes a reversible colour change when an electric current or voltage is applied across the device; being transparent in the oxidised state and coloured in the reduced state.
[0009] When a sufficient negative potential is applied to the first transparent conductive oxide (TCO) electrode layer 2 , whilst the second transparent conductive electrode oxide (TCO) layer 6 is held at ground potential, electrons are injected into the conduction band of the metal oxide semiconductor layer 3 and reduce the adsorbed molecules (the coloration process). The reverse process occurs when a positive potential is applied to the first transparent conductive oxide (TCO) electrode layer 2 and the molecules become bleached (transparent).
[0010] A single electrochromic molecular monolayer on a planar substrate would not absorb sufficient light to provide a strong colour contrast between the bleached and unbleached states. Therefore a highly porous, large surface area, nanocrystalline metal oxide layer 3 is used to promote light absorption in the unbleached state by providing a larger effective surface area for the electrochromophore to bind onto. As light passes through the thick metal oxide layer 3 , it crosses several hundreds of monolayers of molecules coloured by the sensitiser (dye) 4 , giving strong absorption.
[0011] Since the structure of both electrochemical devices is similar, we describe only the method of DSSC manufacture as an example. Equally, this process could be applied with little modification to the ECD manufacture.
[0012] In order to manufacture the DSSC 10 illustrated in FIG. 1 , a metal oxide layer 3 of several microns thickness is deposited onto the first transparent conductive oxide (TCO) electrode layer 2 , using any one of several techniques, such as screen printing, doctor blading, sputtering or spray coating a high viscosity paste. A typical paste commonly consists of water or organic solvent based metal oxide nanoparticle suspensions (5-500 nm diameter), typically titanium dioxide (TiO 2 ), a viscosity modifying binder, such as polyethylene glycol (PEG), and a surfactant, such as Triton-X. Following deposition the paste is dried, to remove the solvent, and then sintered at temperatures up to 450° C. This high temperature process modifies the metal oxide particle size and density, and ensures the removal of the organic binder constituents, such as polyethylene glycol (PEG) to provide a good conductive path throughout and a well defined material porosity. Sintering also provides good electrical contact between the metal oxide particles 3 and the first transparent conductive oxide (TCO) electrode layer 2 .
[0013] After drying and cooling, the porous metal oxide layer 3 is coated with sensitiser (dye) 4 by immersion in a low concentration (≦1 mM) sensitiser (dye) solution for an extended period, typically 24 hours, to allow absorption of the sensitiser (dye) 4 onto the metal oxide layer 3 through a functional ligand structure that often comprises a carboxylic acid derivative. Typical solvents used in this process are acetonitrile or ethanol, since aqueous solutions would inhibit the absorption of the sensitiser (dye) 4 onto the surface of the metal oxide layer 3 .
[0014] The first transparent conductive oxide (TCO) electrode layer 2 , having the porous metal oxide layer 3 and sensitiser (dye) layer 4 formed thereon, is then assembled with the second transparent conductive oxide (TCO) electrode layer 6 . Both electrode layers 2 , 6 are sandwiched together with a perimeter spacer dielectric encapsulant to create an electrode-to-electrode gap of at least 10 μm, before filling with the electrolyte layer 5 . The spacer material is most commonly a thermoplastic that provides an encapsulation seal. Once the electrolyte layer 5 , which is most commonly an iodide/triiodide salt in organic solvent, is introduced, the DSSC is completed by sealing any remaining aperture with either a thermoplastic gasket, epoxy resin or a UV-curable resin to prevent the ingress of water and hence device degradation.
[0015] Most, if not all, of the materials used to fabricate the DSSC can be handled in air and also under atmospheric pressure conditions, removing the necessity for expensive vacuum processes associated with crystalline solar cell fabrication. As a result, a DSSC can be manufactured at a lower cost than a crystalline solar cell.
[0016] The ECD fabrication process is very similar to that for the DSSC, with several exceptions. The porous metal oxide layer 3 is often patterned by screen printing to provide a desired electrode image, allowing the device to convey information by colouring or bleaching selected regions. Additionally, the sensitiser (dye) layer 4 is replaced with an absorbed electrochromophore material layer. Furthermore, a permeable diffuse reflector layer, typically large particles of sintered metal oxide, can be positioned between the first and second electrode layers 2 , 6 to increase the viewed image contrast.
[0017] U.S. Pat. No. 5,830,597, entitled “Method and Equipment for Producing a Photochemical Cell”, by H Hoffmann also discloses a DSSC 100 . As illustrated in FIG. 2 , the DSSC 100 comprises a first substrate 101 of glass or plastic; a first transparent conductive oxide (TCO) layer 102 ; a titanium dioxide (TiO 2 ) layer 103 , a dye layer 104 ; an electrolyte layer 105 ; a second transparent conductive oxide (TCO) layer 106 ; a second substrate 107 of glass or plastic; and insulating webs 108 , 109 . The insulating webs 108 , 109 are used to form individual cells 110 in the DSSC 100 .
[0018] An individual cell 110 formed between the insulating web 108 and the insulating web 109 is different from the adjoining individual cell 110 formed between the insulating web 109 and the insulating web 108 . This is because the TiO 2 layer 103 and the electrolyte layer 105 are interchanged in each adjoining individual cell. 110 . Thus, the electrical polarity of the adjoining individual cells 110 is opposite. This alternate division of different layers results in the formation of conducting layers 111 from the electrically conductive layers 102 and 106 , each conducting layer 111 connecting a positive (negative) pole of one individual cell 110 to the negative (positive) pole of an adjacent individual cell 110 . The resultant structure provides a method of increasing the overall DSSC output voltage, without the necessity of incorporating a multi-layered structure.
[0019] In order to improve the incident photon to current conversion efficiency and control the stability/reproducibility of the DSSC performance, it is important to precisely control the physical-properties of the metal oxide layer, and hence the absorption of the sensitiser (dye) molecule. However, metal oxide layer fabrication using screen-printing often results in a ±5% film thickness variation caused by residual blocked or dirty screen cells, adhesion to the screen during separation from the substrate surface and trapped bubble expansion during drying, caused by the inability to completely outgas a viscous paste. Other methods, such as doctor-blading, also suffer from an inability to provide a well defined thick metal oxide layer without significant spatial deviations. Subsequent porosity and film quality deviations are therefore likely to occur throughout such metal oxide layers, resulting in a degradation of efficiency and image quality for the DSSC and ECD, respectively.
[0020] In the case of the ECD, screen-printing demands are further exacerbated by the requirement to create ever finer metal oxide layer features for higher quality images, i.e. increase the dots-per-inch (dpi) for a pixelated display. As the dpi increases, the smallest feature size becomes limited as the screen mesh size approaches the mesh partition width.
[0021] As a result, fabrication of an electrochemical device based on a functionally sensitised thick porous metal oxide layer, as for the DSSC and ECD, using the aforementioned fabrication techniques are inappropriate from the view points of device reproducibility and adaptability to large size device production.
SUMMARY OF THE INVENTION
[0022] The present invention aims to address the above mentioned problems of manufacturing electrochemical cells (DSSC's and ECD's) of the prior art, to improve the efficiency with which they are made and thus further decrease their fabrication costs.
[0023] In a first embodiment of the present invention an electrochemical cell is provided. The electrochemical cell comprising: a first conductive layer; a metal oxide layer formed on the first conductive layer, the metal oxide layer comprising a plurality of adjacent metal oxide cells, spaced from one another; a functional dye layer formed on the metal oxide layer; a second conductive layer; and an electrolyte between the functional dye layer and the second conductive layer, wherein at least one of the first and second conductive layers is transparent, and wherein the metal oxide layer is formed from a metal oxide particle dispersion liquid.
[0024] In one embodiment the metal oxide particle dispersion liquid is a water based liquid. In another embodiment the metal oxide particle dispersion liquid is an alcohol based liquid. In another embodiment the metal oxide particle dispersion liquid comprises a plurality of metal oxide particles having a diameter of between substantially 5 nm to 500 nm. In another embodiment the plurality of metal oxide particles have a diameter of substantially 18 nm.
[0025] In a further embodiment the metal oxide particle dispersion liquid further comprises a viscosity modifier. In another embodiment the viscosity modifier is polyethylene glycol or polyethylene oxide. In another embodiment the viscosity modifier has a concentration less than 5% w/w. In another embodiment the metal oxide particle dispersion liquid further comprises a binder. In another embodiment the binder is polyethylene glycol or polyethylene oxide. In another embodiment the binder has a concentration less than 5% w/w. In another embodiment the metal oxide particle dispersion liquid further comprises a surfactant to adjust surface tension. In another embodiment the surfactant is Triton-X.
[0026] In one embodiment the electrochemical cell further comprises: separating means formed on the first conductive layer and surrounding each of the plurality of adjacent metal oxide cells. In another embodiment the separating means is a polymer pattern or a polyimide pattern. In another embodiment at least part of the separating means is hydro- and/or oleophobic and wherein the first conductive layer is hydro- and/or oleophilic. In another embodiment the separating means forms a matrix of cells on the first conductive layer. In another embodiment each of the metal oxide cells is substantially square shaped, substantially circular shaped, substantially hexagonal shaped or substantially rectangular shaped. In another embodiment the separating means are banks.
[0027] In one embodiment the electrochemical cell further comprises: an electrocatalytic layer formed the electrolyte and the second conductive layer. In another embodiment the electrocatalytic layer is any one of platinum, ruthenium, rhodium, palladium, iridium or osmium.
[0028] In one embodiment the electrochemical cell further comprises: a first insulating substrate on a side of the first conductive layer opposite to the metal oxide layer. In another embodiment the electrochemical cell further comprises: a second insulating substrate on a side of the second conductive layer opposite to the electrolyte. In a further embodiment at least one of the first and second insulating substrates is glass or plastic. In a further embodiment the metal oxide layer is a semiconductor.
[0029] In one embodiment the metal oxide particle dispersion liquid comprises a plurality of titanium dioxide particles. In another embodiment the metal oxide particle dispersion liquid comprises a plurality of metal oxide particles, and wherein the functional dye layer is formed on a surface of the metal oxide particles. In another embodiment the first and second conductive layers are continuous layers. In another embodiment the first conductive layer is a transparent conductive oxide layer. In another embodiment the second conductive layer is a transparent conductive oxide layer.
[0030] In one embodiment the electrochemical cell is a dye sensitised solar cell. In another embodiment the electrochemical cell is an electrochromic display. In a further embodiment the functional dye layer is an electrochromophore layer.
[0031] In a second embodiment of the present invention a method of forming an electrochemical cell is provided. The method of forming an electrochemical cell comprising: forming a first conductive layer; forming a metal oxide layer from a metal oxide particle dispersion liquid on the first conductive layer, the metal oxide layer comprising a plurality of adjacent metal oxide cells, spaced from one another; forming a functional dye layer on the metal oxide layer; forming a second conductive layer; and providing an electrolyte between the functional dye layer and the second conductive layer, wherein at least one of the first and second conductive layers is transparent.
[0032] In one embodiment the method further comprises: forming separating means on the first conductive layer surrounding each of the plurality of adjacent metal oxide cells. In another embodiment the metal oxide layer is inkjet printed onto the first conductive layer. In another embodiment the metal oxide layer is inkjet printed onto the first conductive layer in one step.
[0033] In one embodiment the method further comprises: providing an electrocatalytic layer between the electrolyte and the second conductive layer. In another embodiment the method further comprises: forming the first conductive layer on a first insulating substrate, whereby the first insulating substrate and the metal oxide layer are on opposite sides of the first conductive layer. In another embodiment the method further comprises: forming the second conductive layer on a second insulating substrate, whereby the second insulating substrate and the electrolyte are on opposite sides of the second conductive layer.
[0034] In a further embodiment the metal oxide layer is formed from a water based metal oxide particle dispersion liquid. In another embodiment the metal oxide layer is formed from an alcohol based metal oxide particle dispersion liquid.
[0035] The method of fabrication of the electrochemical cell of the present invention, using inkjet printing, is advantageous over screen printing fabrication as format scaling (up or down) does not require re-investment in machine hardware. This is because inkjet fabrication is software controlled and the software can be reconfigured without the expense of commissioning new screens. Additionally, inkjet heads are significantly more durable, than patterned screens, as patterned screens last only approximately 100 uses.
[0036] Furthermore, the drop on demand placement enabled by inkjet fabrication is less wasteful than screen printing. Unlike conventional inkjet overwriting, where each deposited layer is dried and then printed over to produce a thick deposition, the inkjet flood filling technique, which doses a confined region with a large volume of liquid to provide the required deposit thickness, has been shown to produce fracture-free metal oxide layers. Moreover, the surface confinement used to enable flood filling, through the use of a bank structure, ensures long range uniform material distribution and therefore uniform and repeatable performance. Additionally, surface confinement through the use of a bank structure ensures enhanced picture quality and contrast by colour separation between the different coloured cells.
BRIEF DESCRIPTION OF THE DRAWINGS
[0037] Embodiments of the present invention will now be described by way of further example only and with reference to the accompanying drawings, in which:
[0038] FIG. 1 illustrates a typical Dye Sensitised Solar Cell (DSSC) of the prior art;
[0039] FIG. 2 illustrates a further DSSC of the prior art;
[0040] FIG. 3 illustrates an electrochemical cell of the present invention;
[0041] FIG. 4 illustrates a process flow diagram for the fabrication of an electrochemical cell of the present invention; and
[0042] FIG. 5 illustrates several pixel cells of a bank structure filled with metal oxide.
DETAILED DESCRIPTION
[0043] The present invention relates to an electrochemical cell such as a Dye Sensitised Solar Cell (DSSC) or an electrochromic display (ECD). One electrochemical cell 400 of the present invention comprises, with reference to FIG. 3 , a first transparent insulating substrate layer 401 ; a first transparent conductive oxide (TCO) electrode layer 402 ; a metal oxide layer 403 ; a sensitiser (dye)/electrochromic material layer 404 ; an electrolyte layer 405 ; a second TCO electrode layer 406 ; and a second transparent insulating substrate layer 407 .
[0044] The first and second transparent insulating substrate layers 401 , 407 are preferably glass or plastic. The metal oxide layer 403 is preferably titanium dioxide (TiO 2 ) and is a semiconductor.
[0045] The metal oxide layer 403 should preferably be a material which promotes intimate adhesion of the sensitiser (dye)/electrochromic material layer 404 on its surface. Additionally, the particles of the metal oxide layer 403 must be reasonably light transmissible. Particles greater then 500 nm are expected to be opaque and are not generally considered appropriate for use in the present invention. Such large particles would also tend to cause inkjet nozzle blocking.
[0046] In a first embodiment of the present invention, a bank structure 410 is formed on the first TCO layer 402 , prior to the application of the metal oxide layer 403 , so that a metal oxide layer 403 is formed of isolated cells. In one embodiment the bank structure 410 may be formed from a polymer or a polyimide.
[0047] Preferably, the bank structure is hydro- and/or oleophobic in some part while the TCO layer 402 is hydro- and/or oleophilic, depending on the nature of the metal oxide ink used to form the metal oxide layer 403 .
[0048] The bank structure 410 can take on any desired shape forming a matrix of individual pixel cells on the first TCO layer 402 , within which the isolated metal oxide cells are formed; such that no metal oxide bridges the bank structure 410 to cause short circuiting.
[0049] When the electrochemical cell is an ECD, it is essential that all the metal oxide cells (pixels) are electrically isolated from one another to control the image formation. While the metal oxide cell electrical isolation is not essential when the electrochemical cell is a DSSC, it is preferable to maintain a uniform metal oxide distribution throughout the active device area.
[0050] The ECD electrochemical cell can be considered as being composed of a plurality of micro-electrochemical cells, and different micro-electrochemical cells may have different coloured electrochromophore layers 404 . Each micro-electrochemical cell is separated from the other micro-electrochemical cells, which together form the ECD, by the bank structure 410 . Each micro-electrochemical cell is preferably between 20 μm to 500 μm across.
[0051] In a further embodiment of the present invention an electrocatalytic layer can be formed between the electrolyte layer 405 and the second TCO layer 406 . The electrocatalytic layer is preferably greater than 2 nm thick and is selected to enhance the electrolyte regeneration. In the case of the DSSC, effective electrocatalytic metals can be selected from the platinum group metals; platinum, ruthenium, rhodium, palladium, iridium or osmium. The use of an electrocatalytic layer improves the overall performance of the electrochemical cell of the present invention.
[0052] The present invention also relates to a method of fabricating the electrochemical cell 400 of the present invention. FIG. 4 illustrates a process flow diagram for the fabrication of an electrochemical cell 400 of the present invention.
[0053] The TCO layer 402 is formed on the first transparent insulating substrate layer 401 , FIG. 4 a . Preferably, the TCO layer 402 has a sheet resistivity of 8-10 Ω.sq. and is made of indium tin oxide or fluorine doped tin oxide. Fluorine doped tin oxide is preferable due to its cheapness and inertness during the high temperature sintering stage.
[0054] The bank structure 410 is then fabricated on the TCO layer 402 , FIG. 4 b . In the first embodiment of the present invention, the bank structure 410 forms a matrix of square pixel cells. In order to form the bank structure 410 on the TCO layer 402 , a photo-reactive polyimide source material is coated on to the TCO layer 402 and dried. A mask, in the shape of the matrix of pixel cells is then applied to the TCO layer 402 . An ultraviolet (UV) light is irradiated through the mask to cause cross-linking of the polyimide in the exposed regions. The unexposed regions are removed by chemical developing, and the bank structure 410 is thermally cured.
[0055] The TCO layer 402 having a bank structure 410 is then treated by oxygen or oxygen plus carbon tetrafluoride plasma to remove residual polyimide in the exposed regions. A carbon tetrafluoride (CF 4 ) plasma treatment is then applied to cause the polyimide bank structure 410 to become hydrophobic, while preserving the hydrophilic nature of the TCO layer 402 .
[0056] The metal oxide layer 403 is then inkjet printed onto the TCO layer 402 having the bank structure 410 formed thereon. The metal oxide ink is jetted into each of the isolated pixel cells to form the metal oxide layer 403 , FIG. 4 c , from an inkjet head. In one embodiment, a water-based aqueous colloidal metal oxide liquid ink of concentration ≦10% volume fraction (v/v) is used. In an alternative embodiment, an alcohol-based colloidal metal oxide liquid ink is used. In both embodiments, preferably, the metal oxide particles dispersed in the liquid are titanium dioxide (TiO 2 ) particles and have a diameter of approximately 18 nm. However, the diameter of the particles can be selected from a range of 5 nm to 500 nm, although the maximum diameter of particles is limited by the inkjet head characteristics.
[0057] Other additives can be added to the metal oxide ink in order to ensure compatibility of the metal oxide ink with the inkjet head and thus improve the stability and accuracy of the metal oxide ink ejection from the inkjet head. For example, a viscosity enhancer, such as a polyethylene glycol (PEG), may be added to the metal oxide ink. In addition, a surfactant, such as Triton-X may be added to the metal oxide ink in order to adjust the surface tension of the ink.
[0058] Other additives can also be added to the metal oxide ink to control the structure of the dried deposit after inkjet printing. For instance, polyethylene oxide (PEO) can be used as a matrix binder material, intercalating the metal oxide particles contained in the ink as the solvent evaporates from the target surface. Subsequent high temperature air anneals would remove this volatile intercalated material to leave a metal oxide film of the desired porosity.
[0059] The volume of all dry material included in these metal oxide inks should be no greater than one quarter of the volume of metal oxide particles in the same solution. Above this fraction the residual material will exceed the volume created between the metal oxide particles, assuming a close packing arrangement of identically sized particles, and will disrupt the electrical connectivity between them upon drying. By example, an aqueous 10% v/v TiO 2 solution should contain no more than 2% w/w PEO. Neglecting the contribution of the TiO 2 , this equates to a pure 3% w/w PEO solution. With such a high PEO concentration as this, any resultant ink to be too viscous to inkjet print normally. Hence, we do not expect the usefulness of inks to be limited by the volumetric fraction of dry material additives, but by the effect that such additives have on the resultant ink physical properties, predominantly viscosity.
[0060] It is possible that the function of metal oxide ink viscosity modification and porosity/binding control can be performed by a single additive. Both PEG and PEO are examples of such materials.
[0061] After inkjet printing the metal oxide deposit is dried and then sintered in air at 300 C to provide the metal oxide layer 403 .
[0062] The thickness of the metal oxide layer 403 is controlled by the concentration of the metal oxide ink, and the deposition volume. The resultant deviation in the peak thickness of the metal oxide layer 403 is less than 1.5% between pixel cells over a 50 cm 2 substrate area.
[0063] The substrate layer 401 comprising the TCO layer 402 , the bank structure 410 and the metal oxide layer 403 is then immersed in sensitiser (dye) 404 for a period of time. The sensitiser (dye) 404 is thereby absorbed onto the surface of the metal oxide layer 403 , FIG. 4 d . For the DSSC example, the substrate was immersed in a 0.3 mM solution of N719 (obtained from Solaronix) in dry ethanol for 24 hours. After immobilisation of the sensitiser (dye) 404 , the substrate is rinsed in ethanol and blown dry using nitrogen.
[0064] The first TCO layer 402 , having the porous metal oxide layer 403 and sensitiser (dye) layer 404 formed thereon, is then assembled with the second TCO layer 406 . Both electrode layers 402 , 406 are sandwiched together with a perimeter spacer to create an electrode-to-electrode gap, before filling with the electrolyte layer 405 . Once the electrolyte layer 405 is introduced, the DSSC is completed by sealing the remaining aperture.
[0065] If an electrocatalytic layer is desired in the electrochemical cell of the present invention, then the electrocatalytic layer is formed on the second TCO layer 406 prior to the electrode layers 402 , 406 being sandwiched together.
[0066] An inkjet head is capable of providing a well defined aqueous colloidal metal oxide ink droplet, with volume deviation less than ±1.5%, to a precise location on the TCO layer 402 . Moreover, this volumetric accuracy of ≦1.5% represents that for a commercial printer head. Several industrial heads and complementary techniques are available which can reduce this figure to ≦1%.
[0067] Inkjet deposition enables accurate positioning of the metal oxide on the TCO layer 402 , within each pixel cell of the bank structure 410 as required. Thus, the thickness of the metal oxide layer 403 can be controlled precisely and a uniform porous metal oxide layer 403 can be obtained.
[0068] When at least part of the bank structure 410 is hydro- and/or oleophobic, and at least part of the TCO layer 402 is hydro- and/or oleophilic, the bank structure 410 repels the deposited metal oxide ink, thus correcting the final position of the deposited metal oxide ink droplets on the target surface and compensating for the inherent ±15 μm droplet lateral divergence from the inkjet nozzle axis. This repulsion is especially beneficial in the case of the ECD to prevent pixel short-circuits caused by metal oxide 403 bridging the bank structure 410 . The bank structure 410 also enables the formation of a narrower gap between ECD pixels than otherwise permitted by the 30 μm spacing necessary for bank-less free-printing, enabling a higher active area ratio to be obtained in the ECD and increased image quality.
[0069] The metal oxide layer 403 should be several microns thick to function effectively. In traditional inkjet printing the thickness of the ink is built up to the desired thickness by using an overwriting technique, wherein each deposited layer is dried and sintered and then overwritten with another layer of ink, and so on, until the desired thickness is reached.
[0070] However, the method of the present invention uses a flood filling technique, whereby a large volume of metal oxide ink is introduced into each pixel cell of the bank structure 410 in one pass. The bank structure 410 prevents the metal oxide ink from spreading into neighbouring pixel cells. Using this process, only a single drying and sintering stage is required to produce the desired thickness of the metal oxide layer 403 .
[0071] FIG. 5 illustrates several pixel cells of a bank structure 410 filled with metal oxide.
[0072] A bank structure 410 having a matrix of square pixel cells produces a quasi-pyramidal dry metal oxide topography when the flood filling technique is used to fill each pixel cell with metal oxide ink. The bank structure 410 acts to confine the deposited metal oxide ink to a local region, within the pixel cells on the TCO layer 402 . Without this confinement, the metal oxide ink would be distributed freely across the TCO layer 402 following deposition and would form a continuous metal oxide layer 403 .
[0073] The bank structure 410 of the present invention increases the metal oxide layer's 403 ability to accommodate bending stress without fracturing, compared to a continuous metal oxide layer 403 . This enables a flexible substrate 401 to be utilised, such as a plastic first insulating substrate 401 .
[0074] In the first embodiment of the present invention, the bank structure 410 comprises a matrix of square pixel cells as illustrated in FIG. 5 . However, the pixel cells are not limited to being square. When the electrochemical cell 400 of the present invention is an ECD, square pixels are preferred as they are compatible with active matrix backplane fabrication technology. However, when the electrochemical cell 400 of the present invention is a DSSC, several different pixel cell shapes can be used, such as a hexagonal, rectangular, circular or square pixel cell shape can be used. A hexagonal pixel cell shape or a square pixel cell shape is preferable for use in a DSSC of the present invention.
[0075] DSSC's of the present invention have been made with an energy conversion efficiency (η), an open circuit voltage (V oc ), a short circuit current (I sc ) and a fill factor (FF) of 5.0%, 0.48 V, 15 mA/cm 2 and 56%, respectively. The variation in energy conversion efficiency of a electrochemical cell of the present invention over a 50 cm 2 substrate area is less than 1.5%. This is due to the process stability of the inkjet fabrication method of the present invention.
[0076] Wider bank structures 410 are deleterious to both ECD operation, by a reduction in image quality, and DSSC operation, by a reduction in efficiency; resulting from a decrease in active area. Therefore, the bank structure 410 has a preferable width from 0.2 μm to 20 μm. 0.2 μm is the resolution limit for cost effective fabrication of the bank structure 410 by photolithography. 20 μm is considered the maximum effective bank structure 410 width before serious degradation of the image and performance becomes inhibitive, compared to the lowest common display-resolutions of 72 dpi. Using inkjet technology hydrophilic pixel cell sizes less than 1 mm 2 are readily achievable, though lengths less than several hundred microns are preferred.
[0077] In the case of DSSC, absorption of light is proportional to the thickness of the porous metal oxide layer 403 . If too thin, a fraction of the incident light will pass unhindered through the metal oxide layer 403 , with a loss of potential efficiency. If too thick, once all of the useful light has been completely absorbed, any remaining metal oxide layer 403 thickness will be redundant. Therefore, preferably the thickness of the deposited metal oxide layer 403 should be between from 0.5 μm to 20 μm.
[0078] Moreover, due to the uniformity of the thickness of the metal oxide layer 403 produced by inkjet printing over screen printing, the optimal metal oxide layer 403 thickness can be thinner when using inkjet printing.
[0079] Furthermore, in the case of screen printing, the ink viscosity must be much higher than that preferred for inkjet printing. Therefore, the material added to increase viscosity must be removed during the sintering process. Consequently, the as-deposited, pre-sintered metal oxide layer 403 thickness must be greater for screen-printing than for inkjet printing.
[0080] Although a bank structure 410 is used to form a matrix of isolated pixel cells on the TCO layer 402 , prior to application of the metal oxide ink, the present invention is not limited to banks. Any method of forming isolated pixel cells on the TCO layer 402 may be used, such by creating troughs in the TCO layer 402 .
[0081] Additionally, although the sensitiser (dye) 4 is formed on the metal oxide layer 403 by immersion of the metal oxide layer 403 in the sensitiser (dye) 404 for a predetermined period of time, the sensitiser (dye) 404 may be formed on the metal oxide layer using different techniques. For example, the sensitiser (dye) 404 may be ink jet printed onto the metal oxide layer 403 following formation of the metal oxide layer 403 .
[0082] Furthermore, it is not essential for the first transparent conductive oxide layer 402 to be formed of an oxide material for the electrochemical cell of the present invention to function. Additionally, it is not essential for the second transparent conductive oxide layer 406 to be transparent or formed of an oxide material for the electrochemical cell of the present invention to function. Indeed, it is not essential to provide the second substrate (or either substrate in the finished device).
[0083] Any suitable material or process can be used for forming the bank structures. However, it is preferred to deposit them as a polymer, and more preferably as a polyimide, pattern.
[0084] Although liquid electrolytes have been discussed above, solid or gel electrolytes are also suitable for use in the present invention and, in this context, any reference in this specification to providing an electrolyte between an electrode/conductive layer and another element includes forming the electrode/conductive layer and/or the other element on the electrolyte.
[0085] The foregoing description has been given by way of example only and it will be appreciated by a person skilled in the art that modifications can be made without departing from the scope of the present invention. | An electrochemical cell and a method of manufacturing the same are provided. The electrochemical cell comprising: a first conductive layer; a metal oxide layer formed on the first conductive layer, the metal oxide layer comprising a plurality of adjacent metal oxide cells, spaced from one another; a functional dye layer formed on the metal oxide layer; a second conductive layer; and an electrolyte between the functional dye layer and the second conductive layer, wherein at least one of the first and second conductive layers is transparent, and wherein the metal oxide layer is formed from a metal oxide particle dispersion liquid. | 8 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to and is a continuation-in-part of U.S. application Ser. No. 13/248,005, filed Sep. 28, 2011 and titled “Folding Sawhorse,” which is hereby incorporated by reference in its entirety. U.S. application Ser. No. 13/248,005 claims the benefit of U.S. application Ser. No. 13/156,326, which is a continuation of U.S. application Ser. No. 10/908,388, which applications are also hereby incorporated by reference in their entirties.
FIELD OF INVENTION
[0002] The present invention relates to sawhorses, scaffolds and trestles. In particular, the present invention relates to sawhorses that are opened for use and folded to collapse for storage.
BRIEF DESCRIPTION OF THE DRAWINGS
[0003] FIG. 1 is a front perspective view of a folding sawhorse according to the present invention.
[0004] FIG. 2 is a back perspective view of a folding sawhorse.
[0005] FIG. 3 is a top view of a folding sawhorse.
[0006] FIG. 4 is a perspective view of a folding sawhorse in a closed position.
[0007] FIG. 5 is a side view of a folding sawhorse in a closed position.
[0008] FIG. 6 is a top view of a load bearing support member of a folding sawhorse.
[0009] FIG. 7 is a side view of a frame of a folding sawhorse.
[0010] FIG. 8 is a side view of a hinge of a folding sawhorse.
[0011] FIG. 9 is a perspective view of a frame of a folding sawhorse.
[0012] FIG. 10 is a top view of a load bearing support member of a folding sawhorse.
[0013] FIG. 11 is a side view of a frame of a folding sawhorse.
[0014] FIG. 12 is a side view of a hinge of a folding sawhorse.
[0015] FIG. 13 is a perspective view of a frame of a folding sawhorse.
[0016] FIG. 14 is a top view of a shelf of a folding sawhorse.
[0017] FIG. 15 is a perspective view of a shelf of a folding sawhorse.
[0018] FIG. 16 is a perspective view of a hinge of a folding sawhorse.
[0019] FIG. 17 is a perspective view of a hinge of a folding sawhorse,
[0020] FIG. 18 is a top view of a shelf of a folding sawhorse.
[0021] FIG. 19 is a perspective view of a shelf of a folding sawhorse.
[0022] FIG. 20 is a perspective view of a hinge of a folding sawhorse.
[0023] FIG. 21 is a perspective view of a hinge of a folding sawhorse.
[0024] FIG. 22 is a perspective view of a tubular member of a hinge for a folding sawhorse.
[0025] FIG. 23 is a side view of a tubular member of a hinge for a folding sawhorse.
TERMS OF ART
[0026] As used herein, the term “stabilizing surface” refers to any structure or component of a folding sawhorse adapted to be in physical contact with the ground or other surface while the sawhorse is in use.
[0027] As used herein, the term “stress bearing structures” refers to any structure which supports or resists a loads or stress, including, but not limited to, bending, tensile stress and compression.
BACKGROUND
[0028] Sawhorses are used as racks or trestles to support construction materials and other objects. With their wide base, sawhorses provide stable support for a work piece while being portable. Non-folding sawhorses, however, require a substantial amount of space for storage and transportation. To ameliorate this problem, sawhorses were designed to fold and collapse.
[0029] Unfortunately, many current folding sawhorses are unable to withstand sideways motion in the load they support. In particular, folding sawhorses with legs positioned on a common side are not in rigid contact with each other which results in the legs pivoting with respect to the upper central member of the sawhorse when the sawhorse is under load.
[0030] Other folding sawhorse designs require the of two sawhorses to support working materials or equipment in a horizontal position. While providing adequate support, the necessity of having two separate sawhorses is cumbersome and onerous.
[0031] Therefore, what is needed is a single folding sawhorse that easily unfolds and supports a variety of working materials. What is further needed is a folding sawhorse that is capable of supporting a bad while withstanding the effects of lateral movement of the particular bad. Finally, what is needed is a folding sawhorse that is constructed from lightweight materials.
SUMMARY OF THE INVENTION
[0032] The present invention is a folding sawhorse comprised of two pivotally connected frames containing a plurality of stress bearing structures on their inner surfaces and forming a 60 degree angle when locking in place by a locking shelf. The frame components are comprised of two parallel vertical members separated at a distance by an upper horizontal brace and parallel lower horizontal brace. A U-shaped bad bearing support is connected to the upper surface of the upper horizontal braces and provides four surfaces across which a load may be distributed when the folding sawhorse is in use. The trapezoidal locking shelf is pivotally connected to the lower horizontal braces and contains a central hinge, allowing the shelf to fold when the sawhorse is collapsed along its central vertical hinge.
DETAILED DESCRIPTION OF INVENTION
[0033] For the purpose of promoting an understanding of the present invention, references are made in the text to exemplary embodiments of a folding sawhorse, only some of which are described herein. It should be understood that no limitations on the scope of the invention are intended by describing these exemplary embodiments. One of ordinary skill in the art will readily appreciate that alternate but functionally equivalent structures and materials may be used. The inclusion of additional elements may be deemed readily apparent and obvious to one of ordinary skill in the art. Specific elements disclosed herein are not to be interpreted as limiting, but rather as a basis for the claims and as a representative basis for teaching one of ordinary skill in the art to employ the present invention.
[0034] It should be understood that the drawings are not necessarily to scale; instead, emphasis has been placed upon illustrating the principles of the invention. In addition, in the embodiments depicted herein, like reference numerals in the various drawings refer to identical or near identical structural elements.
[0035] FIGS. 1-3 illustrate folding sawhorse 10 in the fully opened position. In the exemplary embodiment shown, folding sawhorse 10 is generally V-shaped with a first trestle frame 12 and a second trestle frame 14 connected to one another with a central hinge 16 .
[0036] Frames 12 and 14 are generally rectangular having central rectangular apertures 80 and legs 40 a, 40 b and 52 a, 52 b projecting downward from frames 12 and 14 , respectively. In the exemplary embodiment shown, legs 40 a, 40 b and 52 a, 52 b are integral with frames 12 and 14 , respectively. However, in further exemplary embodiments, legs 40 a, 40 b and 52 a, 52 b may be separate physical components of folding sawhorse 10 which may be permanently or removably interconnected with frames 12 and 14 .
[0037] As illustrated, legs 40 a, 40 b and 52 a, 52 b work together to create a three-point contact with the ground or other surface for while sawhorse 10 is in use. Legs 40 a and 52 a, closest to central hinge 16 , act as a single stabilizing surface, while legs 40 b and 52 b, furthest from central hinge 16 , act as distinct stabilizing surfaces.
[0038] Also illustrated in FIGS. 1-3 are the surfaces of frames 12 and 14 . In the exemplary embodiments shown, frames 12 and 14 contain smooth outer surfaces while the inner surfaces contain a plurality of structural trusses, struts and other stress-bearing structures molded within frames 12 and 14 .
[0039] As illustrated, there are three types of stress-bearing structures included on each of frames 12 and 14 . Running vertically from legs 40 a, 40 b and 52 a, 52 b to the top of frames 12 and 14 are horizontal supports 90 a, which are alternately aligned between vertical supports 90 b. Horizontal supports 90 a and vertical supports 90 b spread and distribute force horizontally over legs 40 a, 40 b and 52 a, 52 b so that weight (when folding sawhorse 10 is in use) is evenly distributed on legs 40 a, 40 b and 52 a, 52 b. Frames 12 and 14 also contain diagonal braces 92 a with vertical struts 92 b running horizontally above the frame apertures 80 . The diagonal braces 92 a with vertical struts 92 b work to distribute weight evenly across load bearing supports 42 and 54 . Finally, the lower portions of frames 12 and 14 contain diamond-shaped support structures 94 which help evenly distribute weight from load bearing supports 42 and 54 and shelf 20 between legs 40 a, 40 b and 52 a, 52 b.
[0040] A center folding shelf 20 controls the opening and closing movements of frames 12 and 14 . Shelf 20 is attached to a lower strut 22 on frame 12 and a lower strut 24 on frame 14 . In particular, shelf 20 is interconnected with strut 22 with a shelf hinge 26 and with strut 24 with shelf hinge 28 . Shelf 20 further includes a central shelf hinge 30 and is generally trapezoidal. Shelf 20 locks sawhorse 10 in an open stable position while also providing a surface upon which a user may place tools and parts associated with a particular job.
[0041] In the exemplary embodiment illustrated, shelf 20 contains a lip to prevent items from rolling on shelf 20 . However, in other further embodiments, shelf 20 may omit lip. In still further exemplary embodiments, shelf 20 may contain apertures or compartments to accommodate specific tools or accessories commonly used in the art.
[0042] FIGS. 4-5 illustrate folding sawhorse 10 in closed position. In operation, sawhorse 10 is opened from a closed position (illustrated in FIGS. 4-5 ) by slightly spreading apart frames 12 and 14 to an unfolded working position (as illustrated in FIGS. 1-3 ). Sawhorse 10 remains in a locked open position without any additional latching mechanism until frames 12 and 14 are returned to a closed position by applying light upward pressure on central shelf hinge 30 . Shelf 20 then roves upwardly, thereby causing frames 12 and 14 to pivot inwardly towards each other until frames 12 and 14 are in a closed position.
[0043] In the preferred embodiment, frame 12 includes a first vertical member 32 opposite and parallel to a second vertical member 34 having an upper horizontal brace 36 and a lower horizontal brace 38 orthogonally configured therebetween. A pair of parallel spaced apart legs 40 a, 40 b extends from and is integrally formed with lower horizontal brace 38 . A load bearing support 42 is formed along the top edge of upper horizontal brace 36 .
[0044] Similarly, frame 14 includes a first vertical member 44 opposite and parallel to a second vertical member 46 having an upper horizontal brace 48 and a lower horizontal brace 50 orthogonally configured therebetween. A pair of spaced apart legs 52 a, 52 b extends from and is integrally formed with lower horizontal brace 50 . A bad bearing support 54 is formed along the top edge of upper horizontal brace 48 .
[0045] The inner surfaces of vertical members 32 , 34 , 44 and 46 contain horizontal supports 90 a and vertical supports 90 b (not shown). Upper horizontal braces 36 and 48 contain diagonal braces 92 a with vertical struts 92 b (not shown). Lower horizontal braces 38 and 50 contain diamond-shaped supports 94 .
[0046] In the exemplary embodiments shown in FIGS. 1-5 , load bearing supports 42 and 54 are U-shaped, thereby forming a channel across the upper edges of horizontal braces 36 and 48 , respectively. When folding sawhorse 10 is in use, an object placed across the top of folding sawhorse 10 will be in physical contact with the four upper surfaces ( 42 a, 42 b and 54 a, 54 b ) of the U-shaped load bearing supports 42 and 54 .
[0047] Frames 12 and 14 pivot about hinge axis 16 along vertical leg edge 18 parallel to legs 40 a, 40 b and 52 a, 52 b and perpendicular to braces 36 , 38 , 48 and 50 . Trapezoidal shelf 20 includes a first side 56 interconnected via hinge 26 to lower horizontal brace 38 of frame 12 , and a second side 58 interconnected via hinge 28 to lower horizontal brace 50 of frame 14 .
[0048] In the open position, trapezoidal shelf 20 is perpendicular to central hinge 16 that interconnects frames 12 and 14 , thereby resulting in a “V” shaped configuration between frames 12 and 14 connected at hinge 16 . In a closed storage position, frame 12 is generally parallel to frame 14 with trapezoidal shelf 20 folded therebetween. In the open position, shelf 20 rigidly secures legs 40 a, 40 b and 52 a, 52 b in position so they do not move with respect to one another. The rigid positioning of legs 40 a, 40 b and 52 a, 52 b combined with central hinge 16 securing frame 12 to frame 14 prevents relative motion between the components of sawhorse 10 , resulting in a rigid support structure designed to accommodate a substantial load.
[0049] In the exemplary embodiments shown, frames 12 and 14 have a length of 30 inches and a height of 31 inches. When locked in its open position, frames 12 and 14 create a 60 degree angle. Legs 40 a, 40 b and 52 a, 52 b are 4 inches wide by 1.75 inches deep, resulting in a surface area for each of 7 inches squared. Because legs 40 a, 40 b and 52 a, 52 b work together to create three stabilizing areas, the resulting stabilizing surfaces are 7 inches squared (for legs 40 b and 52 b ) and 14 inches squared (for combined legs 40 a and 52 a ).
[0050] While the above-dimensions are preferred, in further exemplary embodiments, frames 12 and 14 may have slightly variable dimensions. For example, frames 12 and 14 may be specifically manufactured for use with a certain material or weight. In some exemplary embodiments, the length and height of frames 12 and 14 may range between 25 and 35 inches. In most exemplary embodiments, frames 12 and 14 will have the same length and height.
[0051] Similarly, the 7-inches-squared surface area of legs 40 a, 40 b and 52 a, 52 b is preferred because a smaller surface area will not provide enough stability and it may be difficult to find a level surface to stabilize legs having a larger surface area. However, in further exemplary embodiments, the surface area of legs 40 a, 40 b and 52 a, 52 b may range from 5 to 10 inches squared.
[0052] In still further exemplary embodiments, frames 12 and 14 may create a different angle. For example, frames 12 and 14 may create an angle in the range of 50 to 70 degrees.
[0053] FIGS. 6-9 illustrate the separate components of frame 12 , with frame 14 (not shown) being symmetrically formed. As previously described, load bearing support 42 is formed along top edge of upper horizontal brace 36 . Central hinge 16 interconnects frame 12 with frame 14 .
[0054] FIG. 7 clearly illustrates the different stress bearing structures integrally molded with frame 12 . The inner surfaces of vertical members 32 , 34 , 44 and 46 contain horizontal supports 90 a (not shown) with vertical supports 90 b. Upper horizontal braces 36 and 48 contain diagonal braces 92 a (not shown) with vertical struts 92 b (not shown). Lower horizontal braces 38 and 50 contain diamond-shaped supports
[0055] FIGS. 14-17 illustrate the components of shelf side 56 of shelf 20 . Central shelf hinge 30 connects side 56 to shelf side 58 . Hinge 26 interconnects side 56 to frame 12 . Similarly, as illustrated in FIGS. 18-21 , central shelf hinge 30 connects side 56 to shelf side 58 . Hinge 28 interconnects side 58 to frame 14 . FIGS. 22 and 23 illustrate a tube member 60 which is part of hinge 16 .
[0056] In the exemplary embodiments shown, hinges 30 , 26 and 28 are created by a plurality of looped members 99 through which tube member 60 passes to form pivotal joints. As illustrated in FIGS. 22 and 23 , tube member 60 is generally cylindrical having notched segments 62 alternated with smooth segments 64 and provides a surface around which frames 12 and 14 and shelf sides 56 and 58 may pivot to go from the open position to the closed position,
[0057] In the exemplary embodiments described, sawhorse 10 is manufactured from a lightweight plastic material. In further exemplary embodiments, however, sawhorse 10 may be manufactured from other materials, including wood. Similarly, shelf 20 is described in the exemplary embodiments as trapezoidal, but may be any other shape while still functioning as a locking mechanism between frame 12 and frame 14 . Frames 12 and 14 may also be constructed as single continuous panels without separate vertical members and horizontal braces. | A folding sawhorse created by two pivotally connected frames containing a plurality of stress bearing structures on their inner surfaces forms a 60 degree angle when locked in place by a locking shelf. The frame components include two parallel vertical members separated at a distance by an upper horizontal brace and parallel lower horizontal brace. A U-shaped load bearing support is connected to the upper surface of the upper horizontal braces and provides four surfaces across which a load may be distributed when the folding sawhorse is in use. The trapezoidal locking shelf is pivotally connected to the lower horizontal braces and contains a central hinge, allowing the shelf to fold when the sawhorse is collapsed along its central vertical hinge. | 4 |
CROSS REFERENCE TO RELATED APPLICATION
This application is a continuation of U.S. patent application Ser. No. 13/973,685, entitled “Dental Guard System and Method for Forming” filed Aug. 22, 2013, which issued as U.S. Pat. No. 9,345,556, which claims the benefit of U.S. Patent Application Ser. No. 61/692,121, filed Aug. 22, 2013, entitled “Dental Guard System and Method for Forming.”
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a nighttime dental guard, impression tray, storage case and process of forming the dental guard using a microwave oven.
2. Problem Solved
The present invention overcomes the problems with the numerous other dental guards on the market in that it is made from a material which can absorb microwave energy and soften such that it can be molded by a user's teeth. The other products on the market do not work when subject to microwave heating. They must be heated in a pot of boiling water. The present invention is heated by microwave energy and not boiling water.
SUMMARY OF THE INVENTION
It is, therefore, an object of the present invention to provide a method of forming a user conformable dental guard. The method includes obtaining a storage case with a handle, wherein the storage case is made from a thermoplastic material that does not change shape when subjected to microwave energy during the method of forming, and inserting a dental guard and an impression tray in which the dental guard is positioned into the storage case. The dental guard softens when subject to microwave energy and has an upper surface and a lower surface. The method also includes filling the storage case with water and placing the storage case, with the water, the dental guard and the impression tray therein, into a microwave oven. The storage case, the water, the dental guard and the impression tray are then subjected to microwave energy for a period of time sufficient to soften the dental guard. The handle is then grasped and the storage case is removed from the microwave oven. The method also includes flushing the storage case with water to slightly cool the dental guard, removing the dental guard and impression tray from the storage case and inserting the dental guard and impression tray into the user's mouth. The dental guard is molded by application of force by the user's teeth to the upper surface of the dental guard and a lower surface of the impression tray.
It is also an object of the present invention to provide a method of forming a user conformable dental guard wherein after the application of force the dental guard is removed from the impression tray.
It is another object of the present invention to provide a method of forming a user conformable dental guard wherein the storage case includes a base and a cover with vent holes, and wherein the step of inserting includes closing the cover upon the base after the dental guard and impression tray have been placed within the storage case.
It is a further object of the present invention to provide a method of forming a user conformable dental guard wherein the step of filling of the storage case with water is performed by pouring the water through the vent holes in the cover.
It is also an object of the present invention to provide a method of forming a user conformable dental guard wherein the vent holes function to insure the storage case is filled with a correct amount of water as any excess water will simply flow out of the vent holes when the cover is closed upon the base.
It is another object of the present invention to provide a method of forming a user conformable dental guard wherein the vent holes allow for the venting of water vapor when the storage case, the water, the dental guard and the impression tray are subjected to microwave energy.
It is a further object of the present invention to provide a method of forming a user conformable dental guard wherein the step of flushing includes grasping the handle and flushing the storage case with tap water.
Other objects and advantages of the present invention will become apparent from the following detailed description when viewed in conjunction with the accompanying drawings, which set forth certain embodiments of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view showing the storage case containing the impression tray and dental guard prior to forming.
FIG. 2 is a top perspective view of an impression tray.
FIG. 3 is a front view of an impression tray.
FIG. 4 is a top view of an impression tray.
FIG. 5 is an upside down rear view of an impression tray.
FIG. 6 is a side view of an impression tray.
FIG. 7 is a cut away view along line 7 - 7 of FIG. 4 of an impression tray.
FIG. 8 is a rear view of an impression tray showing the beveled upper edges of exterior and interior upstanding wall members in detail.
FIG. 9 is a top perspective view of the dental guard prior to forming.
FIG. 10 is a perspective view of an open storage case containing an impression tray.
FIG. 11 is a front view of a closed storage case.
FIG. 12 is a top perspective view of the dental guard prior to forming.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The detailed embodiments of the present invention are disclosed herein. It should be understood, however, that the disclosed embodiments are merely exemplary of the invention, which may be embodied in various forms. Therefore, the details disclosed herein are not to be interpreted as limiting, but merely as a basis for teaching one skilled in the art how to make and/or use the invention.
In accordance with the present invention, and with reference to FIGS. 1 to 11 , a dental guard system 10 is shown. The dental guard system 10 includes a user conformable dental guard 100 , an impression tray 200 and storage case 300 . The dental guard 100 once formed provides users with protection from undesirable jaw clenching and/or tooth grinding while they sleep; that is, bruxism.
Referring to FIG. 1 , the present dental guard system 10 includes an impression tray 200 and a formable dental guard 100 . The formable dental guard 100 is shaped and dimensioned for positioning within the impression tray 200 during the forming process. The impression tray 200 is preferably formed from a relatively rigid biocompatible thermoplastic, for example, polypropylene or polyethylene, that will not change shape when subjected to heat or microwave energy. As will be appreciated based upon the following disclosure, the formable dental guard 100 is also manufactured from a biocompatible thermoplastic. However, the biocompatible thermoplastic from which the formable dental guard 100 is formed is a material permitting softening of the thermoplastic to allow for custom forming of the formable dental guard 100 upon the application of heat and/or microwave energy.
The present dental guard system 10 also includes a storage case 300 which is shaped and dimensioned for use in the forming process, while also providing a storage case for the dental guard 100 after it has been formed in accordance with the present invention. As such, and as with the impression tray 200 , the storage case 300 is preferably formed from a relatively rigid biocompatible thermoplastic that will not change shape when subjected to heat or microwave energy when forming a dental guard of the present invention, for example, polypropylene.
With regard to the impression tray 200 shown in FIGS. 2-8 , it is preferably an injection molded biocompatible thermoplastic. As discussed above, the impression tray is preferably manufactured from polypropylene or polyethylene. The impression tray 200 is substantially U-shaped and includes cavity 202 in which the formable dental guard 100 sits while applying microwave energy and heat, as well as during the forming process. As such, the impression tray 200 includes a first lateral side section 204 and second lateral side section 206 , the first and second lateral side sections 204 , 206 being connected by an arcuate center section 208 . It is appreciated the impression tray 200 is integrally formed. As such, the first lateral side section 204 includes an exterior upstanding wall member 210 and an interior upstanding wall member 212 , the exterior and interior wall members 210 , 212 being connected by a base member 214 extending therebetween. Similarly, the second lateral side section 206 includes an exterior upstanding wall member 210 and an interior upstanding wall member 212 , the exterior and interior wall members 210 , 212 being connected by a base member 214 extending therebetween. The arcuate center section 208 also includes an exterior upstanding wall member 210 and an interior upstanding wall member 212 , the exterior and interior wall members 210 , 212 being connected by a base member 214 extending therebetween. The base member 214 of the respective first lateral side section 204 , the second lateral side section 206 and the arcuate center section 208 each include an upper surface 214 a upon which the lower surface 110 of the dental guard 100 sits during the forming process and a lower surface 214 b shaped and dimensioned for engaging the lower teeth of a user during the forming process. The base member 214 is flat in first and second lateral side sections 204 , 206 , but curves upwardly at 214 c in arcuate center section 208 as best shown in FIG. 7 . This results in upper surface 214 a in the arcuate center section being slightly convex. The bottom surface 110 of the dental guard 100 matches the contour of upper surface 214 a.
The upper edge 220 of exterior upstanding wall member 210 in lateral side sections 204 , 206 and the upper edge 230 of interior upstanding wall member 212 in lateral side sections 204 , 206 maybe beveled in order to aid in directing the rear teeth approximate the first lateral side section 204 and second lateral side section 206 of the impression tray 200 into the dental guard 100 when forming. The beveled edges function as a wedge to force one's teeth inward into contact with the dental guard to be formed. Additionally, the exterior upstanding wall 210 in the arcuate center section 208 includes a raised area 222 having an alignment notch 225 used for centering the front of the impression tray 200 between the two front teeth of a user.
As is appreciated, the impression tray 200 , that is, the first lateral side section 204 , the second lateral side section 206 and the arcuate center section 208 are shaped and dimensioned so that the upper teeth of a user register with the dental guard 100 positioned therein. That is, the impression tray 200 , with the dental guard 100 positioned within the cavity 202 defined thereby, is shaped and dimensioned for positioning between the upper and lower teeth of the wearer.
In accordance with a preferred embodiment, during the process of customizing and forming the dental guard for an individual user the impression tray 200 and the dental guard 100 are placed in the wearer's mouth and the impression tray 200 is shaped and dimensioned so that the lower teeth of the wearer contact the lower surfaces 214 b of the base member 214 of the first lateral side section 204 , the second lateral side section 206 and the arcuate center section 208 .
In practice, the storage case 300 while open, with the dental guard 100 and impression tray 200 contained therein, is filled with water to completely cover the dental guard 100 and then the storage case 300 is closed. As will be appreciated based upon the following detailed disclosure of the storage case 300 , it is also possible to fill the storage case 300 with water with the cover member 302 closed over base member 303 by pouring water through the vent apertures (or holes) 304 formed in the cover member 302 until the storage case 300 is filled and the dental guard 100 and impression tray 200 are covered with water. The vents 304 also function to insure the storage case is filled with the correct amount of water as any excess water will simply flow out of the vents 304 when the cover 302 is closed. The base member 303 of storage case 300 also includes a handle section 306 to allow for easy gripping and handling of the storage case 300 . The handle section 306 allows one to grip the storage case 300 without having to come into contact with the camber formed by the cover member 302 and base member 303 . Thus, a user can avoid contact with the heated water contained in the storage case during the dental guard forming process.
The water filled storage case 300 while closed, with the dental guard 100 and impression tray 200 therein, is placed within a microwave oven until the dental guard 100 is sufficiently softened by the microwave energy for fitting. The microwave energy acts upon the dental guard 100 while the water functions dissipate heat. In accordance with a preferred embodiment of the present invention, the water filled storage case 300 is placed in a conventional household microwave oven and subjected to high energy for 45 to 90 seconds, depending upon the microwave oven used, to soften the dental guard 100 for fitting. The time can vary based on the age and wattage of any particular microwave oven. We have found the range of time can vary between 45 and 90 seconds, however 75 seconds seems to work for most microwave ovens.
The storage case 300 is removed from the microwave oven by grasping handle section 306 and is briefly flushed with cold or lukewarm water via vent apertures 304 to slightly cool the dental guard 100 and impression tray 200 . In accordance with a preferred embodiment, the storage case 300 , and the dental guard 100 and impression tray 200 maintained therein, are flushed with cold or lukewarm tap water for approximately 3 seconds.
The user then opens the storage case 300 and removes the impression tray 200 with the dental guard 100 maintained therein. In particular, the user immediately picks up the impression tray 200 with the dental guard 100 still held within the impression tray 200 , and carefully places it in his or her mouth by sliding the dental guard 100 /impression tray 200 backward in his or her mouth until the front teeth contact the exterior upstanding wall member 210 at raised area 222 of the arcuate center section 208 while using alignment notch 225 to center the impression tray 200 between their two front teeth. While looking in a mirror and using alignment notch 225 for a point of reference, or by feel the user aligns the center of the dental guard 100 /impression tray 200 below the two front teeth and the sides of the dental guard below the upper molars. The user then bites down on the dental guard 100 for approximately 1 minute to customize and shape the dental guard 100 to specifically fit the user. The dental guard 100 and the impression tray 200 are then removed from the user's mouth. Cold tap water is then poured over the dental guard 100 and impression tray 200 for 15 seconds to facilitate the setting of the molded dental guard 100 . The dental guard 100 is then allowed to cool and is then removed from the impression tray 200 and allowed to sit at room temperature for 2 hours after which time the dental guard 100 is ready for use. The impression tray 200 may then be discarded and the storage case 300 used for storing the dental guard 100 when the dental guard 100 is not in use. If the user makes a mistake and needs to reform the dental guard, the impression tray 200 can be used as a mold to attempt to reform the dental guard material back to a pre-molded state. This allows the user to start the process over to correct any fitting mistakes.
More particularly, the dental guard 100 , prior to forming in the procedure disclosed above, is U-shaped and includes a first lateral guard section 104 and second lateral guard section 106 , the first and second lateral guard sections 104 , 106 being connected by an arcuate guard section 108 . Prior to custom forming, the dental guard 100 also includes a smooth upper surface 102 and a smooth lower surface 110 , with an interior side wall 112 and an exterior side wall 114 extending therebetween. During the forming processing the lower surface 110 is in contact with the impression tray 200 and, therefore, remains smooth after the dental guard 100 is custom formed as discussed above. The smooth upper surface 102 is provided with an arcuate alignment groove 116 along the arcuate guard section 108 of the dental guard 100 for engagement with the front teeth of the user so as to enhance alignment of the dental guard 100 during the forming processing.
As best seen in FIG. 9 , dental guard 100 includes angled interior and exterior side walls 112 , 114 . Side wall 112 starts at edge 113 of the upper surface 102 and tapers down and outward to edge 115 of lower surface 110 . Side wall 114 starts at edge 117 of the upper surface 102 and tapers down and outward to edge 119 of lower surface 110 , resulting in the width of upper surface 102 being smaller than the width of lower surface 110 . In cross section the dental guard prior to forming appears as a truncated triangle. This shape results in edges 115 , 119 of the lower surface 110 of the dental guard 100 snapping into the impression tray 200 such that they are frictionally retained between upstanding side walls 210 , 212 of the impression tray 200 . The upper edges 113 , 117 of the upper surface 102 do not contact upstanding side walls 210 , 212 of the impression tray 200 . Thus, side walls 112 , 114 only contact upstanding side walls 210 , 212 of the impression tray 200 approximate lower edges 115 , 119 resulting in a space between side walls 112 , 114 of the dental guard and upstanding side walls 210 , 212 of the impression tray 200 . As such, during the forming process the side walls 112 , 114 of dental guard 100 can move outward, when bit into, before contacting the upstanding side walls 210 , 212 of the impression tray 200 . This results in a lower profile finished product which is more comfortable to the user as the dental guard material moves laterally outward before moving upward. That is, the interior and exterior portions of the dental guard 100 which fit about a user's teeth after forming extend a shorter distance up a user's teeth and remain well below the gum line.
In accordance with a preferred embodiment, the dental guard 100 is made from a propylene based elastomer having moderate elastomeric properties. The propylene based elastomer is an olefinic elastomer having an ethylene content of around 11.0% by weight. The elastomer has a melt mass-flow rate (g/10 min.) of 7.0 (230° C./2.16 kg) and does not degrade when subject to microwave radiation, but does become soft and moldable.
Once formed by the application of force by the teeth of a user, the dental guard 100 includes an upper surface 102 with cavities conforming to the shape and spacing of the user's upper teeth. In particular, the upper surface 102 is no longer smooth but includes a plurality of recesses registering with and conforming to the teeth of the user. The lower surface 110 and the side walls 112 , 114 of the dental guard 100 remain substantially smooth as they are supported within the cavity 202 of the impression tray 200 during the forming process. The lower surface 110 becomes hardened and compacted as a result of the user biting down into the dental guard. After the fitting process takes place, this hardened surface is what keeps the user from biting through the tray and grinding his or her teeth during the night while wearing the device.
As discussed above, the storage case 300 is shaped and dimensioned for storing the dental guard 100 prior to the forming processing, during the forming process, and after the forming process when the dental guard 100 is stored after use on a nightly basis. The storage case 300 includes a closed base 303 defining a cavity 308 in which the dental guard 100 is placed during use. In particular, the closed base 303 includes a plurality of upstanding side walls 310 extending from a perimeter of a base member 314 . The upstanding side walls 310 and the base member 314 define a cavity shaped and dimensioned for receiving the dental guard 100 , as well as the impression tray 200 with the dental guard 100 positioned therein.
The storage case 300 is further provided with a cover member 302 secured to the closed base 303 via a living hinge connection 316 . The perimeter edge 318 of the cover member 302 is shaped and dimensioned to mate with the upper ends 320 of the side walls 310 when the cover member 302 is brought into engagement with the storage case base 303 . The perimeter edge 318 of the cover member 302 opposite the edge of the cover member 302 with the living hinge 316 is provided with a fastening notch 322 shaped and dimensioned to engage a fastening notch 324 formed along the upper end 320 of the side wall 310 . In this way, the cover member 302 may be secured to the closed base 303 so as to enclose the cavity defined by the closed base 303 .
While the closed base 303 is formed without holes or other apertures so as to provide a cavity 308 in which water may be contained, the cover member 302 includes a plurality of venting apertures or holes 304 allowing for the venting of water vapor when the system 10 is subjected to microwave energy and heated in accordance with the present invention. Thus, excess pressure in the storage case 300 and over heating of the dental guard is prevented.
In accordance with a preferred embodiment, the dental guard 100 is impregnated with flavoring, such as mint, that enhances the usability of the dental guard 100 .
While the preferred embodiments have been shown and described, it will be understood that there is no intent to limit the invention by such disclosure, but rather, is intended to cover all modifications and alternate constructions falling within the spirit and scope of the invention. | A method of forming a user conformable dental guard includes obtaining a storage case with a handle, and inserting a dental guard and an impression tray in which the dental guard is positioned into the storage case. The method includes filling the storage case with water and placing the storage case and its contents into a microwave oven. The storage case and its contents are then subjected to microwave energy for a period of time sufficient to soften the dental guard. The method includes removing the storage case from the microwave over, flushing the storage case with water to slightly cool the dental guard, removing the dental guard and impression tray from the storage case and inserting the dental guard and impression tray into the user's mouth. The dental guard is molded by application of force by the user's teeth. | 1 |
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention relates to spin drying apparatus for drying plate-like or wafer-like elements, such as semiconductor wafers, during the fabrication of semiconductor components. Wafers used for the manufacture of integrated circuits are subjected to a plurality of fabrication steps including the steps of etching, coating, doping, plating, etc. until the desired multilayered configuration is achieved. After many of the steps, it is desirable to clean the wafer in order to remove contaminants and other particles generated during the previous operation to prepare the wafer for the following operations. The wafers must be cleaned, often on both sides, generally employing a liquid cleaner. After the cleaning step the wafer must be dried in a manner which does not leave contaminants on the surface of the wafer. The cleanliness requirements for semiconductor wafers is such that even films or stains generated by the evaporation of the cleaning fluid can be deleterious.
Heretofore centrifugal drying of wafers has been considered the optimal method of drying semiconductor wafers because the centrifugal force helsp to overcome the surface tension and the resultant clinging of moisture around the edge of a wafer that can result from other forms of drying. Generally, spin drying has been accomplished in the prior art by a vacuum chuck which grips the wafer on the lower face thereof. It has been found that holding the wafer in this manner results in staining of that face of the wafer because the liquid trapped between the chuck and the wafer which either cannot be removed or, during spinning, leaks out from the chuck and is dried as its spreads over the wafer face leaving stains which are unacceptable.
Further, it has been found that the increasing wafer sizes now being utilized to improve semiconductor production efficiency are increasingly difficult to safely hold with vacuum chucks. Any imbalance with larger wafers quickly generate forces which overcome the vacuum force, resulting in the destruction of the wafer as it is flung from the chuck.
One solution for this problem has been to use a spin dryer arranged to grip the edge of the wafer during spinning. A representative type of spin dryer employing edge gripping is disclosed in IBM Technical Disclosure Bulletin, Vol. 18, No. 6 of November 1975 at pages 1979 and 1980. This device includes a plurality of radial arms extending outwardly from a central shaft which is coupled to a drive means for imparting spinning motion to the arms and a wafer held thereby. However, it has been found that with spin dryers of this type, employing radially extending arms to support the wafer at the edge thereof, the arms generates sufficient turbulent air flow that particulate contaminants (solid or liquid) may be picked up by the turbulent air and redeposited upon the cleaned and/or dried surface of the wafer. As the complexity of semiconductor chips increases, along with an ever-decreasing size for the respective components thereon, it becomes more and more important to ensure that the wafers are not only adequately cleaned and dried but are protected against recontamination by contaminants anywhere during the cleaning and drying cycle. It will thus be apparent that the recontamination of already cleaned and dried wafer surfaces by contaminants stirred up by the operation of the spin drying apparatus itself can be extremely unsatisfactory, reducing the yield of the semiconductor devices.
SUMMARY OF THE INVENTION
Accordingly, the present invention provides a spin drying apparatus for drying semiconductor wafers wherein the wafers are contacted only at the edge thereof by a plurality of radially extending arms and wherein means is provided for preventing the generation of a fan-like effect from the rotation of the arms during the spin drying step.
According to one aspect of the present invention, spin drying apparatus is provided for drying a plate-like element, such as a semiconductor wafer, which apparatus comprises a shaft arranged for rotary motion having a drive motor at one end and a rotating head assembly at the other end. The head assembly comprises a head element arranged coaxially at the end of the shaft, which assembly has a plurality of radial arms extending outwardly therefrom. A plurality of movable arms are pivotally connected one to each of the radial arms, and each have a plate-engaging portion. A biasing means is provided for biasing the plate-engaging portions of the movable arms to a plate-engaging position, and means is provided for moving the movable arms against the force of the biasing means to selectively move the plate-engaging portions from the plate-engaging position. A containment means closely surrounds the radially extending arms and includes a cover element for substantially eliminating the generation of air flow around the plate-like element by the rotation of said radially extending arms.
According to another aspect of the present invention, spin drying apparatus is provided for drying a semiconductor wafer and comprises a vertical hollow shaft, arranged for rotary motion and having a drive motor at the lower end and a rotating head assembly at the upper end thereof. The head assembly includes a hollow head element coaxially arranged at the upper end of the hollow shaft and a plurality of pairs of spaced radial arms extending outwardly therefrom. A plurality of T-shaped arms are pivotally connected, one between each pair of arms at the outer ends thereof. Each of the T-shaped arms has an axially extending wafer-engaging leg portion and another leg portion extending radially between the pairs of radial arms into said head element. An actuating means is provided which includes an actuator rod disposed coaxially within the hollow shaft, as well as means in the head element for engaging the inner ends of the radially extending portions of the T-shaped arms. Means is provided for biasing the actuating means coaxially of the shaft towards the motor to move the wafer-engaging leg portions toward the center of the head assembly to a wafer-engaging position. Pin means is disposed through the lower end of the actuator rod, which pin means extends outwardly through the shaft and is attached to a collar which is engageable by a fork means disposed about the shaft. An actuator means is arranged to move the fork axially of the shaft to engage the collar and to move the actuating means upwardly against the force of the biasing means, thereby moving the wafer-engaging leg portions outwardly from the wafer-engaging position. A first containment means peripherally surrounds the rotating head assembly and has an open upper end with a diameter greater than the diameter of the rotating head assembly, This containment means has a downwardly and outwardly sloping intermediate portion adjacent the wafer-engaging leg portion of the T-shaped arms and a drain means is disposed in the lower portion thereof. A second containment means is closely and stationarily disposed about the rotating arms and is spaced inwardly from the lower portion of the first containment means. The second containment means terminates at an upper end just above the pivotal connection between the arms of the head assembly. A cover element is provided for the second containment means which is connected to and extends from the center of the head assembly outwardly beyond the axially extending wafer-engaging leg portions of the T-shaped arms and terminates in close proximity to the upper end of the second containment means. The second containment means and the cover element substantially prevent air flow around the wafer which would otherwise have been generated by the rotation of the head assembly. The T-shaped arms are provided with counterweights disposed on the opposite side of the pivotal connections from the wafer-engaging leg portions which provide a centrifugal force upon rotation of the head assembly that substantially equals or slightly exceeds the centrifugal force on the wafer-engaging leg portions during rotation. Thus, the centrifugal force of the counterweights tends to cause the wafer-engaging leg portions to grip the plate member. Means is also provided for elevating the rotating head assembly to a position wherein the wafer-engaging leg portions are disposed above the open upper end of the first containment means, and a first pair of nozzle means are arranged for directing a liquid onto both surfaces of the wafer during a first portion of the spin cycle while a second pair of nozzle means direct an inert gas onto both surfaces of the wafer during a second portion of the spin cycle.
Various means for practicing the invention and other features and advantages thereof will be apparent from the following detailed description of illustrative preferred embodiments of the invention, reference being made to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a plan view of a spin dryer according to the present invention; and
FIG. 2 is an elevation view, partly in section, taken along line 2--2 of FIG. 1.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to FIGS. 1 and 2 a preferred embodiment of the spin dryer apparatus is illustrated. The spin dryer comprises a rotating head assembly 130 disposed at the upper end of a substantially vertical hollow rotatable shaft 126. The rotating head assembly 130 includes a substantially cylindrical hollow head member 160 which is connected at the upper end of the shaft 126, and is provided with a plurality of pairs of spaced radially arms 124 extending outwardly therefrom. A plurality of T-shaped arms 122 are pivotally mounted at 123 between each pair of radial arms 124. Each of the T-shaped arms comprises an axially extending wafer-engaging leg portion having a wafer-engaging tip 125 at the outer end thereof, and a radially extending leg portion which extends into the head element 160. The wafer-engaging tip 125 at the outer end of the axially extending portion of the T-shaped arm is arranged to engage only the edge of a wafer to hold it in position for spin drying.
The shaft 126 is driven by a stepper motor 128 connected thereto by coupling 129 at the lower end thereof. The shaft 126 is provided with a central bore through which extends an actuator rod 162. The rod 162 has an enlarged upper end portion 164 within the cavity of head member 160. The end portion 164 is provided with an annular recess 166 which engages with the inner ends 168 of the radial portion of T-shaped arms 122. A biasing means, such as compression spring 170, is disposed around the upper end of rod 162 within an enlarged bore 172 in the upper end of the shaft 126. Spring 170 is compressed between a shoulder 174 at the upper end, and a collar 176 at the lower end connected to rod 162. Thus, spring 170 exerts a downward force on rod 162, to downwardly rotate the horizontal, radial portions of T-shaped arms 122, thereby drawing the wafer-engaging tips 125 toward the center of the head assembly into the wafer-engaging position. The lower end of the actuator rod 162 extends to the lower end of shaft 126 and terminates in sliding engagement with a bushing 178. Just above the lower end of rod 162, shaft 126 is provided with a pair of diametrically opposite slots 180 through the wall thereof. A horizontal pin 182 is connected through the rod 162 at this point and extends outwardly through the slots 180 in shaft 126 and connects to a collar 208.
Actuating means 184, either a solenoid or a pneumatic or hydraulic cylinder, is disposed on the far side of shaft 126 as illustrated in FIG. 2, with an operating shaft (not shown) extending upwardly therefrom parallel with shaft 126. At the upper end of the actuator shaft a fork 186 is provided having arms which extend around either side of shaft 126 just below collar 208. Upon operation of actuator 184, the fork is raised into engagement with collar 208, lifting rod 162 within shaft 126. As the upper end portion 164 is raised, the radially extending leg portions of T-shaped arms 122 are pivoted upwardly whereby the wafer-engaging tips 125 at the upper ends of the axially extending leg portions of arms 122 are rotated outwardly, thereby releasing their grip on a wafer, or in anticipation of the insertion of a new wafer into the spinner apparatus. When the actuator 184 is de-energized, the fork 186 is lowered, disengaging collar 208 and permitting spring 170 to force the rod 162 down, rotating the radially extending leg portions of arms 122 about the pivots 123 whereby the wafer-engaging tips 125 are again in wafer-engaging position.
The portions 127 of arms 122 below the pivot 123 are carefully designed to counterbalance and counteract any tendency of the upper portions of the arms to be pulled outward by centrifugal force during the spinning operation, with the possible resultant reduction in force gripping the wafer. Preferably the counterweights are so configured that the centrifugal force acting on the counterweight portion substantially equals or is slightly greater than the centrifugal force on the wafer-engaging tips 125, whereby the centrifugal force of the counterweight tends to cause the wafer-engaging tips to grip the wafer with at least as much, or slightly greater force than that provided by the spring 170 alone.
The spinner head assembly 130 is surrounded by a first containment means comprising a stationary cylindrical collector bowl 132 which has an open upper end with a diameter sufficiently greater than the diameter of the rotating head assembly that it may be moved upwardly therethrough to receive and discharge wafers, in a manner to be described hereinbelow. The cylindrical collector bowl 132 is provided with a downwardly and outwardly sloping intermediate portion 133 adjacent the wafer-engaging tips 125 of the T-shaped arms. The bowl is arranged to confine any moisture centrifugally removed from the wafer and to prevent its escape into the remainder of the apparatus surrounding the spin dryer, or redeposition onto the wafer surface. Thus any particles, solid or liquid, which are centrifugally discharged from a surface of the wafer strike the sloping shoulder portion 133 of the bowl and are deflected downwardly to the bottom of the collector bowl where they are removed by a suitable drain, not shown, which is provided in the bottom of the containment means.
As noted above, it has been found that with centrifugal spin dryers of the type disclosed herein, utilizing radial arms which grip the edges of the wafers, that problems have been encountered because of the air flow generated by the centrifugal pumping action of the rotating radial arms. It has been found that this air flow results in a turbulence around the wafer which entrains particulate liquid and/or solid material which may then be redeposited upon the wafer surface. With the present invention such air pumping and turbulent air flow is substantially eliminated by a second containment means comprising a stationary inner cylindrical shield member 200 which is disposed about the radially extending arms of the head assembly. The shield member is mounted to the stationary housing 206 for shaft 126 and is spaced inwardly from the lower portion of the cylindrical collector bowl 132. The upper end of the cylindrical shield member terminates just above the pivotal connection 123 between the radial arms 124 and the T-shaped arms 122. A cover element 202 for the second containment means is mounted on the head assembly 160 and extends from the center thereof outwardly beyond the axially extending wafer-engaging leg portions of the T-shaped arms and terminates in close proximity to the upper end of the shield member 200. The cover element 202 is arranged to rotate with the head assembly. As illustrated, the cover element 202 is provided with a sloping outer periphery and is provided with openings around the axially extending leg portions large enough to permit movement thereof for engaging and disengaging a wafer.
The entire spinner assembly, including the motor 128 is arranged to be lifted by a pneumatic or hydraulic cylinder 134 to lift the wafer-engaging tips 125 above the top of the collector bowl 132 for receiving and discharging wafers from the spin dryer apparatus. The spin dryer apparatus is supported and guided for a vertical movement by a pair of vertical guide rods 190. Two pair of bearing blocks 192 and 194 extend from the side of the spinner assembly and are provided with bearings which ride on the rods 190. The cylinder 134 is disposed between the rods and is connected by a bracket 196 to the side of the spinner assembly. The upper end of the piston rod (hidden behind rod 190) is fixed to the mounting frame for the spinner assembly. Thus, when the cylinder is actuated it is drawn up the piston rod, carrying the spinner assembly with it until the wafer engaging tips 125 reach the position illustrated in phantom, above the top edge of the collector bowl, where it is accessible to a wafer transfer mechanism for transfer either to or from the spin drying assembly.
Two pairs of spray nozzles 136, 138 and 139, 140 are provided to spray both surfaces of the wafer. The first pair of nozzles 136 and 138 are arranged to spray water onto both surfaces of the wafer to provide a final rinse before the drying cycle. The second pair of nozzles 139 and 140 spray both surfaces with an inert gas such as nitrogen to assist in the drying during the spin drying of the wafer. In a preferred operational cycle, the wafer is first spun at a slow speed while water is sprayed from nozzles 136 and 138 for a sufficient time to wash the wafer surface and then the speed of the motor is increased to centrifugally dry the wafer surfaces with the inert gas provided by nozzles 139 and 140 assisting in the drying process.
It will thus be seen that the present invention provides a spin drying apparatus which provides the advantages of gripping the wafer at the edges only and yet prevents the problem of recontamination by air pumped by the rotating radial arms.
The control system for the spin dryer takes advantage of the use of stepper motor 128 to control the spin cycle as well as the stopping position of the wafer-engaging arms. Thus, the stop position of the rotating head may be selected so that the wafer-engaging arms do not interfere with the wafer transfer mechanism transferring wafers to and from the spin drying mechanism.
The invention has been described with reference to specific embodiments and variations, but it should be apparent that other modifications and variations can be made within the spirit and scope of the invention, which is defined by the following claims. | A spin drying apparatus for drying semiconductor wafers wherein the wafers are contacted only at the edge thereof by a plurality of radially extending arms and wherein means is provided for preventing the generation of turbulent air flow by the fan-like effect of the rotation of the arms during the spin drying step and the recontamination of already cleaned and dried wafer surfaces by contaminants stirred up by the operation of the spin drying apparatus itself. | 6 |
BACKGROUND OF THE INVENTION
The present invention relates to a process for preparing compounds of the molecular structure represented by the formula: ##STR2## wherein X is selected from the group consisting of: (A) WHERE THE COMPOUNDS ARE TETRAHYDROPYRAN TYPE COMPOUNDS ##STR3## (b) where the compounds are 1,4-dioxane type compounds: ##STR4## and (C) WHERE THE COMPOUNDS ARE TETRAHYDROFURAN TYPE COMPOUNDS: ##STR5## WHEREIN R is selected from the group consisting of alkali metal, ammonium, trialkanolammonium, and lower alkyl, branched or straight chain, with up to about C 20 in the chain, comprising:
(a) preparing a suitable halo dicarboxy ester of an aldehyde of the general formula ##STR6## wherein M is halogen, X is as defined above, and R' is lower alkyl, preferably ethyl or methyl.
(b) cyclizing the compound of (a) to the cyclic cyano diester intermediate of the formula: ##STR7## wherein X and R' are as given above, and (C) HYDROLYZING THE INTERMEDIATES TO Step b) to the corresponding salts, and if desired, converting the salts to the corresponding triesters or acids.
The salt compounds produced in accordance with the process of the present invention have utility as water softeners, detergent builders, calcium and magnesium sequestrants, scale dissolvers, and the like. The compounds may be used alone or as additives to a variety of solid or liquid detergent formulations. In such formulations the compounds enhance the cleaning capacity of the detergent by providing a builder, threshold or other effect. The esters are useful in synthesizing the pure salt forms of the compounds. The cyclic cyano diester intermediates are useful in preparing the end product tri-salts, esters or acids.
DESCRIPTION OF THE PRIOR ART
The preparation of some of the compounds within the scope of the general formula set forth above is described in U.S. patent application Ser. No. 756,947 filed Jan. 5, 1977 in the names of Marvin M. Crutchfield and Charles J. Upton. In that application the inventors describe a process for producing compounds, such as the trisodium and triester-2,2,6-tetrahydropyran-tricarboxylates by a process of basic carboxylation to produce the partial esters followed by hydrolysis to the salt forms. The salts in turn are capable of being esterified to the corresponding full esters.
The present invention comprises a novel and highly effective route to the synthesis of the subject compounds which is entirely dissimilar to the phenate carboxylation approach taken by Crutchfield and Upton.
SUMMARY OF THE INVENTION
The invention provides a highly effective method for synthesizing compounds having a molecular structure represented by the formula: ##STR8## wherein X and R are as described above.
The method for preparing the subject compounds generally comprises,
(a) preparing a suitable halo dicarboxy ester of an aldehyde of the general formula ##STR9## wherein M is halogen, and R' is lower alkyl, preferably ethyl or methyl. (b) cyclizing the compound of a) to form the cyclic diester intermediate of the formula: ##STR10## wherein X and R' are as described above, (c) hydrolyzing the intermediates of Step (b) to the corresponding salts, and
(d) if desired, esterifying the salts of Step c) to the corresponding esters.
Among the preferred compounds (and intermediates) of the above general formula which may be prepared in accordance with the present process, are the following: ##STR11##
In the above formulae R is as described above, but is preferably CH 3 or C 2 H 5 for the cyano intermediate compound and H, Na, CH 3 or C 2 H 5 for the end product compound.
DETAILED DESCRIPTION OF THE INVENTION
A detailed description of the process of the present invention is embodied in the following illustrative working examples.
EXAMPLE 1
Preparation of Trisodium 2,2,6-Tetrahydropyrantricarboxylate
(a) Preparation of γ-Chlorobutyraldehyde Diethyl Acetal
The named compound was prepared by the method of Loftfield, J. Am. Chem. Soc., 73 1365 (1951), with minor modifications, according to the following general reactions: ##STR12##
In carrying out this step of the preparation a 3l baffled 3-neck, round bottom flask was fitted with a gas dispersion tube, mechanical stirrer and reflux condenser. The flask was charged with 282g (2 moles) of γ-chlorobutyryl chloride, 1450 ml toluene, 30g of 5% Pd/BaSO 4 , and 3.1 ml of quinoline/sulfur catalyst poison (catalyst poison was prepared by refluxing 1g sulfur with 6g quinoline for 5 hours and diluting to 70 ml with xylene). Hydrogen was then bubbled through the stirred reaction mixture and the temperature raised to reflux. The off-gases were bubbled into a 2l flask containing 1.5l water. 5N NaOH was added to neutralize the HCl as it was given off. After 3 hours, HCl evolution had stopped and the reaction mixture was allowed to cool at room temperature under a N 2 atmosphere.
A solution of 200g CaCl 2 in 1250 ml abs. EtOH was added and the stirring was continued overnight. The reaction mixture was filtered to remove the catalyst and the filtrate was washed with 800 ml water and 2 × 400 ml 5% NaHCO 3 solution. The aqueous phases were combined and extracted with 500 ml toluene. The organic phases were combined and washed with 400 ml 5% NaHCO 3 , 400 ml saturated NaCl and dried over anhydrous K 2 CO 3 . The mixture was filtered and the bulk of the toluene was removed on a rotary evaporator. The crude product was then distilled through an 18 inches silvered vacuum jacketed column packed with Berl saddles. The product (283g) was collected at 83°-4° at water aspirator pressure (89°-92°/14mm). This is a 78% yield based on raw materials. A later similar run gave 81%. 'H nmr was consistent with the structure.
(b) Preparation of δ,δ-Dicarbethoxyvaleraldehyde Diethyl Acetal
The named compound was prepared by reacting the γ-chlorobutyraldehyde diethyl acetal prepared in accordance with Step a), above, with sodium diethyl malonate according to the following reaction: ##STR13##
To carry out the foregoing preparation 168g (1.05 mole of diethyl malonate and 15g (0.1M) NaI were added to a solution of 23g (1M) of Na and metal dissolved in 750 ml ethanol. After about 5 minutes at 50° C., 190g (1.05M) of γ-chlorobutyraldehyde diethyl acetal was added. The temperature was raised to reflux and after 1.5 hours an additional 80g (0.5M) of diethyl malonate was added. The reaction mixture was refluxed overnight. The next day glc indicated unreacted acetal, so additional Na/EtOH was added and the mixture was refluxed for 3 more hours. The ethanol was then removed on a rotary evaporator and the residue taken up in a mixture of 200 ml H 2 O and 200 ml ether. The layers were separated and the ethereal layer was washed with 2 × 200 ml 5% NaHCO 3 . The aqueous washes were combined with the original aqueous layer and extracted with 200 ml ether. The ethereal solutions were combined and washed with 5% NaHCO 3 and saturated NaCl. After drying over K 2 CO 3 and removing the ether on a rotary evaporator, 366g of 60-70% pure product remained.
This crude product was distilled under vacuum and the product collected at 115°-124° at 0.1mm Hg. The product (223g, 70% yield) gave a 'H nmr consistent with the structure.
(c) Preparation of δ-Bromo-δ,δ-Dicarbethoxyvaleraldehyde Diethyl Acetal
The named compound was prepared by reacting δ,δ-dicarbethoxyvaleraldehyde diethyl acetal as prepared in Step b) with sodium ethoxide and then reacting the resulting sodium compound with bromine according to the following reactions: ##STR14##
These reactions were carried out in the following manner:
To a slurry of 45g 50% NaH (washed with 4 × 100 ml pentane) in 750 ml DMF was added 259g of the diethyl acetal of Step b) and 4.5 ml ethanol. The mixture was stirred at <25° for 2 hours and then an additional 4.5 ml EtOH was added. Since this caused increased H 2 evolution, the mixture was stirred an additional 6 hours, after which 9 more ml of EtOH were added. The reaction mixture was cooled to about 10° and a solution of 144g Br 2 in 200 ml DMF was added while the temperature was maintained at <15°. The reaction mixture was allowed to stir overnight at room temperature.
The reaction mixture was diluted with 1l of H 2 O and extracted with 3 × 1l benzene. The benzene extracts were washed with 2 × 1l H 2 O and 2 × 1l saturated NaCl. The benzene was removed on a rotary evaporator leaving 135g crude product which by glc was about 85% pure. The 'H nmr was in agreement with the structure. Experience with a previous run had shown that decomposition occurred during distillation so this material was used without further purification.
The choice of DMF as a solvent for this step was not optimum since DMF reacts with NaOEt as evidenced by the presence of considerable amounts of dimethyl amine at the time of the Br 2 addition.
(d) Preparation of δ-Bromo-δ,δ-Dicarbethoxyvaleraldehyde
The named compound was prepared by the hydrolysis of the diethyl acetal prepared in accordance with Step (c), above, by the following reaction: ##STR15##
In this step a solution of 305g of crude diethyl acetal in 300 ml benzene was stirred overnight at room temperature with 2.5l of 4N HCl. The reaction mixture was extracted with 5 × 500 ml benzene. The benzene extracts were washed with 1 × 500 ml H 2 O, 2 × 500 ml 5% NaHCO 3 , and 2 × 500 ml saturated NaCl. The solution was dried over CaSO 4 and the benzene removed on a rotary evaporator having 240g of crude product. The 'H nmr was consistent with the structure. The material was used without further purification.
(e) Preparation of Diethyl 6-cyano-2,2-tetrahydropyran dicarboxylate
The named compound was prepared by cyclizing the aldehyde prepared in accordance with Step d) supra, using sodium cyanide in dimethyl sulfoxide according to the following reaction: ##STR16##
To a slurry of 50g of NaCN in 700 ml DMSO was added 222g crude aldehyde in 80 ml DMSO. The temperature rose spontaneously to 65° at which it was held by controlling the rate of addition of VI. The temperature was then held at 65° for an additional 4 hours.
The reaction mixture was diluted with 1.5l H 2 O and extracted with 6 × 500 ml benzene. The combined extracts were washed with 500 ml saturated NaHSO 3 , 2 × 500 ml 5% NaHCO 3 , 3 × 500 ml saturated NaCl and then dried over CaSO 4 . The benzene was removed on a rotary evaporator having 145g crude product about 50-55% pure.
After several vacuum distillations 65g of 98% pure product was obtained. B.p. 119-121 mm Hg. The 'H nmr was consistent with the structure.
(f) Preparation of Trisodium 2,2,6-Tetrahydropyrantricarboxylate
The named compound was prepared by hydrolysis of the 6-cyano-2,2-tetrahydropyrandicarboxylate prepared in accordance with Step (e) above, by the following reaction: ##STR17##
To a solution of 81g of 50% NaOH and 80 ml H 2 O still warm from mixing was added a solution of 65g of VII in 200 ml MeOH. After stirring overnight at room temperature the solution was warmed to insure that ammonia evolution had ceased. When no ammonia could be smelled, the solution was allowed to cool and stand overnight at room temperature. This solution was poured into MeOH and an oil was obtained which solidified on further treatment with MeOH as the trisodium salt.
(g) Preparation of Triethyl 2,2,6-Tetrahydropyrantricarboxylate (IX)
The named compound was prepared by esterification of the trisodium salt of Step (f). The salt was added to a solution of 600 ml of ethanol and 160 ml acetyl chloride and refluxed for 3 hours. The excess HCl was neutralized by adding solid NaHCO 3 and water until CO 2 evolution ceased. Additional H 2 O was added until almost all of the solids had dissolved. The aqueous solution was then extracted with 3 × 500 ml benzene. The extracts were washed with 300 ml 5% NaHCO 3 and 2 × 300 ml saturated NaCl and filtered. Most of the benzene was removed on a rotary evaporator and the residue dried over CaSO 4 . The remaining benzene was removed and the residue (50g) was found to be 95% pure. This was vacuum distilled to give a 30.6g fraction which was 97% pure. Other fractions of 93-95% purity were also obtained but not combined with the purest cut. The 'H nmr and IR were identical to those obtained for material prepared by the phenate carboxylation route employed by Crutchfield and Upton and described in previously identified Application Serial No.
EXAMPLE 2
Ammonium, triethanolamine, other soluble alkali metal salts, and the acid form of the cyclic tricarboxylate conpounds of this invention are prepared by passing an aqueous solution of the corresponding sodium salt through a column of cationic exchange resin charged with the desired cation, followed by isolation of the salt from the aqueous solution by evaporation or crystallization.
EXAMPLE 3
The trisodium 2,2,5-tetrahydrofurantricarboxylate may be prepared as follows:
(a) Preparation of γ,γ-dicarbethoxybutyraldehyde
First, 100 ml acrolein was added to a solution of 180g diethyl bromomalonate, 14g tributylamine, and 600 ml ethanol while cooling in an ice bath. After 2-3 hours, an additional 1.5g tributylamine and 20 ml acrolein was added. The stirring was continued for an additional 1 to 2 hours without additional cooling. The reaction mixture was neutralized with 7 ml glacial acetic acid and the ethanol and unreacted acrolein were removed on a rotary evaporator. The residue was diluted with 500 ml benzene and washed with 3 × 100 ml H 2 O and 2 × 100 ml saturated NaCL solution. The benzene solution was dried over CaSO 4 and rotary evaporated to yield 207g of yellow oil which was indicated to be 48% product by glc.
(b) Preparation of 4-cyano-2,2-dicarbethoxytetrahydrofuran
To a slurry of 30g of NaCN in 500 ml dimethylsulfoxide (DMSO) was added a solution of 150g of the crude bromoaldehyde product of Step a) in 100 ml DMSO. The reaction was exothermic and cooling was required to maintain the temperature below 70° during addition. After the addition was complete heating was required to maintain the temperature at 60°-70° for 3.5 hours. The reaction mixture was allowed to cool to room temperature and then was poured into 600 ml H 2 O. This solution was extracted with ether. The ethereal extracts were combined, washed with water and saturated NaCl, and dried over CaSO 4 . After removing the ether on a rotoevaporator 87.3g of red brown oil remained which contained 91% product by glc. Vacuum distillation (120°-150°/0.05 mm Hg) gave the product as a colorless oil. 'Hnmr analysis was consistent with the structure.
(c) Preparation of Trisodium 2,2,5-Tetrahydrofurantricarboxylate
To a warm solution of 64.1g of 50% NaOH in 200 ml H 2 O was added 60g of the product of Step b) diluted with 20 ml ethanol. The solution was initially two phase but became homogeneous after stirring several minutes. The solution was maintained at 60°-70° under a stream of N 2 for 3 hours. The resulting yellow solution was poured into 450 ml MeOH. An oil formed which on further workup under MeOH gave a yellow solid. The solid was dissolved in H 2 O and treated twice with charcoal. The pale yellow solution was treated repeatedly with ethanol until it solidified. The solid was washed with ether and dried overnight in a vacuum oven at 80°. The solid was ground in a blender and dried an additional 3 hours in the vacuum oven. The yield was 59g of off-white powder.
'Hnmr indicates some ethanol was still present as well as 1/2 mole H 2 O. Thermographic analysis showed a 5.9% weight loss up to 350° at which point decomposition occurred. There appears to be a very thermally stable 1/2 hydrate which does not break down until about 250°. Glc analyses of the salt indicated 84% of the trisodium 2,2,5-tetrahydrofurantricarboxylate and 15% dicarboxylate. Dicarboxylate probably resulted from decarboxylation of some of the tricarboxylate during hydrolysis and/or charcoal treating. The divalent ion electrode titration gave the following values: A = 54 mV; B = 37 mV; C = 6.2 ml; D = 7.4 ml for an intensity-capacity index of 92% STP.
The salt appears to have a water solubility of slightly greater than 50% and when a 50% solution is allowed to evaporate, crystals of the product form. The solution could be evaporated to dryness and the product did not appear to be hydroscopic. Purification by crystallization should be possible.
EXAMPLE 4
Preparation of Trisodium 1,4-Dioxane-2,2,6-tricarboxylate
Trisodium 1,4-dioxane-2,2,6-tricarboxylate and its esternitrile precursor is prepared in the same manner as described in Example 1 for trisodium 2,2,6-tetrahydropyrantricarboxylate except that Compound X: ##STR18## is substituted for Compound V in Step (d) of Example 1. Compound X is prepared as follows: ##STR19##
A solution of 27g of (I) as described in A. Ya. Yakubovich and I. N. Belyreva, Zhur, Obshchei Khim. 31, 2119-22 (1961) CA: 56, 313e (1962) in 25 ml tetrahydrofuran (THF) is added to a slurry of 2.4g of NaH in 100 ml THF. When evolution of H 2 has ceased, 19.7g of II is added and the mixture solution warmed to reflux temperature of the THF. The reaction mixture is refluxed until neutral. The solvent is removed on a rotary evaporator. The residue is taken up in ether, washed with water and saturated NaCl solution and dried over CaSO 4 . The ether is removed on a rotary evaporator leaving the crude product. | A compound of the formula ##STR1## wherein R' is lower alkyl, is useful as an intermediate in the preparation of a corresponding tricarboxylate, which is a useful detergent builder. | 2 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the priority of Korean Patent Application No. 2004-63101, filed on Aug. 11, 2004, in the Korean Intellectual Property Office, the disclosure of which is incorporated herein in its entirety by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] Embodiments of the present invention relate to a recording and/or reproducing apparatus and method, e.g., a hard disk drive, and more particularly, to a head gimbal assembly (HGA) protecting member and method preventing damage to an HGA and a method of implementing the HGA protecting member in the hard disk drive.
[0004] 2. Description of the Related Art
[0005] A hard disk drive (HDD) is a data storage device for a computer, for example, to read data from a hard disk and/or write data on/to the hard disk by using a magnetic head. The hard disk drive can include a base provided with a head gimbal assembly (HGA). The magnetic head can be movably supported on the disk by the HGA. Typically, an HGA protecting member is mounted to the HGA to prevent the HGA and/or components related to the HGA from being damaged in the course of transporting the HGA or while installing the HGA to the base.
[0006] FIGS. 1 and 2 respectively illustrate a perspective view and a rear view of the HGA with a conventional HGA protecting member mounted thereto.
[0007] Referring to FIGS. 1 and 2 , the HGA 10 can include an actuator 16 rotatable a desired angle around a pivot 12 , on a base (not shown) of a hard disk drive, two pairs of suspensions 20 , 25 , 30 and 35 fixed to one end of the actuator 16 , and a motor coil 14 on the other end of the actuator 16 , with the pivot 12 interposed between the motor coil 14 end and the suspensions end of the actuator 16 . The base of the hard disk drive can be provided with a magnet (not shown), to rotate the HGA 10 in a direction according to the Fleming's left-hand rule by interaction between a current input to the motor coil 14 and a magnetic field generated by the magnet.
[0008] The suspensions 20 , 25 , 30 and 35 can be provided with corresponding end-taps 21 , 26 , 31 and 36 , which are supported by a ramp (not shown) when the HGA 10 is parked. Flexures 22 , 27 , 32 and 37 can be attached to opposite ends of the paired suspensions 20 , 25 , 30 and 35 , and sliders 23 , 28 , 33 and 38 can be attached to the corresponding flexures 22 , 27 , 32 and 37 , such that paired sliders oppose each other. Magnetic heads (not shown) can be mounted to each of the sliders 23 , 28 , 33 and 38 to write and/or read data to/on the disk.
[0009] During operation of the hard disk drive, the sliders 23 , 28 , 33 and 38 can be maintained in a floating state at a desired height above the rotating disk. The floating state can be maintained by the balance of power acting on the sliders. In order to keep the balance of force, the paired suspensions 20 and 25 (as well as paired suspensions 30 and 35 ) are bent to approach the paired of sliders 23 and 28 (and corresponding paired sliders 33 and 38 ), with the paired sliders facing to each other.
[0010] Therefore, while transporting the HGA 10 or while installing the HGA in the base, the facing sliders 23 and 28 and facing sliders 33 and 38 may collide with each other, even after weak impacts. Accordingly, an HGA protecting member 40 may be mounted to the HGA 10 in order to prevent such collision during such transport or installation.
[0011] The HGA protecting member 40 typically includes a pair of fingers 43 and 44 along an end thereof. The lower finger 43 is inserted between the pair of lower suspensions 20 and 25 , while the upper finger 44 is inserted between the pair of upper suspensions 30 and 35 . Although the conventional HGA protecting member 40 is installed on the HGA 10 , paired flexures 22 and 27 and paired flexures 32 and 37 , as well as paired sliders 23 and 28 and paired sliders 33 and 38 , attached thereto, are not supported by the fingers 43 and 44 . Therefore, the HGA may still be in danger of being damaged by impact. Also, since the end-taps 21 , 26 , 31 and 36 of the respective suspensions 20 , 25 , 30 and 35 are not near the support points of the fingers 43 and 44 , collision of the end-taps is still possible.
SUMMARY OF THE INVENTION
[0012] Embodiments of the present invention provide an HGA protecting member and method preventing damage of a flexure, suspension, and end-tap of an HGA.
[0013] Embodiments of the present invention also provide a member and method for installing an HGA in a hard disk drive by use of an HGA protecting member.
[0014] To achieve the above and/or other aspects and advantages, embodiments of the present invention include a head gimbal assembly (HGA) protecting member to be mounted to an HGA including an actuator, at least one pair of suspensions coupled to the actuator, a flexure having a stationary end fixed to each of the suspensions and a free end, with a slider attached between the stationary end and the free end of the flexure, the HGA protecting member including a finger to restrict movement of the suspension, the finger including a flexure supporting portion to support the free end of the flexure.
[0015] The suspension may include an end-tap, and the finger includes an end-tap supporting portion to support the end-tap. In addition, the finger may further include a stepped portion formed between the flexure supporting portion and the end-tap supporting portion.
[0016] The finger may have a tapered shape so that the finger is insertable between adjacent suspensions without damaging the adjacent suspensions. Further, the HGA protecting member may also include a mounting boss inserted into a through-hole formed at the actuator of the HGA.
[0017] To achieve the above and/or other aspects and advantages, embodiments of the present invention include a head gimbal assembly (HGA) protection method for an HGA including an actuator, at least one pair of suspensions coupled to the actuator, a flexure having a stationary end fixed to each of the suspensions and a free end, with a slider attached between the stationary end and the free end of the flexure, the HGA protection method including restricting movement of the suspension with a flexure supporting portion supporting the free end of the flexure.
[0018] The restricting of movement may be performed by a finger inserting between adjacent suspensions without damaging the adjacent suspensions.
[0019] The restricting of movement further may also support an end-tap at an end of the suspension.
[0020] To achieve the above and/or other aspects and advantages, embodiments of the present invention include a method of implementing an HGA for a hard disk drive, the HGA including an actuator, at least one pair of suspensions coupled to the actuator, a flexure having a stationary end fixed to each of the suspensions and a free end, with a slider attached between the stationary end and the free end of the flexure, the method including instituting a first HGA protection restricting movement of the suspension, the restricting being implemented by a first finger including a flexure supporting portion supporting the free end of the flexure, wherein the first finger is inserted between adjacent suspensions so that the flexure supporting portion firmly supports the free end of the flexure, installing the HGA including the first HGA protection in a base of the hard disk drive, and ceasing the first HGA protection of the HGA.
[0021] The ceasing of the first HGA protection may include removing the first finger from between the adjacent suspensions.
[0022] Further, the suspension may include an end-tap and the first finger includes an end-tap supporting portion supporting the end-tap, wherein the first finger is inserted between the adjacent suspensions so that the end-tap supporting portion supports the end-tap. The first finger may include a stepped portion formed between the flexure supporting portion and the end-tap supporting portion.
[0023] The first finger may have a tapered shape so that the first finger is insertable between the adjacent suspensions without damaging the adjacent suspensions.
[0024] In addition, the HGA protection may further include having a mounting boss inserted into a through-hole of the actuator of the HGA, wherein when the first HGA protection is implemented, the mounting boss is in the through-hole, and when the first HGA protection is ceased, the mounting boss is not in the through-hole.
[0025] The method may further include instituting a second HGA protection supporting a portion of the suspension between parts attached to the actuator and the flexure using a second finger inserted between the adjacent suspensions, wherein the second finger is inserted between the adjacent suspensions, prior to the HGA being installed in the base of the hard disk drive, to support the portion of the suspension between the parts attached to the actuator and the flexure, and ceasing the second HGA protection by removing the second finger between the adjacent suspensions.
[0026] The method of implementing the HGA for the hard disk drive may be a method of installing the HGA into the hard disk drive using an HGA protecting member to institute the HGA protection, wherein upon installation of the HGA into the hard disk drive the hard disk drive can be operable upon removal of the HGA protecting member from the HGA.
[0027] Additional aspects and/or advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0028] These and/or other aspects and advantages of the invention will become apparent and more readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
[0029] FIGS. 1 and 2 illustrate respective perspective and rear views of an HGA with a conventional HGA protecting member;
[0030] FIG. 3 illustrates a perspective view of an HGA protecting member, according to an embodiment of the present invention;
[0031] FIGS. 4 and 5 illustrate respective top and front views of an HGA with the HGA protecting member, according to an embodiment of the present invention;
[0032] FIGS. 6 and 7 illustrate respective top and rear views of an HGA with an HGA protecting member, according to another embodiment of the present invention; and
[0033] FIG. 8 illustrates a top view of an HGA with an HGA protecting member, according to still another embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0034] Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the like elements throughout. The embodiments are described below to explain the present invention by referring to the figures.
[0035] FIG. 3 illustrates a perspective view of an HGA protecting member 100 , according to an embodiment of the present invention, with FIGS. 4 and 5 illustrating respective top and front views of an HGA with the HGA protecting member 100 .
[0036] Referring to FIGS. 3 through 5 , the HGA protecting member 100 can be made of a plastic resin by molding, for example, and can include a mounting boss 105 for insertion into a first through-hole 17 of an actuator 16 , and fingers 110 and 140 for insertion between paired adjacent suspensions 20 and 25 and paired adjacent suspensions 30 and 35 . Also, the HGA protecting member 100 can be provided with a handle 102 . The first through-hole 17 of the actuator 16 can be used so that the suspensions 20 , 25 , 30 , and 35 can attach to the actuator 16 by swaging.
[0037] As the shape and function of each of the fingers 110 and 140 may be similar to each other, only the insertion of finger 140 between the suspensions 30 and 35 will now be described in detail. Thus, the following description of the finger 140 can be applied to insertion of the finger 110 between the suspensions 20 and 25 . The finger 140 can be formed with a wedge shape with inclined surfaces 142 and 152 to be easily inserted between the pair of adjacent suspensions 30 and 35 . The finger can also include lower and upper flexure supporting portions 143 (shown in FIG. 5 ) and 144 extending from the inclined surface 142 , and lower and upper end-tap supporting portions 153 (shown in FIG. 5 ) and 154 extending from the inclined surface 152 . A stepped portion is formed between the lower flexure supporting portion 143 and the lower end-tap supporting portion 153 , with the lower end-tap supporting portion 153 being located lower than the lower flexure supporting portion 143 . Another stepped portion is formed between the upper flexure supporting portion 144 and the upper end-tap supporting portion 154 , with the upper end-tap supporting portion 154 being located higher than the upper flexure supporting portion 144 . The stepped portions formed between the respective upper and lower flexure supporting portions 143 and 144 and the respective upper and lower end-tap supporting portions 153 and 154 can be designed to correspond to the thickness of the flexures 32 and 37 supported to the respective flexure supporting portions 143 and 144 .
[0038] The HGA protecting member 100 can be mounted to the HGA 10 to protect the HGA 10 while the HGA 10 is being made and while the HGA 10 is being installed in a base (not shown) of the hard disk drive, for example. The HGA protecting member 100 can be mounted to the HGA by inserting the mounting boss 105 into the first through-hole 17 of the actuator 16 and inserting the finger 110 between the suspensions 20 and 25 and the finger 140 between the suspensions 30 and 35 .
[0039] Flexures 32 and 37 can be attached to the suspensions 30 and 35 located under/over the finger 140 , respectively, so that the flexures face each other. The flexures 32 and 37 include stationary ends 32 a and 37 a, fixed to the suspensions 30 and 35 , and free ends 32 b and 37 b. The free ends 32 b and 37 b are extended to front ends of the suspensions 30 and 35 , but may not be extended to end-taps 31 and 36 , provided at the front ends of the suspensions 30 and 35 , respectively. Sliders 33 and 38 are mounted between the stationary ends 32 a and 37 a and the free ends 32 b and 37 b of the flexures 32 and 37 , respectively, so that the sliders face each other.
[0040] When the finger 140 is inserted between the suspensions 30 and 35 , the free ends 32 b and 37 b of the flexures 32 and 37 are spaced apart each other by way of the inclined surface 142 . The end-taps 31 and 36 are similarly spaced apart by way of the inclined surface 152 . The flexure supporting portions 143 and 144 can support the free ends 32 b and 37 b of the flexures 32 and 37 , respectively, thereby preventing the free ends 32 b and 37 b from excessively wobbling up and down. Similarly, the end-tap supporting portions 153 and 154 support the end-taps 31 and 36 , respectively, thereby preventing the end-taps 31 and 36 from excessively wobbling up and down.
[0041] The HGA 10 , with the HGA protecting member 100 mounted thereto, can be installed in the base (not shown) of the hard disk drive, and is rotatable around a pivot 12 . The finger 110 can be removed from the suspensions 20 and 25 and the finger 140 can be removed from suspensions 30 and 35 . The mounting boss 105 can also be removed from the first through-hole 17 to detach the HGA protecting member 100 from the HGA 10 .
[0042] The HGA protecting member 100 , according to an embodiment of the present invention, may be installed on the HGA 10 together with a conventional HGA protecting member 40 , previously described with reference to FIGS. 1 and 2 , so as to more safely protect the HGA from being damaged.
[0043] FIGS. 6 and 7 respectively illustrate top and rear views showing an HGA with an HGA protecting member 200 , according to other embodiments of the present invention. A structure of the HGA can be similar to that of a conventional HGA, so the detailed description thereof will not be further discussed herein.
[0044] Referring to FIGS. 6 and 7 , the HGA protecting member 200 can be made of a plastic resin by molding, for example, and may include a mounting boss (not shown) insertable into a second through-hole 18 of an actuator 16 , and a pair of fingers 210 and 240 insertable between paired adjacent suspensions 20 and 25 and paired adjacent suspensions 30 and 35 . A hole for mounting the conventional HGA protecting member 40 (see FIGS. 1 and 2 ) to the HGA 10 may also be used as the second through-hole 18 , according to an embodiment of the present invention.
[0045] The shape and function of the pair of fingers 210 and 240 are similar to those of the fingers 110 and 140 , according to an above embodiment, so the detailed description thereof will be further omitted herein.
[0046] The HGA protecting member 200 can be mounted on the HGA 10 to protect the HGA 10 , e.g., until the HGA 10 is completed and installed in a base (not shown) of the hard disk drive.
[0047] When the finger 240 is inserted between the suspensions 30 and 35 , the free ends 32 b and 37 b of the flexures 32 and 37 are spaced apart from each other by way of the inclined surface 242 , and the end-taps 31 and 36 are spaced from each other by way of the inclined surface 252 . Also the flexure supporting portions 243 and 244 can support the free ends 32 b and 37 b of the flexures 32 and 37 , respectively, thereby preventing the free ends 32 b and 37 b from wobbling up and down. Similarly, end-tap supporting portions 253 and 254 can support the end-taps 31 and 36 , respectively, thereby preventing the end-taps 31 and 36 from wobbling up and down. This description of the finger 240 may be similarly applied to another finger 210 .
[0048] The HGA 10 , with the HGA protecting member 200 mounted thereto, can be installed in the base (not shown) of the hard disk drive, and may be rotated around the pivot 12 . The finger 210 may be removed from the suspensions 20 and 25 and finger 24 may be removed from suspensions 30 and 35 . The mounting boss (not shown) can be removed from the second through-hole 18 , detaching the HGA protecting member 200 from the HGA 10 .
[0049] FIG. 8 illustrates a top view of an HGA with an HGA protecting member 300 , according to another embodiment of the present invention.
[0050] Referring to FIG. 8 , the HGA protecting member 300 may include a first finger 340 for supporting the flexure 37 and the end-top 36 , and a second finger 380 for supporting the portion of the suspension 35 between parts attached to the actuator 16 and the flexure 37 . The first finger 340 may be similar to the finger 140 (see FIG. 3 ) of an above embodiment, and the second finger 380 may be similar to the finger 44 (see FIG. 2 ) of a conventional HGA protection member, for example. Accordingly, the detailed description of the corresponding first and second fingers will be omitted further herein.
[0051] With the above description, when the HGA protecting member embodiments of the present invention are mounted on an HGA, a finger of the HGA protecting member can support a flexure of the HGA and an end-tap of a suspension, thereby preventing the suspension, the end-tap, and the flexure from wobbling during transport or during installation of the HGA, thereby preventing damage of the flexure and the slider, as well as the magnetic head mounted onto the slider.
[0052] Further, an installation of the HGA in the hard disk drive using the HGA protecting member may prevent damage of the HGA in the course of installing the HGA in the base of the hard disk drive. Additional embodiments are also available, e.g., an HGA protecting member may include only one pair of suspensions and may be provided with only one finger.
[0053] Thus, although a few embodiments of the present invention have been shown and described, it would be appreciated by those skilled in the art that changes may be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the claims and their equivalents. | An HGA protecting method and member and method of implementing the protecting method and member in a hard disk drive. The HGA includes an actuator, at least one pair of suspensions coupled to the actuator, a flexure having a stationary end fixed to each of the suspensions and a free end, and a slider attached between the stationary end and the free end of the flexure. The HGA protecting member may include a finger restricting excessive movement of the suspension. The finger may further have a flexure supporting portion supporting the free end of the flexure. | 6 |
FIELD OF THE INVENTION
The present invention relates to an epoxy resin composition for sealing semiconductor elements. The epoxy resin composition of the present invention manifests the low stress, high heat and moisture resistant characteristics required for sealing semiconductor elements.
BACKGROUND OF THE INVENTION
Recently, owing to the tendency of electric and electronic components to be small and thin, IC and LSI packages have become varied. Especially, while the size of a chip has become larger, the package has become thinner and varied with high pin numbers.
The mounting technology has also varied according to surface mounting technology. Recently, Thin Small Out-line J-Bend Packages(TSOJ) having a thickness of about 1 mm are being produced. TSOJ, which is a medium stage type between a Small Out-line J-Bend Package(SOJ)/Quad Flat Package(QFP) and a Tape Automated Bonding(TAB), will be used as the main type of package in the memory element field in the near future.
The resin composition for sealing such semiconductor elements requires strict low stress, high heat and moisture resistant properties over the prior art compositions.
The method for decreasing inner stress by adding plasticizers such as a modified silicone oil or CTBN[Japanese Laid-open Patent Publication Nos. (Sho) 63-230725, 62-7723, 62-132961 and 62-260817] and the method for lowering the thermal expansion coefficient by increasing the amounts of fillers [Japanese Laid-open Patent Publication No. (Sho) 62-106920] are known as low stress techniques. However, such methods have serious problems such as low heat resistance, moldability and abrasion of equipment.
The method for improving heat resistance by using polyfunctional epoxy resins [Japanese Laid-open Patent Publication Nos. (Sho) 62-477, 62-7719 and 62-7723] and the method for increasing heat resistance by using a bismaleimide [Japanese Laid-open Patent Publication Nos. (Sho) 54-142298 and 58-215452] are well known. However, these methods have problems in that due to an increase in the glass transition temperature of the resin composition the moisture resistant property decreases.
SUMMARY OF THE INVENTION
The object of the present invention is to provide an epoxy resin composition suitable for sealing super thin high integrated circuits, with the use of a high performance epoxy resin capable of providing low stress, high heat and high moisture resistance characteristics.
The present invention is directed to an epoxy resin composition comprising o-cresol-novolak type epoxy resin, phenol-novolak type curing agent, curing accelerator and inorganic filler, characterized in that a high performance epoxy resin selected from a group consisting of an epoxy resin having formula (I-a), an epoxy resin having formula (I-b) and an epoxy resin having formula (I-c) is incorporated into the o-cresol-novolak type epoxy resin. ##STR2## wherein, R 1 and R 2 represent independently H or (CH 2 ) n CH 3 radical, and
n represents 0 or an integer of 1 or above.
DETAILED DESCRIPTION OF THE INVENTION
The high performance epoxy resins (I-a), (I-b) and (I-c) used in the present invention may be synthesized by the following routes. That is, each of the epoxy resins having the structural formulas (II-a), (II-b) and (II-c) (available from Nippon Chemical Co.) and a non-polar organic solvent, such as CCl 4 and C 2 H 4 Cl 2 , are added to a round bottom flask equipped with a dropping funnel and a reflux condenser and dissolved by stirring. To this mixture 0.1 to 1% by weight of benzoyl peroxide (manufactured by Aldrich Chemical Co.) is added as a catalyst, then N-bromosuccinimide (NBS; manufactured by Aldrich Chemical Co.) is added dropwise, followed by reflux for 2 to 6 hrs. The resulting Br-substituted epoxy resins represented by the structural formula (III-a), (III-b) and (III-c), respectively, are dissolved in dry diethyl ether or tetrahydrofuran. Upon complete dissolution with the addition of magnesium metal, o-methylhydroxylamine (available from Aldrich Chemical Co.) is added thereto, and reacted for 4 to 8 hrs. with stirring, while the mixture is slightly heated. ##STR3## The resultant amine group-substituted epoxy resin and maleimide represented by the formula (IV) (Mitsubishi Petrochemical Co., Ltd.) are dissolved in DMF and reacted for several hours with reflux to obtain the high performance epoxy resins represented by the formulas (I-a), (I-b) and (I-c). ##STR4## wherein, R 1 and R 2 have the same meaning in formula (I).
The epoxy resin composition of the present invention is based on the epoxy resin component obtained by mixing o-cresol-novolak type epoxy resin with the high performance epoxy resins represented by the formulas (I-a), (I-b) and (I-c). The epoxy resin composition of the present invention further includes a phenol-novolak type curing agent, a curing accelerator such as triphenylphosphine belonging to organic phosphine compounds, a filler such as high purity molten silica, a modifier such as epoxy-modified silicone oil, a mold release agent, a colorant, and an organic or inorganic flame retardant.
The preferred constitutional example of the present epoxy resin composition is as follows:
______________________________________o-cresol-novolak type epoxy resin 0.1-20% by weighthigh performance epoxy resin 0.1-20% by weightcuring agent 1.0-10.0% by weightcuring accelerator 0.1-1.0% by weightcoupling agent 0.5-2.0% by weightcolorant 0.1-0.5% by weightfiller 65.0-85.0% by weightmold release agent 0.1-1.0% by weightorganic flame retardant 1.0-5.0% by weightinorganic flame retardant 0.5-3.0% by weightplasticizer 0.5-5.0% by weight______________________________________
The above resin composition is the most preferred for the resin composition of the present invention. The epoxy resin to be used in the present invention should be a good heat resistant o-cresol-novolak type resin, especially a highly pure epoxy resin having 190 to 220 epoxy equivalent weight with an impurity content below 10 ppm. As to the curing agent, a phenol-novolak type resin, which has a softening point of 80° to 100° C., 100 to 120 hydroxyl equivalent weight and below 10 ppm impurity content, may be used.
A high performance epoxy resin to be used specifically in the present invention includes imide-epoxy resin, and the amount to be used is preferably between 0.1 and 20.0% by weight, and more preferably between 1.0 and 10.0% by weight, based on the total weight of the resin composition. If the amount is less than 0.1% by weight, the heat and moisture resistance are very poor, and if the amount is greater than 20% by weight, phenomena such as resin bleed and mold fouling occur. Thus, moldability decreases and problems related to the gel time and conditions at post-curing result.
It is preferable to use high purity fused silica as the filler in the resin composition of the present invention. Fused silica having a particle size of 10 to 30 μm is preferable.
Curing accelerators include amines, imidazole derivatives and organic phosphine compounds being conventionally used. In the present invention, it is preferable to use triphenylphosphine, and 2-methylimidazole and 2-methyl-4-ethylimidazole as organic phosphine compounds and imidazole derivatives, respectively.
The coupling agent to be used in the surface treatment of inorganic fillers includes silane-based coupling agents. It is the most preferable to use γ-glycidoxy-propyltrimethoxysilane. As plasticizers, silicone rubber or epoxy-modified silicone oil is conventionally used. In the present invention, plasticizers are used to increase the compatibility according to the high integration of semiconductors, and include an adduct of phenol-novolak resins and epoxy-modified silicone oil.
The epoxy resin composition of the present invention may further comprise 0.1 to 1.0% by weight of carnauba wax or Montan wax as a mold release agent, 0.1 to 0.5% by weight of carbon black as a colorant, brominated epoxy resin as an organic flame retardant and antimony trioxide as an inorganic flame retardant.
The resin composition of the present invention can be prepared by surface treating inorganic fillers with coupling agents, homogeneously mixing them with the remaining components in a Henschel mixer or other premixer, melt mixing the mixture at 90° to 110° C. for about 5 to 20 min. with a kneader or roll mill, cooling and pulverizing.
The resultant powdery composition may then be tableted by a tableting machine. In use, the obtained resin composition tablet is preheated with a high frequency preheater, and molded with a molding press at 170° to 180° C. for 90 to 120 sec. to seal the semiconductor elements.
As mentioned above, since the resin composition prepared by the present invention includes a high performance epoxy resin, in addition to the conventional cresol-novolak type epoxy resin, it has a high glass transition temperature and improved moisture resistance, and thus, can provide a resin composition suitable for sealing super-thin, high integrated semiconductor elements.
EXAMPLES
Hereinafter, the present invention will be described in detail by virtue of examples, which should not be construed as limiting the scope of the present invention.
Physical properties of the epoxy resin composition obtained from the examples are measured with the following methods:
1) Spiral flow: Measured at 175° C. of molding temperature and 70 kg.f/cm 2 of molding pressure with a mold prepared according to EMMI standard
2) Tg: Measured with TMA equipment
3) E(kg.f/mm 2 ): Measured with UTM according to ASTM D 190
4) Thermal expansion coefficient α(°C -1 ): Measured according to ASTM D 696
5) Moisture content(%): Measured the saturated moisture content, after standing the molded article for 48 hrs. in 121° C., 2 atm. vapor
6) Resistant to cracking: Measured from the crack numbers produced in the 2,000 times thermal impact test on the molded chip under the test conditions having one cycle of -55° C., 30 min. and 150° C., 30 min.
The plasticizer in Table I is an epoxy-modified silicone oil; "KBM-403" is a silane coupling agent.
EXAMPLES 1-4
Constitutional components having the composition described in Table 1 are mixed in a Henschel mixer to give a powdery composition, except that epoxy resin represented by the formula (I-a) is used as the high performance epoxy resin of the present invention. The powdery composition is kneaded for 10 min. at 100° C., cooled, and ground to give epoxy resin molding materials. Physical properties thereof are listed on Table 2.
COMPARATIVE EXAMPLE 1
This Comparative Example 1 is conducted in the same manner as Examples 1-4, except that the high performance epoxy resin (I-a) of the present invention is not included. The physical properties thereof are also listed in Table 2.
EXAMPLES 5-8
Constitutional components having the composition set forth in Table 1 are mixed in a Henschel mixer to give a powdery composition, except that the epoxy resin (I-b) of the present invention is used as the high performance epoxy resin. The powdery composition is applied to the same test as Examples 1-4. The results are given in Table 2.
COMPARATIVE EXAMPLE 2
Comparative Example 2 is conducted in the same manner as Examples 5-8, except that the epoxy resin composition does not contain the high performance epoxy resin (I-b) of the present invention. The physical properties thereof are also shown in Table 2.
EXAMPLES 9-12
Constitutional components having the composition disclosed in Table 1 are mixed in a Henschel mixer to obtain powdery composition, except that the epoxy resin (I-c) of the present invention is used as the high performance epoxy resin. The powdery composition is applied to the same test as Examples 1-4. The results are presented in Table 2.
COMPARATIVE EXAMPLE 3
Comparative Example 3 is conducted in the same manner as Examples 9-12, except that the epoxy resin (I-c) of the present invention is excluded from the epoxy resin composition. The physical properties thereof are also demonstrated in Table 2.
TABLE 1__________________________________________________________________________ (Unit: % by weight) Comparative Example Nos. Example Nos.Components 1 2 3 4 5 6 7 8 9 10 11 12 1 2 3__________________________________________________________________________o-Cresol-novolak 13.57 12.57 8.07 3.07 14.57 13.07 8.07 3.07 12.57 10.57 8.07 3.07 15.07 15.07 15.07epoxy resinHigh performance 1.5 2.5 7.0 12.0 0.5 2.0 7.0 12.0 2.5 4.5 7.0 12.0 -- -- --epoxy resin(Imide-basedepoxy resin)Phenol-novolak 5.83 5.83 5.83 5.83 5.83 5.83 5.83 5.83 4.83 4.83 4.83 4.83 5.83 5.83 4.83curing agentTriphenylphosphine 0.4 0.4 0.4 0.4 0.38 0.38 0.38 0.38 0.4 0.4 0.4 0.4 0.4 0.38 0.4Fused silica 73.8 73.8 73.8 73.8 73.8 73.8 73.8 73.8 74.8 74.8 74.8 74.8 73.8 73.8 74.8Plasticizer 1.2 1.2 1.2 1.2 1.15 1.15 1.15 1.15 1.2 1.2 1.2 1.2 1.2 1.15 1.2Brominated 1.25 1.25 1.25 1.25 1.30 1.30 1.30 1.30 1.25 1.25 1.25 1.25 1.25 1.30 1.25epoxy resinKBM 403 (manufactured .11 1.11 1.11 1.11 1.11 1.11 1.11 1.11 1.21 1.21 1.21 1.21 1.11 1.11 1.21by Shin-etsuChemical Co., Ltd.)Carnauba wax 0.23 0.23 0.23 0.23 0.23 0.23 0.23 0.23 0.13 0.13 0.13 0.13 0.23 0.23 0.13Sb.sub.2 O.sub.3 0.85 0.85 0.85 0.85 0.85 0.85 0.85 0.85 0.85 0.85 0.85 0.85 0.85 0.85 0.85Carbon black 0.26 0.26 0.26 0.26 0.26 0.26 0.26 0.26 0.26 0.26 0.26 0.26 0.26 0.26 0.26__________________________________________________________________________
TABLE 2__________________________________________________________________________ Example Nos.Content 1 2 3 4 5 6 7 8__________________________________________________________________________Spiral flow (in.) 45 44 43 40 45 44 43 40Tg (°C.) 197 195 193 200 187 190 193 203α (×10.sup.-5 /°C.) 1.4 1.3 1.2 1.1 1.4 1.3 1.2 1.1E (kgf/mm.sup.2) 1200 1150 1250 1250 1200 1150 1250 1250Moisture content (%) 0.40 0.42 0.41 0.38 0.42 0.43 0.40 0.38* Resistance to crack 2/600 1/600 1/600 0/600 2/600 1/600 0/600 0/600(2000 times)__________________________________________________________________________ Comparative Example Nos. Example Nos.Content 9 10 11 12 1 2 3__________________________________________________________________________Spiral flow (in.) 45 44 43 40 45 45 45Tg (°C.) 197 195 193 200 180 170 180α (×10.sup.-5 /°C.) 1.4 1.3 1.2 1.1 1.7 1.7 1.7E (kgf/mm.sup.2) 1200 1150 1250 1250 1200 1200 1200Moisture content (%) 0.40 0.42 0.41 0.38 0.5 0.5 0.5* Resistance to crack 2/600 1/600 1/600 0/600 6/600 6/600 6/60(2000 times)__________________________________________________________________________ * Denominator represents the number of samples, and numerator represents the failure numbers.
As can be seen from the above results, the epoxy resin composition of the present invention has superior moldability and high heat and moisture resistance over the compositions of the comparative Examples, and also has improved resistance to cracking. | An epoxy resin composition for sealing semiconductor elements comprising o-cresol-novolak type epoxy resins, curing agents, curing accelerators, plasticizer and a high performance epoxy resin selected from a group consisting of epoxy resins represented by the formulas (I-a), (I-b) and (I-c) is disclosed.
Use of the high performance epoxy resin in an amount of from 0.1 to 20.0% by weight improves the heat and moisture resistance of the epoxy resin composition. ##STR1## wherein, R 1 and R 2 represent independently H or (CH 2 ) nCH 3 radical, and
n represents 0 or an integer of 1 above. | 2 |
BACKGROUND OF THE INVENTION
This invention is directed to compounds which act as antagonists of the leukotrienes and inhibitors of the syntheses of LTA 4 , B 4 , C 4 , D 4 , E 4 , and F 4 .
The leukotrienes and their biological activities, especially their roles in various disease states and conditions have been described. For example, see EP No. 140,684 (May 8, 1985), which is incorporated herein by reference.
Several classes of compounds exhibit ability to antagonize the action of leukotrienes in mammals, especially humans. See for example: United Kingdom Patent Specification Nos. 2,058,785 and 2,094,301; and European Patent Application Nos. 56,172, 61,800 and 68,739.
EP No. 110,405 (June 13, 1984) describes anti-inflammatory and antiallergic substituted benzenes which are disclosed to be leukotriene inhibitors, i.e., inhibitors of the 5-lipoxygenase pathway.
SUMMARY OF THE INVENTION
It has now been found that the 4-substituted phenoxyquinoline compounds of the present invention exhibit surprisingly and unexpectedly enhanced biological activity as leukotriene synthesis inhibitors and antagonists of their action when compared to positional isomers thereof, such as 3-substituted phenoxyquinoline of EP No. 110,405.
The present invention relates to compounds having activity as leukotriene and SRS-A antagonists or inhibitors, to methods for their preparation, to intermediates useful in their preparation and to methods and pharmaceutical formulations for using these compounds in mammals (especially humans).
Because of their activity as leukotriene antagonists and inhibitors, the compounds of the present invention are useful as anti-asthmatic, anti-allergic, and anti-inflammatory agents and are useful in treating allergic rhinitis and chronic bronchitis and for amelioration of skin diseases like psoriasis and atopic eczema. These compounds are also useful to antagonize or inhibit the pathologic actions of leukotrienes on the cardiovascular and vascular systems for example, actions such as result in angina. The compounds are also useful as cytoprotective agents.
Thus, the compounds of the present invention may also be used to treat or prevent mammalian (especially, human) disease states such as erosive gastritis; erosive esophagitis; inflammatory bowel disease; ethanol-induced hemorrhagic erosions; hepatic ischemia; noxious agent induced damage or necrosis of hepatic, pancreatic, renal, or myocardial tissue; liver parenchymal damage caused by hepatoxic agents such as CCl 4 and D-galactosamine; ischemic renal failure; disease-induced hepatic damage; bile salt induced pancreatic or gastric damage; trauma- or stress-induced cell damage; and glycerol-induced renal failure.
DETAILED DESCRIPTION
The compounds of this invention are best realized by Formula I: ##STR2## wherein:
R 1 is H, halogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, --CF 3 , --OR 2 , --SR 2 , --NR 2 R 2 , --CHO, --COOR 2 , --(C═O)R 2 , --C(OH)R 2 R 2 , --CN, --NO 2 , substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, or substituted or unsubstituted phenethyl;
R 2 is H, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, --CF 3 , substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, or substituted or unsubstituted phenethyl;
R 3 is --OR 4 , --SR 4 , or --NR 4 R 4 ;
R 4 is H, or C 1 -C 6 alkyl, --(C═O)R 2 , unsubstituted phenyl, or unsubstituted benzyl;
m is 1-6; and the pharmaceutically acceptable salts thereof.
Alkyl, alkenyl, and alkynyl are intended to include linear, branched, and cyclic structures. Thus, alkyl would include n-butyl, sec-butyl, tert-butyl, cyclobutyl, etc.
Substituted phenyl, benzyl, and phenethyl include 1-2 substituents selected from C 1 -C 6 alkyl, --R 3 , --NO 2 , SCF 3 , halogen, --COR 3 , --CN, or --CF 3 .
Halogen includes F, Cl, Br and I.
It is intended that the definitions of any substituent (e.g., R 1 , R 2 , m, etc.) in a particular molecule is independent of its definitions elsewhere in the molecule. Thus, --NR 4 R 4 represents --NHH, --NHCH 3 , --N(CH 3 )(C 2 H 5 ), etc.
Preferred compounds of Formula I are those wherein R 2 is H, R 3 is OH, and m is 4.
The compounds of Formula I are active as antagonists of SRS-A and especially of leukotrienes D 4 . These compounds also have inhibitory activity on leukotriene biosynthesis. The activity of the compounds of Formula I can be detected and evaluated by methods known in the art. See for example, Kadin, U.S. Pat. No. 4,296,129.
The ability of the compounds of Formula I to antagonize the effects of the leukotrienes and to inhibit the biosynthesis of leukotrienes makes them useful for inhibiting the symptoms induced by the leukotrienes in a human subject. The compounds are valuable therefore in the prevention and treatment of such disease states in which the leukotrienes are the causative factor, e.g. skin disorders, allergic rhinitis, and obstructive airway diseases. The compounds are particularly valuable in the prevention and treatment of allergic bronchial asthma. It will be understood that in this paragraph and in the discussion of methods of treatment which follows, references to the compounds of Formula I are meant to include the pharmaceutically acceptable salts.
The cytoprotective activity of a compound may be observed in both animals and man by noting the increased resistance of the gastrointestinal mucosa to the noxious effects of strong irritants, for example, the ulcerogenic effects of aspirin or indomethacin. In addition to lessening the effect of non-steroidal anti-inflammatory drugs on the gastrointestinal tract, animal studies show that cytoprotective compounds will prevent gastric lesions induced by oral administration of strong acids, strong bases, ethanol, hypertonic saline solutions and the like.
Two assays can be used to measure cytoprotective ability. These assays are; (A) an ethanol-induced lesion assay and (B) an indomethacin-induced ulcer assay and are described in EP No. 140,684.
The magnitude of a prophylactic or therapeutic dose of a compound of Formula I will, of course, vary with the nature of the severity of the condition to be treated and with the particular compound of Formula I and its route of administration. It will also vary according to the age, weight and response of the individual patient. In general, the daily dose range for anti-asthmatic, anti-allergic or anti-inflammatory use and generally, uses other than cytoprotection, lie within the range of from about 0.01 mg to about 100 mg per kg body weight of a mammal, preferably 0.1 mg to about 20 mg per kg, and most preferably 1 to 20 mg per kg, in single or divided doses. On the other hand, it may be necessary to use dosages outside these limits in some cases.
The exact amount of a compound of the Formula I to be used as a cytoprotective agent will depend on, inter alia, whether it is being administered to heal damaged cells or to avoid future damage, on the nature of the damaged cells (e.g., gastrointestinal ulcerations vs. nephrotic necrosis), and on the nature of the causative agent. An example of the use of a compound of the Formula I in avoiding future damage would be co-administration of a compound of the Formula I with a non-steroidal anti-inflammatory drug that might otherwise cause such damage (for example, indomethacin). For such use, the compound of Formula I is administered from 30 minutes prior up to 30 minutes after administration of the NSAID. Preferably it is administered prior to or simultaneously with the NSAID, (for example, in a combination dosage form).
The effective daily dosage level for compounds of Formula I inducing cytoprotection in mammals, especially humans, will generally range from about 0.1 mg/kg to about 100 mg/kg, preferably from about 1 mg/kg to about 100 mg/kg. The dosage may be administered in single or divided individual doses.
Any suitable route of administration may be employed for providing a mammal, especially a human with an effective dosage of a leukotriene antagonist. For example, oral, rectal, transdermal, parenteral, intramuscular, intravenous and the like may be employed. Dosage forms include tablets, troches, dispersions, suspensions, solutions, capsules and the like.
The pharmaceutical compositions of the present invention comprise a compound of Formula I as an active ingredient or a pharmaceutically acceptable salt thereof, and may also contain a pharmaceutically acceptable carrier and optionally other therapeutic ingredients. The term "pharmaceutically acceptable salts" refers to salts prepared from pharmaceutically acceptable non-toxic acids including inorganic acids and organic acids.
When the compound of the present invention is basic, salts may be prepared from pharmaceutically acceptable non-toxic acids, including inorganic and organic acids, such acids include acetic, benzensulfonic, benzoic, camphorsulfonic, citric, ethanesulfonic, fumaric, gluconic, glutamic, hydrobromic, hydrochloric, isethionic, lactic, maleic, malic, mandelic, methanesulfonic, mucic, nitric, panoic, pantothenic, phosphoric, succinic, sulfuric, tataric acid, p-toluenesulfonic and the like. Particularly preferred are hydrobromic, hydrochloric, phosphoric and sulfuric acids.
The compositions include compositions suitable for oral, rectal, ophthalmic, pulmonary, nasal, dermal, topical or parenteral (including subcutaneous, intramuscular and intravenous) administration, although the most suitable route in any given case will depend on the nature and severity of the conditions being treated and on the nature of the active ingredient. They may be conveniently presented in unit dosage form and prepared by any of the methods well-known in the art of pharmacy.
For use where a composition for intravenous administration is employed, a suitable dosage range for anti-asthmatic, anti-inflammatory or anti-allergic use is from about 0.01 mg to about 10 mg (preferably from about 0.1 mg to about 10 mg) of a compound of Formula I per kg of body weight per day and for cytoprotective use from about 0.1 mg to about 20 mg (preferably from about 1 mg to about 20 mg and more preferably from about 1 mg to about 10 mg) of a compound of Formula I per kg of body weight per day.
In the case where an oral composition is employed, a suitable dosage range for anti-asthmatic, anti-inflammatory or anti-allergic use is, e.g. from about 0.01 mg to about 100 mg of a compound of Formula I per kg of body weight per day, preferably from about 0.1 mg to about 100 mg per kg and for cytoprotective use from about 0.1 mg to about 100 mg (preferably from about 1 mg to about 100 mg and more preferably from about 10 mg to about 100 mg) of a compound of Formula I per kg of body weight per day.
For administration by inhalation, the compounds of the present invention are conveniently delivered in the form of an aerosol spray presentation from pressurized packs or a nebuliser. The preferred composition for inhalation is a powder which may be formulated as a cartridge from which the powder composition may be inhaled with the aid of a suitable device. In the case of a pressurized aerosol, the dosage unit may be determined by providing a valve to deliver a metered amount.
In practical use, the compounds of Formula I can be combined as the active ingredient in intimate admixture with a pharmaceutical carrier according to conventional pharmaceutical compounding techniques. The carrier may take a wide variety of forms depending on the form of preparation desired for administration, e.g., oral or intravenous. In preparing the compositions for oral dosage form, any of the usual pharmaceutical media may be employed, such as, for example, water glycols, oils, alcohols, flavoring agents, preservatives, coloring agents and the like in the case of oral liquid preparations, such as, for example, suspensions, elixirs and solutions; or carriers such as starches, sugars, diluents, granulating agents, lubricants, binders, disintegrating agents and the like in the case of oral solid preparations such as, for example, powders, capsules and tablets. Because of their ease of administration, tablets and capsules represent the most advantageous oral dosage unit form, in which case solid pharmaceutical carriers are obviously employed. If desired, tablets may be sugar coated or enteric coated by standard techniques.
In addition to the common dosage forms set out above, the compounds of Formula I may also be administered by controlled release means and/or delivery devices such as those described in U.S. Pat. Nos. 3,845,770; 3,916,899; 3,536,809; 3,598,123; 3,630,200 and 4,008,719, the disclosures of which are hereby incorporated herein by reference.
Pharmaceutical compositions of the present invention suitable for oral administration and by inhalation in the case of asthma therapy may be presented as discrete units such as capsules, cachets or tablets each containing a predetermined amount of the active ingredient, as a powder or granules or as a solution or a suspension in an aqueous liquid, a non-aqueous liquid, an oil-in-water emulsion or a water-in-oil liquid emulsion. Such compositions may be prepared by any of the methods of pharmacy but all methods include the step of bringing into association the active ingredient with the carrier which constitutes one or more necessary ingredients. In general, the compositions are prepared by uniformly and intimately admixing the active ingredient with liquid carriers or finely divided solid carriers or both, and then, if necessary, shaping the product into the desired presentation. For example, a tablet may be prepared by compression or molding, optionally with one or more accessory ingredients. Compressed tablets may be prepared by compressing in a suitable machine, the active ingredient in a free-flowing form such as powder or granules, optionally mixed with a binder, lubricant, inert diluent, lubricating, surface active or dispersing agent. Molded tablets may be made by molding in a suitable machine, a mixture of the powdered compound moistened with an inert liquid diluent. Desirably, each tablet contains from about 25 mg to about 500 mg of the active ingredient and each cachet or capsule contains from about 25 to about 500 mg of the active ingredient.
The following are examples of representative pharmaceutical dosage forms for the compounds of Formula I:
______________________________________Injectable Suspension mg/ml______________________________________Compound of Formula I 2.0Methylcellulose 5.0Tween 80 0.5Benzyl alcohol 9.0Methyl paraben 1.8Propyl paraben 0.2Water for injection to a total volume of 1 ml______________________________________Tablet mg/tablet______________________________________Compound of Formula I 25.0Microcrystalline Cellulose 325.0Providone 14.0Microcrystalline Cellulose 90.0Pregelatinized Starch 43.5Magnesium Stearate 2-2.5 500______________________________________Capsule mg/capsule______________________________________Compound of Formula I 25.0Lactose Powder 573.5Magnesium Stearate 1.5 600______________________________________
In addition to the compounds of Formula I, the pharmaceutical compositions of the present invention can also contain other active ingredients, such as cyclooxygenase inhibitors, non-steroidal anti-inflammatory drugs (NSAIDs), peripheral analgesic agents such as zomepirac diflunisal and the like. The weight ratio of the compound of the Formula I to the second active ingredient may be varied and will depend upon the effective dose of each ingredient. Generally, an effective dose of each will be used. Thus, for example, when a compound of the Formula I is combined with an NSAID the weight ratio of the compound of the Formula I to the NSAID will generally range from about 1000:1 to about 1:1000. Combinations of a compound of the Formula I and other active ingredients will generally also be within the aforementioned range, but in each case, an effective dose of each active ingredient should be used..
NSAIDs can be characterized into five groups:
(1) the propionic acid derivatives;
(2) the acetic acid derivatives;
(3) the fenamic acid derivatives;
(4) the biphenylcarboxylic acid derivatives; and
(5) the oxicams
or a pharmaceutically acceptable salt thereof. NSAIDs which are within the scope of this invention are those disclosed in EP No. 140,684.
Pharmaceutical compositions comprising the Formula I compounds may also contain inhibitors of the biosynthesis of the leukotrienes such as are disclosed in EP No. 138,481 (Apr. 24, 1985), EP No. 115,394 (Aug. 8, 1984), EP No. 136,893 (Apr. 10, 1985), and EP No. 140,709 (May 5, 1985), which are hereby incorporated herein by reference.
The compounds of the Formula I may also be used in combination with leukotriene antagonists such as those disclosed in EP No. 106,565 (Apr. 25, 1984) and EP No. 104,885 (Apr. 4, 1984) which are hereby incorporated herein by reference and others known in the art such as those disclosed in European Patent Application Nos. 56,172 (July 21, 1982) and 61,800 (Oct. 6, 1982); and in U.K. Patent Specification No. 2,058,785, which are hereby incorporated herein by reference.
Pharmaceutical compositions comprising the Formula I compounds may also contain as the second active ingredient, antihistaminic agents such as benadryl, dramamine, histadyl, phenergan and the like. Alternatively, they may include prostaglandin antagonists such as those disclosed in European Patent Application No. 11,067 (May 28, 1980) or thromboxane antagonists such as those disclosed in U.S. Pat. No. 4,237,160. They may also contain histidine decarboxylase inhibitors such as α-fluoromethylhistidine, described in U.S. Pat. No. 4,325,961. The compounds of the Formula I may also be advantageously combined with an H 1 or H 2 -receptor antagonist, such as for instance cimetidine, ranitidine, terfenadine, famotidine, aminothiadiazoles disclosed in EP No. 40,696 (Dec. 2, 1981) and like compounds, such as those disclosed in U.S. Pat. Nos. 4,283,408; 4,362,736; and 4,394,508. The pharmaceutical compositions may also contain a K + /H + ATPase inhibitor such as omeprazole, disclosed in U.S. Pat. No. 4,255,431, and the like. Each of the references referred to in this paragraph is hereby incorporated herein by reference.
Compounds of the present invention can be prepared according to the methods taught in EP No. 110,405 or according to the following scheme. ##STR3##
Referring to Scheme I, anisole II is condensed with an acid chloride of formula III using a suitable condensation reagent such as AlCl 3 to provide ketone of Structure IV. The methyl ether in IV is removed with a strong acid such as HBr to provide phenol V. Phenol V is coupled with quinoline of Structure VI using a suitable condensation catalyst such as diethylazodicarboxylate/φ 3 P to provide VII. In cases where R 1 , is to provide carbonyl groups they are used in their protected forms. The ketone in Structure VII is reduced using a reducing agent such as sodium borohydride (or, alternatively, VII may be reacted with an organometalic reagent such as R 2 MgBr) to provide quinoline derivatives I. In cases where R 1 and R 2 contain carbonyl groups in a protected form they are regenerated at this stage to provide I. The hydroxyl group in VIII is transformed to OR 4 , --SR 4 , or --NR 4 R 4 using standard techniques.
Referring to Scheme II, an aniline of general structure VIII is reacted with crotonaldehyde and strong acid such as hydrochloric acid (6N) to provide the quinaldine of general structure IX.
IX is oxidized (A) with a strong oxidant such as potassium permanganate in a polar solvent such as aqueous, t-butanol to provide the acid of general formula X. Reduction of X with a reducing agent such as lithium aluminum hydride in an inert solvent such as diethyl ether provides the alcohols of general structure VI.
Alternatively (B), the quinaldines IX can be oxidized with an oxidizing agent such as hydrogen peroxide or m-chloroperbenzoic acid to provide the N-oxide of general formula XI. Reaction of XI with acetic anhydride provides the acetate of general structure XII. Hydrolysis of the acetate with aqueous base such as sodium hydroxide in a solubilizing cosolvent such as tetrahydrofuran or methanol provides the alcohols of general formula VI.
The following examples further define the invention and are provided as illustrative and not as limiting.
Temperatures are in degrees Celsius.
EXAMPLE 1
2-[4-(1-Hydroxyhexyl)phenoxymethyl)]quinoline
Step 1: Preparation of 1-(4-methoxyphenyl)hexanone
To a solution of anisole (22 g) in dichloro methane (11) and hexanoyl chloride (33 g) at -20° was added portionwise over 30 minutes aluminum chloride (32 g). The reaction was stirred 2 hours at -20° and then quenched with ice and 11 1N HCl. The organic layer was separated, dried (Na 2 SO 4 ), and evaporated. Chromatography of the residue using 5% ethylacetate in hexane afforded 20 g of the title compound: m.p.=32°-35°.
p.m.r. (CDCl 3 ) 0.9(m,3H), 1.4(m,4H), 1.7(m,2H), 2.8(t,2H), 3.8(t,3H), 6.9(d,2H), 7.9 p.p.m. (d,2H).
Step 2: Preparation of 1-(4-hydroxyphenyl)-hexanone
A solution of 1-(4-methoxyphenyl)hexanone (5 g) in acetic acid (50 ml) and 48% HBr was heated overnight at 120°. The reaction mixture was poured onto ice and extracted with ethylacetate (500 ml). The ethyl acetate layer was washed with NaHCO 3 (200 ml), dried, and evaporated. Chromatography of the residue using 30% ethylacetate in hexane afforded 1.7 g of the title compound.
p.m.r. (CDCl 3 ) 0.9(m,3H), 1.4(m,4H), 1.8(m,2H), 2.95(t,3H), 6.2-7.0(bs,lH), 6.9(d,2H) and 7.9 p.p.m. (d,2H).
Step 3: Preparation of 2-[4-(1-oxohexyl)phenoxymethyl)quinoline
To a solution of quinolinylmethanol (1.1 g), triphenylphosphine (1.8 g), and the hexanone of Step 2 above (1.3 g) at 0° in tetrahydrofuran was added dropwise diethylazodicarboxylate (1.1 ml) over 10 minutes. The reaction mixture was stirred 1 hour at room temperature and evaporated. Chromatography of the residue using 25% ethylacetate in hexane afforded the title compound 1.7 g: m.p.=78°-80°.
p.m.r. (CDCl 3 ) 0.9(3H), 1.4(m,4H), 1.8(m,2H), 2.9(t,3H), 5.35(s,2H), 7.1(d,2H), 7.5-8.2 p.p.m. (m,8H).
Step 4:
To a solution of the hexanone of Step 3 above (530 mg) in ethanol (20 ml) and tetrahydrofuran (3 ml) was added sodium borohydride (200 mg) and cerium chloride (20 mg). The reaction mixture was stirred at room temperature 4 hours and poured onto saturated NH 4 Cl and stirred 5 minutes at room temperature. Sodium hydroxide (50 ml of 1N) was added. The mixture was extracted with ethylacetate dried and evaporated. Recrystallization of the residue from hexane/ethylacetate afforded the title compound: m.p.=93°-94°.
Anal. for C 22 H 25 NO 2 Calc'd: C, 78.77; H, 7.52; N, 4.17. Found: C, 79.10; H, 7.85; N, 4.11.
EXAMPLE 2
COMPARATIVE ASSAY
The enhanced biological activity of the 4-substituted phenyl compound of the present invention can be demonstrated by comparison with their 3-substituted phenyl isomers. For example, 2-[4-(1-hydroxyhexylphenoxymethyl)]quinoline (see Example 1) was compared to its 3-(1-hydroxyhexylphenoxymethyl) analog in the PMN (leukotriene inhibitor) assay.
The data from this assay are shown in Table 2-1.
Rat Peritoneal Polymorphonuclear (PMN) Leukocyte Assay
Rats under ether anesthesia are injected (i.p.) with 8 ml of a suspension of sodium cascinate (6 grams in ca. 50 ml water). After 15-24 hr. the rats are sacrificed (CO 2 ) and the cells from the peritoneal cavity are recovered by lavage with 20 ml of buffer (Eagles MEM containing 30 mM HEPES adjusted to pH 7.4 with NaOH). The cells are pelleted (350×g, 5 min.), resuspended in buffer with vigorous shaking, filtered, through lens paper, recentrifuged and finally suspended in buffer at a concentration of 10 cells/ml. A 500 μl aliquot of PMN suspension and test compound are preincubated for 2 minutes at 37° C., followed by the addition of 10 μM A-23187. The suspension is stirred for an additional 4 minutes then bioassayed for LTD 4 content by adding an aliquot to a second 500 μl portion of the PMN at 37° C. The LTB 4 produced in the first incubation causes aggregation of the second PMN, which is measured as a change in light transmission. The size of the assay aliquot is chosen to give a submaximal transmission change (usually -70%) for the untreated control. The percentage inhibition of LTB 4 formation is calculated from the ratio of transmission change in the sample to the transmission change in the compound-free control.
TABLE 2-1______________________________________COMPARISON OF ACTIVITYPMN ASSAY % Inhibition of LTD.sub.4 FormationCompound 5* 1* 0.2* 0.04* 0.008* 0.0016*______________________________________Example 1 100 100 100 89 49 153-Analog 100 100 100 39 -1 --______________________________________ *Doses are in μg/ml.
These data demonstrate a marked improvement in activity that is at least a 5-fold increase in the leukotriene inhibitor assay. | Compounds having the formula: ##STR1## are selective antagonists of leukotrienes of D 4 and inhibitors of the syntheses of LTA 4 , B 4 , C 4 , D 4 , E 4 , and F 4 . These compounds are useful as anti-asthmatic, anti-allergic, anti-inflammatory agents, and cytoprotective agents. | 2 |
[0001] This application claims priority to copending U.S. patent application Ser. No. 12/012,783 filed Feb. 5, 2008, to U.S. patent application Ser. No. 11/004,619 filed Dec. 3, 2004 that claims priority to U.S. provisional patent application 60/526,794 filed Dec. 3, 2003.
BACKGROUND OF THE INVENTION
[0002] Pill containers, as well as certain types of liquid containers and the like, involve snap-on and threaded closures. Snap-on and threaded closures, which may be put on and off easily on the container, are of great convenience to the user. Snap-on and threaded closures, however, enable children to open such containers easily and to be exposed to potentially harmful contents. Containers which employ snap-on and threaded closures therefore should be resistant to opening by children, especially children under age 5.
[0003] A child resistant package must satisfy specific test standards to comply with protocol specified by the U.S. Consumer Product Safety Commission (“CPSC”). These standards are child resistance effectiveness (CRE) and older adult use effectiveness (‘OAUE). CRE is the percentage of children in a group that are unable to open the package within a specified time. CRE is measured by asking pairs of children in a specified age group (30% aged 42-44 months, 40% aged 45-48 months, and 30% aged 49-51 months) to open the package in a specified time period both before and after a nonverbal demonstration. Currently, the CPSC requires a CRE of 85 percent before a demonstration and 80 percent after a demonstration. OAUE is the percentage of adults in a group that is able to open and close the package. OAUE is measured by asking individual adults in a specified age group (typically 60-75 years) to open and close a package using instructions supplied with it in a specified time period. Currently, the CPSC requires an OAUE of ninety percent based on pictorial or written instructions.
[0004] Maze type packages are known in the art. These types of packages employ mazes formed of intersecting grooves. Two types of motion typically are employed to open such a package: (1) rotation and (2) linear (usually axial) motion. The sequence of steps employed typically includes alternating a rotary motion with an axial motion. Although maze type packages exist in the prior art, a need continues for maze type packages which are both child resistant and easily opened by adults, particularly elderly adults.
BRIEF DESCRIPTION OF THE DRAWINGS
[0005] FIG. 1 is an exploded view of a package having a container and a closure;
[0006] FIG. 2 is a top view of the container of FIG. 1 ;
[0007] FIG. 3 is a top view of closure 15 ; FIG. 3 a is a cross sectional view of the closure shown in FIG. 1 taken on line A-A;
[0008] FIG. 4 is a side view of the container of FIG. 1 that shows a configuration of a maze of ribs on the neck of the container of FIG. 1 ;
[0009] FIG. 5 is a cross sectional view of the container of FIG. 1 showing a rib 23 ;
[0010] FIG. 5A is an enlarged view of a rib of the maze shown in FIG. 4 ;
[0011] FIG. 6 is a cross section view of an embodiment of stud 27 of closure 15 ;
[0012] FIGS. 7( a )- 7 ( c ) are cross sectional views of alternative shapes of ribs 23 ;
[0013] FIG. 8 is a cross sectional assembly view of the package of FIG. 1 that shows the closure attached to the container.
[0014] The invention can be more clearly understood by reference to the drawings forming a part of this disclosure wherein like characters indicate like parts throughout the several views.
SUMMARY OF THE INVENTION
[0015] The present invention relates to packages such as child resistant packages which provide ease of use by older adults, particularly adults over 60 years of age. The packages are sufficiently child resistant to provide adequate protection of child health yet not so complex as to be uneconomical or excessively inconvenient for adults, particularly elderly adults over 60 years of age. In particular, the present invention relates to child resistant packages which employ a maze of intersecting circumferential and axial grooves.
[0016] The packages include a generally cylindrical container member and a coaxial closure member which may be rotated relative to the container member. The container member and the closure member engage to prevent relative axial movement there between except in predetermined positions.
[0017] The closure member advantageously may be snap closed onto the container by pushing the closure downwardly on to the container. The package may be easily opened by people who are slightly handicapped or lack total manual dexterity, such as those who are arthritic. Further advantages of the invention will become apparent from a consideration of the drawings and ensuing detailed description.
DETAILED DESCRIPTION OF THE INVENTION
[0018] The closure and container components of the package may be made from materials such as glass, metal, plastics such as polyethylene and polypropylene, as well as paper and the like. The container and the closure components need not be made from the same material. The term package refers to the container with the closure.
[0019] Referring to FIGS. 1-8 , there is shown an embodiment of package 1 which includes container 5 and closure 15 . Container 5 may be of any shape and dimension. Typically, container 5 is a cylindrical receptacle of common diameter throughout its length, or of bottle-like form with neck 17 of reduced diameter. Preferably, and as illustrated in FIGS. 1-8 , container 5 includes body 19 and neck 17 joined to body 19 . Neck 17 is dimensioned to receive closure 15 thereover. Neck 17 includes opening 18 for permitting access to the contents of container 5 . Although neck 17 is shown in FIG. 1 as having a narrower diameter than body 19 , the configuration of neck 17 is not so limited.
[0020] On the outer surface of neck 17 are molded or otherwise provided elevated ribs 23 . Ribs 23 form maze 21 of intersecting axial and circumferential grooves (A)-(K) as shown in FIG. 4 . Ribs 23 have lower surfaces 24 which are generally flat, preferably within ten degrees of perpendicular to the circumferential surface of neck 17 . Ribs 23 may vary in cross-sectional shape. Preferably, ribs 23 have a cross section that is generally trapezoidal as shown in FIG. 7( a ). Other possible cross sections include but are not limited to hemispherical and stepped as shown in FIGS. 7( b ) and 7 ( c ), respectively. Ribs 23 preferably include downwardly, outwardly tapered portion 25 as shown in FIG. 5A . The angle (β) of tapered portion 25 may vary from about one degree to about 89 degrees, preferably about 30 degrees to about 60 degrees, most preferably about 45 degrees.
[0021] In the embodiment shown in FIG. 4 , maze 21 includes a number of circumferential and axial grooves (A)-(K) defined by ribs 23 . Maze 21 includes lowermost circumferential groove (A), a series of three upper, circumferential grooves (C), (E) and (G), and axial grooves (B), (D), (F), (H) and (K). It is understood, however, that the number of circumferential and axial grooves are not limited to those shown in FIG. 4 . Circumferential grooves such as grooves (C), (E) and (G) may be horizontal or angled in a range of about 1 degree to about 20 degrees to the horizontal, preferably about 2 to about 3 degrees to horizontal. Most preferably, the circumferential grooves are horizontal.
[0022] In FIG. 4 , lowermost groove (A) of maze 21 includes detent 35 . Detent 35 functions to secure studs 27 of closure 15 in locking region 9 between detent 35 in groove (A) and inner wall surface 90 of neck 17 . Detent 35 most preferably is positioned from inner wall surface 90 of neck 17 by a distance that is about equal to the width of stud 27 so as to enable stud 27 to be secured in locking region 9 without requiring any lateral movement of stud 27 in lowermost groove A. Detent 35 , however, may be located a distance of about 11% to about 51% of the length of lowermost groove A distal to surface 90 of neck 17 , preferably a distance of about 23% to about 51% of the length of lowermost groove A distal to surface 90 of neck 17 , more preferably a distance of about 29% to about 51% of the length of lowermost groove A distal to surface 90 of neck 17 . Detent 35 preferably has a trapezoidal cross section as shown in FIG. 4 . Detent 35 , however, may have a variety of other cross sections such as hemi-spherical, ellipsoidal, square, rectangular and triangular.
[0023] Groove (F) may extend above the upper surface of groove (E) as shown in FIG. 4 . Groove (F), alternatively, may terminate at the upper surface of groove (E). Groove (C) may extend on each side of the intersection with groove (B). Similarly, groove (E) may extend to each side of the intersection of groove (D). Grooves such as (A), (C) and (E), together with studs 27 described below, limit unintended movement of closure 15 . In addition, this minimizes the likelihood that a child can forcibly pry closure 15 off of container 5 .
[0024] Closure 15 may be of generally conventional design which has a closed top 16 and cylindrical sidewalls 22 . Closure 15 has a diameter sufficient to fit over neck 17 . In this embodiment, closure 15 is unlined. In other embodiments closure 15 may be lined or linerless (e.g., plug seal). As shown in FIG. 3 , two inwardly projecting, diametrically opposed studs 27 are provided on sidewall 22 . In this embodiment, there are two diametrically opposed, individual mazes 21 , preferably identical mazes 21 , each of which extend 180 degrees around the circumference of neck 17 . In an alternative embodiment, studs 27 may number four and may be located at ninety degrees to each other. In this embodiment, there are four mazes, preferably identical mazes, each of which extend 90 degrees around the circumference of neck 17 . However, this is not so limited and any number of studs may be used, such as, 3 , 5 , 6 and the like that preferably are equidistant from each other. Preferably, there are an equal number of equally spaced, identical mazes 21 on the container neck 17 as studs 27 on the closure sidewall.
[0025] Studs 27 preferably have a trapezoidal cross section as shown in FIG. 6 . As shown in FIG. 6 , stud 27 has an inwardly, downwardly tapered, portion 28 and a generally flat, horizontal upper portion 29 . Preferably, upper portion 29 is within thirty degrees of perpendicular, most preferably perpendicular to sidewall 22 of closure 15 . The tapered portion 28 of stud 27 enables studs 27 to ride over ribs 23 of maze 21 when closure 15 is pushed downwardly onto container 5 . This enables a user to easily snap close closure 15 onto container 5 into a secured position in the locking region. Studs 27 have a length L and a thickness T. The length L of stud 27 is sufficient to prevent a child from manually prying closure 15 from container 5 . The thickness of stud 27 corresponds to the width of lowermost groove A so as to achieve a snug fit of stud 27 in groove A. The snug fit is sufficient to prevent child from rocking closure 15 off of container 5 .
[0026] The angle (α) of tapered portion 28 , as shown in FIG. 6 , may vary from about 1 degree to about 89 degrees, preferably about 30 degrees to about 60 degrees, most preferably about 45 degrees.
[0027] Studs 27 preferably are of a depth and height which correspond approximately with the depth and height, respectively, of lowermost groove (A) of maze 21 as shown in FIGS. 4 and 5 . This enables upper surfaces 29 of studs 27 to be in the preferred position of being adjacent and generally parallel to the upper surfaces of a groove of maze 21 .
[0028] When securing closure 15 onto neck 17 of container 5 , closure 15 is first placed onto neck 17 to cause stud 27 of closure 15 to engage axial groove (K) as in FIG. 1 . Axial groove (K) may be identified by arrow 50 . Downward pressure then is applied to closure 15 to cause stud 27 on closure 15 to ride over ribs 23 to engage the locking region in lowermost groove (A). Lowermost groove (A) includes detent 35 to retain stud 27 in the locking region. Studs 27 and ribs 23 cooperate to enable closure 15 to be snap closed easily onto container 5 . This encourages adults who lack dexterity to secure closure 15 onto container 5 to prevent children from gaining access to the contents of container 5 .
[0029] The child resistant package is opened by rotating and lifting closure 15 relative to container 5 . In this way, studs 27 on closure 15 pass through maze 21 to separate closure 15 from container 5 . In the embodiment shown in FIG. 8 , closure 15 first is rotated counterclockwise to cause stud 27 to ride over detent 35 in lowermost circumferential groove (A) to unlock closure 15 . Closure 15 then is rotated counterclockwise to cause stud 27 to engage first axial groove (B). Closure 15 then is lifted to cause stud 27 to engage first upper groove (C). Closure 15 is further rotated counterclockwise in groove (C) to cause stud 27 to engage second axial groove (D). Closure 15 then is lifted to cause stud 27 to engage second upper groove (E). Closure 15 then again is rotated to cause stud 27 to engage third axial groove (F). At this point, closure 15 is lowered to cause stud 27 to engage third upper groove (G). Subsequently, closure 15 is rotated to cause stud 27 to engage fourth axial groove (H). Closure 15 then is lifted to remove closure 15 from container 5 . This series of rotary and lifting motions provides the closure of the invention with high child resistance. Moreover, adults with limited manual dexterity may easily open the closure of the invention.
[0030] The child resistant package of the invention may be employed in any application where child-resistant benefits are desired to prevent access to the contents of a container. The package therefore may be used for storing of pharmaceutical products, agricultural products, toxic household chemicals, automotive products and other products with certain levels of specific ingredients which are covered within the CPSC guidelines that may be harmful to children. The child-resistant concept also may be used to prevent access to the operating mechanism of devices such as butane lighters, household cleaners, and other devices.
[0031] Numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein. | The present invention discloses a maze type package that may be child resistant. The package includes a cylindrical container member that includes a plurality of mazes thereon. The coaxial closure member includes studs for engaging the mazes and to releasably secure the closure to the container. | 1 |
RELATED APPLICATIONS
This application claims the priority of U.S. Provisional Application No. 60/993,368, filed Sep. 13, 2007.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to light emitting systems for helmets, and more particularly, to light emitting systems with LED modules for helmets.
2. Description of the Prior Art
Various attempts have been made in the art to provide lighting equipments that are useful in low light or no light environment. The lighting devices in the art generally include hardware that is mounted on the helmet. Moore et al., (U.S. Pat. No. 7,221,263) teaches a bicycle or motorcycle helmet that uses accelerometers to activate multiple arrays of LEDs that require high amounts of current for the light output.
The prior art also includes helmets with LED lights that are designed to act as an indicator to give various signals, for example, a brake signal, turn signal, or strobe positioning lights. These devices generally include a plurality of auxiliary components and fixed mechanisms to hold them to helmet surfaces as well as mechanisms to activate them remotely.
The helmets lighting systems in the prior art generally require additional mounting hardware to affix the lighting system to helmets. Such systems are preferred in a mining safety or other applications requiring no additional fixture attachments to helmets. A plurality of physical switches mounted on exterior battery cases are a big concern for electronic failure, water damage, and opens the potential for batteries to dislodge and short causing sparks which could ignite flammable gasses.
Burdick, (U.S. Pat. No. 6,982,633) teaches a motorcycle helmet having a ring of lights with a battery is mounted around the entire circumference of the helmet. However, this system is not suitable for various sized helmets, and in addition, requires substantial energy to keep it lighted continuously for a week or more without heavy batteries which would make it unwieldy to mount on a helmet.
Rodriguez et al. (U.S. Pat. No. 6,244,721) and Hanabusa, (U.S. Pat. No. 4,901,210) use a band holding exposed LEDs connected to the helmet with wires connecting to a battery mounted inside or outside of the helmet. The LEDs are powered by an open coin cell battery holder mounted on the rear of the helmet. Both methods include exposed connections and batteries to the air, which is most undesirable in explosive gas environments due to spark potential. Furthermore, these LEDs light the peripheral areas rather than lighting the area directly in front of an observer.
The helmet lighting systems in the prior art generally have large power consumption, bulky mounting mechanisms, user unfriendliness, and are fragile. Such helmet lighting systems have not been acceptable for use in the mining safety industry or underground construction sites. There are several areas where light is needed for utility functions for the wearers themselves. Prior art devices that address utility light output on helmets generally include heavy batteries and exposed wiring connections that may represent a spark hazard in potential explosive gas environments.
The prior art include lighting systems for safety apparel that use Electro-luminescence (EL) strips sewn into the fabric surfaces to blink on and off. In such lighting systems several “AA” batteries to activate the blinking of the strips are used. It is observed that such systems are prone to breakage, are very dim to view at even moderate distances, and contain wiring prone to breakage that must run the entire length of the EL strip. EL has no IR energy output frequency so is not used with FLIR equipment and it requires wires to run the full length of the light output putting dangerous conductive surfaces near the heart and chest areas of workers.
In order to light up surface areas of items such as clothing or backpacks, suitcases, exterior portions of transport vehicles, and the like, incandescent lights, LEDs, or EL are employed in the prior art. However, the extensive wiring and high current draw that reduces the battery life make these lighting systems unsuitable for mining and hazardous operating conditions. Safety jackets presently used by airlines are made with a flashing beacon attached that activates upon contact with water. It is observed that the lifespan of such devices is quite short (measured in hours) because they have no way of shutting them off. Furthermore, they do not contain IR output for long distance detection from aircraft. The prior art safety helmet lighting systems fail to assist search and rescue personnel in locating distressed or injured workers in dust-filled, fog-like, or inclement conditions that prevents visible light from penetrating. Emergency circumstances such as explosions, cave-ins, dense fog, smoke from fires, etc. can prevent light from penetrating the opaque air-borne conditions, thus, preventing rescuers from finding people quickly in need of immediate assistance.
A lighting system having light weight batteries is needed that provides light for extended periods of time and that allows others around to identify the position and orientation of the user. A lighting system is further needed that is intrinsically safe for use in potentially explosive gaseous environments and that is flexible to mount on safety helmets of various sizes.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a front perspective of a preferred embodiment of a LED lighting system of the present invention;
FIG. 2 is a top view of a module of the LED lighting system of FIG. 1 ;
FIG. 3 is a side view of the module of FIG. 2 ;
FIG. 4 is a top view of the module of FIG. 2 that shows the electronics of the module;
FIG. 5 is a top perspective of another alternative embodiment of LED lighting system of FIG. 1 with two modules;
FIG. 6 is a top perspective of another embodiment of LED lighting system of FIG. 5 ;
FIG. 7 is a top view of another embodiment of the LED light emitting system of FIG. 1 with four modules; and
FIG. 8 is a top perspective view of the LED lighting system of FIG. 7 mounted on the helmet.
SUMMARY OF THE INVENTION
A LED lighting system for emitting visible and invisible energy frequencies in low visibility and hazardous environments having a predefined object with an exterior surface, an elastic band attached to the exterior surface of the object, a LED module connected to the elastic band for emitting infra red and visible light in low visibility and hazardous environments is provided.
Each of the LED modules includes a shell that is securely mounted on a base plate preferably with a gasket. The body of the shell also includes at least one pair of LEDs. The module includes a quiescent circuit, a magnetic reed switch and at least one coin cell. In a preferred embodiment of the present invention the module is coupled with a first band and a second band. The second band includes a snap attachment to open and close the band around an object.
In another embodiment of the present invention, the LED light emitting system includes a pair of modules that are coupled with a pair of elastic bands. The first module has a first end and a second end so that the first end includes a first loop and a second end includes a second loop. The second module has a first end with a first loop and a second with a second loop. A first end of a first band is coupled with the second loop of the first module. A second end of the first band is coupled with the first loop of the second module. A first end of a second band is coupled with the first loop of the first module and a second end of the second band is coupled with the second loop of the second module.
Each of the magnetic rings is in close proximity to the magnetic reed switch of the respective module in the first position of the magnetic ring. In the first position, the magnetic ring is in close proximity with the reed switch that closes the electronic circuit to switch on the respective LEDs of the module. The magnetic ring is moved away from the reed switch of the respective module in the second position to open the reed switch and shut off the respective LEDs.
In another alternative embodiment of the present invention, the LED lighting system includes at least two pairs of LED modules that are coupled with at least two pairs of flexible bands. Each of the LED modules has an associated magnetic ring and a stopper. A first pair of modules and second pair of modules are approximately symmetrically positioned with respect to a vertical axis-YY. A first and a second module of the first pair include at least two white LEDs each. A third and a fourth module of the second pair of modules includes at least one color LED and one IR diode each.
A stopper is associated with each of the modules. The stopper advantageously restricts the motion of the respective rings along a predefined path on the band. The lighting system of the present invention is mountable on helmets, poles or similar objects of various sizes and with the elastic flexible bands. The white LEDs emit continuous white light to light up surrounding areas. A plurality of color LEDs are used to distinguish the rank of people working in dark areas. The packed electronics in the shell of the module reduces the possibility of accidents due to electric spark in hazardous environment.
DETAILED DESCRIPTION OF THE INVENTION
Although specific terms are used in the following description for sake of clarity, these terms are intended to refer only to particular structure of the invention selected for illustration in the drawings, and are not intended to define or limit the scope of the invention.
Referring to FIG. 1 , a LED lighting system in accordance with an embodiment of the present invention is shown. The LED lighting system 10 includes a LED module 12 , a first band 14 , a second band 16 and a snap attachment 18 . A magnetic ring 20 and a stopper 22 that are associated with the LED module 12 are preferably positioned on first band 14 . The magnetic ring 20 is movable between the module 12 and the stopper 22 along the first band 14 as indicated by arrow 1 . Bands 14 and 16 are preferably flexible at least in part and preferably made of elastic material. The LED light emitting system 10 has a closed configuration and an open configuration.
The module 12 includes a pair of opposed loops that are mounted on opposed ends of the LED module 12 . First band 14 is coupled to module 12 with a first loop 24 and second band 16 is coupled to module 12 with a second loop 26 . The ends of the bands 14 and 16 are removably coupled with the snap attachment 18 . A free end of first band 14 includes a female part 28 of the attachment 18 and a free end of the second band 16 includes a male part 30 of the attachment 18 . The male part 30 is inserted in the female part 28 with a snap fit to close the attachment 18 to define the close configuration of the LED light emitting system. The snap attachment is opened by pressing a trigger on the male part 30 to open the LED light emitting system 10 . It is, however, understood that connecting mechanisms, for example, a riveted snaps, Velcro, magnetic coupling can also be employed instead of the snap attachment 18 .
Referring to FIGS. 2 and 3 , the LED light utility module 12 in accordance with a preferred embodiment of the present invention is described. The LED module 12 includes a box shaped shell 32 that is securely mounted on an approximately rectangular base plate 34 . It is, however, understood that the shell 32 of round, oval, and other shapes are also contemplated. The shell 32 is preferably made of plastic material. A rubber gasket is preferably positioned between the shell 32 and the base plate 34 . The base plate 34 is preferably made of plastic material. Each light module is removable from a series of attachable modules that are connected with one or more module/modules with elastic bands.
The module 12 is a completely sealed with a non-replaceable type battery. The module 12 also includes associated electronic arrangement that is positioned on the base plate 34 to operate the LEDs. The covering shell 32 has a pair of plastic lensed light emitting diodes (LEDs). A first LED 36 emits visible light preferably constantly in a predetermined color and a second LED 38 intermittently blinks to emit IR energy. The IR LEDs blinks when the power is on.
As shown in FIG. 4 , the module 12 includes a quiescent circuit 40 , a magnetic reed switch 42 and a coin cell 44 . The quiescent circuit 40 includes current lowering resistors. The magnetic reed switch 42 is preferably a tiny glass sealed vacuum that is approximately (2 mm×10 mm) in size. The sealed vacuum of the reed switch 42 encloses magnetic contacts that close when any magnetic field is brought in close proximity with the reed switch 42 . A magnetic field is used to activate the LEDs inside the sealed unit of the module 12 .
The magnetic ring 20 has a first position and a second position as indicated by the arrow 1 ′- 2 ′. In the first position, magnetic ring 20 is in close proximity to the magnetic reed switch 42 and the magnetic ring 20 is away from the reed 42 switch in the second position. In the first position, the circuit is closed to allow the power from coin cell 44 to flow from a negative terminal to the two LEDs 36 and 38 and thereby returning to the positive terminal on the coin cell(s) 44 through the reed switch 42 and a quiescent circuit 40 .
The magnetic ring 20 is moved to the second position to turn off the LEDs 36 and 38 in the module 12 . The second position is achieved by moving the magnetic ring 20 away from the side of the module 22 , thus, removing the magnetic field necessary to keep the reed switch 42 closed. In the second position the reed switch 42 opens and the LEDs 36 and 38 shut off.
In another alternative embodiment of the light emitting system 10 , the module 12 includes only one cord or band and snap attachment 18 . The continuous cord is threaded through the first loop 24 of the module 12 and the cord exits through the second loop 26 of the module 12 continuing to the snap attachment 18 . The module 12 also includes a hook and loop type Velcro self-stick removable piece on an outer surface of base plate 34 . The self stick attachment is well known in the art. The self stick attachment advantageously allows sticking the module 12 to a desired object.
Now referring to FIG. 5 , another alternative embodiment of the LED light emitting system 10 in accordance with the present invention is shown. In this one embodiment, the LED system 50 includes a first LED module 52 , a second LED module 54 , a first band 56 and a second band 58 . A first magnetic ring 60 is associated with first module 52 and a second magnetic ring 62 is associated with second module 54 . In one embodiment, each of magnetic rings 60 and 62 are movable along band 58 . A first stopper 64 and a second stopper 66 are also positioned near respective magnetic rings 60 and 62 on the second band 58 .
The first LED module 52 has a first end 68 and a second end 70 . First end 68 includes a first loop 72 and the second end 70 includes a second loop 74 . First band 56 having a first end 78 and a second end 80 , and the second band 58 with a first end 84 and a second end 86 are coupled with the modules 52 and 54 to define the lighting system 50 of the present invention. The band 58 is preferably made of elastic material to allow adjustment while mounding the system 50 on a desired object.
The first end 78 of the first band 56 is coupled with second loop 74 of the first module 52 , and the second end 80 of the first band 56 is coupled with the first loop 88 of the second module 54 . The first end 84 of the second band 58 is coupled with first loop 72 of the first module 52 , and the second end 86 of the second band 58 is coupled with the second loop 90 of the second module 54 . The length of the second band 58 is approximately four times the length of first band 56 . The length of the first band 56 is approximately 5″ and the length of the second band 58 is approximately 20″. It is, however, understood that the lengths of the bands may vary with the application.
Referring to FIG. 6 , in another embodiment of the LED light emitting system 50 , the second band 58 includes a snap attachment 92 that is adapted to facilitate mounting and removal of the LED light emitting system 50 on an object, such as, a helmet or a pole. The snap attachment 92 divides the second band 58 into two parts. The two parts are removably connected to open and close the band 58 . The snap attachment 92 has a male part 94 and female part 96 . The male part 94 and female part 96 are snap-fitted to close the band 58 . The system 50 is preferably positioned on a desired object and then the band 58 is closed with the snap attachment 92 . The snap attachment is opened to remove the band 58 , thereby, removing the LED lighting system 50 .
Now referring to FIGS. 7 and 8 , another embodiment of the lighting system in accordance with the present invention is shown. In this one embodiment, the lighting system 100 includes at least two pairs of LED modules coupled with at least two pairs of flexible bands. In the light emitting system 100 , each module snaps or attaches to successive module to form a light emitting rope in various frequencies dependent upon which modules are snapped together.
The lighting system 100 has a first end 102 and a second end 104 . A first pair of modules includes a first module 106 and a second module 108 . Modules 106 and 108 define a first portion 110 of the LED lighting system 100 along with respective magnetic rings and stoppers. Modules 106 and 108 are approximately symmetrically positioned in the LED lighting system 100 with respect to a vertical axis-YY. Modules 106 and 108 are approximately equidistant from the first end 102 . Each of the modules 106 and 108 preferably include two white LEDs.
A second pair of modules includes a third module 112 and a forth module 114 . Modules 112 and 114 define a second portion 116 of the LED lighting system 100 along with respective magnetic rings and stoppers. Modules 112 and 114 are approximately symmetrically positioned in the LED lighting system 100 with respect to vertical axis-YY. Modules 112 and 114 are approximately equidistant from the second end 104 . Each of the modules 112 and 114 preferably respectively include a color LED and an IR diode.
Now referring to FIGS. 1 to 8 , the lighting system 10 of the present invention is mounted on an object such as a helmet preferably on a bottom ring of the helmet. The light emitting system 10 is attached to the exterior surface of various types of helmets by pulling the unit over the exterior surface to the surrounding brim or base of the helmet. The self stick removable Velcro attachment advantageously helps to position the module 12 to any desired object. The self sticking attachment prevents the module 12 from drifting due to a shock.
Modules are removable to allow for independent operation. The modules are removed by uncoupling the loops from the respective bands. Each of the modules is advantageously detachable from the other modules of the light emitting system 10 . The detached module is an independent light source for other applications. The stand alone module is attachable to a desired object preferably with an attaching means, for example, Velcro strips, two-way adhesive strips etc.
The flexible elastic bands securely hold the system on the body of the helmet. A user positions the system 10 according to the requirement on the helmet. In the first position, the LEDs are on to emit respective light. The lighting system 10 is deactivated by moving the magnetic ring 20 from the first position to the second position. In the first position, the magnetic field of ring 20 activates the magnetic reed switch 42 to blink the LEDs. LEDs 36 and 38 can be switched off by moving the magnetic ring 20 to the second position.
The stoppers 22 associated with each of the modules 12 advantageously prevent the motion of the respective rings 20 beyond the position of the stopper 22 on the band 14 . The lighting system 10 of the present invention easily adapts to helmets of various sizes and configurations without need of any mounting hardware. The electronic circuitry and the batteries are completely encased in air-tight body shell 32 without any exposed wires, connections, batteries, or switches.
Two frequencies of Infrared band and visible light are preferably emitted by the light emitting system 10 of the present invention. The first IR frequency is approximately in a range of 850 nm.-1200 nm. that is invisible to the naked eye. The second visible frequency is in the visible light spectrum. The LEDs 36 and 38 emit special visible and invisible energy frequencies that penetrate opaque materials such as dust and fog so rescuers can find distressed and injured people quickly in adverse visibility environments. The LED lighting system 10 is mountable on various objects to increase their visibility as well as low-profile to prevent accidental impact with external objects.
The light emitting system 10 of the present invention preferably includes two small coin cells 44 powering multiple light emitting diodes (LEDs) 36 and 38 connected to a current reducing resistor 40 and a magnetic reed style switch 42 for activation. The module 12 preferably includes multiple LEDs giving off visible white light energy and/or LEDs giving off IR energy or a combination of both white light and IR LEDs. By employing LEDs emitting continuous white light, the visible energy is projected outward away from the user for utility use to light up surrounding areas and is visible to surrounding workers.
Various colors and combinations of LEDs may be incorporated into the light emitting system 10 for attachment to helmets. For example, a yellow LED color output module may be placed on the rear of the elastic band to signify to surrounding workers the orientation position of fellow workers in pitch black environments such as is found in mines. Other colors may signify and distinguish the rank of people working in dark areas between engineers, construction, medical, and safety personnel.
The system 10 of the present invention is safe enough to avoid accidents in hazardous environment. The electronic and electrical components are not in contact with surrounding air due to the shell 32 . No spark hazard can exist where a possible shorting of contacts could accidentally set off an explosion. The use of magnetic ring 20 and reed switch 42 eliminates possibility of electric spark.
The shell 32 is made of non-conductive compound. The shell 32 encapsulates the interior portion of the module preferably through an airtight rubber gasket. The shell 32 and base plate 34 arrangements in the module makes the module robust. The system 10 can withstand high impact, hostile weather and extreme environmental conditions including under water, chemical and physical abrasiveness, and is not prone to connection failures due to extreme temperature changes.
LED light module 12 is removable from a series of attachable modules to adjust according to the size of an object on which it is being mounted. The elastic band also adds flexibility of mounting on objects of various sizes to the LED light system 10 . The light modules 12 can be coupled with other light modules of different LED light to form a light emitting rope using the method described above.
The IR LEDs 38 conserve energy by blinking on and off. IR LEDs are not able to be seen with normal eye and do not offer any distraction by blinking on and off. The IR blinking LED 38 is preferably replaceable with a RED LED to increase visibility. The system is attachable to a helmet worn by miners or construction workers. Although the IR LED 38 cannot be seen without use of special detection equipment, it is designed to blink a high intensity flash in the IR frequency spectrum to allow searchers/rescuers/emergency personnel to locate the device through environments such as dust-filled, smoke laden, blizzard, and other conditions that make it impossible to see normal light in the visible spectrum with the naked eye.
In more adverse conditions where smoke and dust prevail such as in a coal mine, the pulsing IR diode 38 acts like a beacon in the fog penetrating opaque materials to be detected using special FLIR (Forward Looking Infrared) equipment such as the type used in the military for night vision exercises.
A lighting system 50 with two pairs of modules on the helmet worn by miners offers an advantage of peripheral vision lighting, and additional orientation positioning for other miners to observe. The smaller diameter light output penetrates through fog and smoke far more efficiently than brighter reflective lensed type lights used for miner helmets. The small diameter LEDs 36 and 38 are easily seen through fog as single points of light therefore the positions of the people wearing them are easily determined.
The lighting system 10 of the present invention requires extremely low current draw. Gasket positioned in between the shell 32 and the base plate 34 advantageously makes the system 10 a waterproof system. The system 10 does not require external switches to activate and deactivate the LED lights. The light emitting LED system is tiny enough to be mounted on, such as, for example, a belt pack, vest, backpack, jacket, duffel bag, raincoat, safety vest. The light emitting LED system 10 is intended for use with fireman waterproof coats, DOT safety vests, police and emergency worker vests, electrical workers, linemen, as well as duffel bags, securing straps for transport vehicles, sails, belt packs, and back packs.
The embodiments of the invention shown and discussed herein are merely illustrative of modes of application of the present invention. Reference to details in this discussion is not intended to limit the scope of the claims to these details, or to the figures used to illustrate the invention. | This invention relates to a miniature, battery operated, air tight light emitting module having a LED/LEDS that projects at least two different frequencies of light energy. The LEDs are mounted in a protective air-tight shell. The LEDs are activated by a magnetic field of associated magnetic rings. The attachment mechanism to hold the module(s) to safety hard hats and helmets consists of an elastic band allowing a module or series of modules to be attached to the exterior surface of various types of helmets. | 5 |
FIELD OF INVENTION
This invention relates to food processing equipment and more particularly to cooling systems for can and similar food containers.
BACKGROUND OF INVENTION
Since man first began preserving foods in can type containers, the rapid cooling of these containers after heating to preserve the contents thereof has been a problem. If the cans are not cooled evenly, hot spots will develop which can cause spoilage. Long cooling conveyors have traditionally been used with liquid coolants such as water being used to speed up the cooling process.
The above systems are usually linear thus requiring large amounts of space for installation of the same. They also do not usually include any recirculation means since once the water is heated during the cooling process, it will cost more to cool it for recycling than it would to use additional fresh water while dumping the hot water. Thus large space requirements and large volumes of water have been required to effectively operate these prior known systems.
Although attempts have been made to reduce the floor space required by normal can cooling systems as well as means for reducing the water consumption thereof, up until now no completely suitable system has been developed.
BRIEF DESCRIPTION OF INVENTION
After much research and study into the above-mentioned problems, the present invention has been developed to provide a can cooling system which takes up a minimum of floor space and recirculates its cooling liquid thus greatly reducing the volume of such liquid required for any given number of units processed.
The above is accomplished through the utilization of multiple lanes in stacked configuration with the hot cans being introduced at the bottom and the cool cans being removed from the top. This combination additionally is less expensive to produce and maintain.
In view of the above, it is an object of the present invention to provide a cooling system for can type containers requiring a minimum of floor space.
Another object of the present invention is to provide a can type cooling system so constructed that the path followed by each can is a stacked zig-zag pattern.
Another object of the present invention is to provide a stacked path can type cooling system wherein the cans enter the lower portion thereof and exit the upper portion thereof.
Another object of the present invention is to provide a cooling system wherein the cooling liquid is applied to the cooler cans and then sequentially to the hotter cans.
Another object of the present invention is to provide a stacked conveyor can cooling system which imparts a spinning motion to the can as it is cooled thereby evenly cooling the interior contents thereof.
Another object of the present invention is to provide a stacked can cooling system including a cooling liquid recirculation means.
Other objects and advantages of the present invention will become apparent and obvious from a study of the following description and the accompanying drawings which are merely illustrative of such invention
BRIEF DESCRIPTION OF FIGURES
FIG. 1 is a partially cutaway perspective view of the improved cooling system of the present invention;
FIG. 2 is an enlarged perspective view of the track assembly and pusher bars of the present invention;
FIG. 3 is an enlarged sectional view of the track portion of the present invention;
FIG. 4 is a somewhat schematic representation of the pusher bar drive system of the present invention;
FIG. 5 is a somewhat schematic representation of the track paths of the present invention;
FIG. 6 is perspective view showing the pusher bar drive system; and
FIG. 7 is a somewhat schematic view of the cooling portion of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
With further reference to the drawings, the improved cooling system of the present invention, indicated generally at 10, includes a plurality of upright frames 11 which in turn support a plurality of horizontal frames 12.
A plurality of track support frames 13 extend across the cooler system and are supported by horizontal frames 12 on opposite ends of such support frames
Track rails 14 are mounted on track support frames 13 and are parallely disposed to each other as can clearly be seen in FIGS. 2 and 3. The horizontal portion of these rails form four tiers indicated generally from top to bottom as 15, 16, 17, and 18.
The track rails 14 on the top three tiers 15, 16, and 17 are all disposed parallel to each other and parallel to the horizontal frames 12. The track rails on the bottom tier 18 are disposed parallel to each other but at slight angle to the horizontal frames 12, said angle exactly equaling the distance between two of the rails from one end thereof to the other. This angulation of the lower tier of track rails effectively forms a cross-over or lane change so that cans entering the lower tier from the tier and lane directly above will be one lane over when they are again moved back up to tier 17. This lane switch is shown in dotted lanes in FIG. 5 and will hereinafter be described in greater detail.
Disposed between the two upper tiers 15 and 16 at opposite ends thereof, as seen clearly in FIG. 4, are idler sprockets 19 and 20. These idler sprockets are paired with one being on each side of the tiers and are mounted on shafts 19' and 20', respectively.
Second pairs of idler sprockets 21 and 22 are disposed at opposite ends of the lower two tiers 17 and 18 and are paired as are idler sprockets 19 and 20. These last mentioned sprockets are rotatively mounted on their respective idler shafts 21' and 22'.
A pair of drive sprockets 23 are disposed on opposite sides of intermediate tiers 16 and 17 adjacent idler sprockets 19 and 21. This pair of chain drive sprockets 23 are fixedly mounted on drive shaft 24. One end of this drive shaft projects outwardly from the side of the cooling system 10 and has fixedly mounted thereon large drive sprocket 25.
Drive chain 26 is trained over large drive sprocket 25 as well as over small drive sprocket 27 as can clearly be seen in FIG. 6. This last mentioned drive sprocket is driven by reducer 28 which in turn is driven by motor 29 in the normal manner of such devices.
A pusher bar chain 30 is trained about each pair of sprockets from drive sprocket 23, over idler sprockets 19, 20, 21, and 22, and back to drive sprocket 23 as seen clearly in FIG. 4. Extending between and secured to the pairs of pusher bar chains 30 are a plurality of spaced pusher bars 31. The spacing between these pusher bars is such that without internal adjustments the cooler 10 of the present invention will accommodate a wide range of different size containers.
The track rails forming the upper tier 15 are curved downwardly approximately 90 degrees adjacent idler sprocket 20 at one end and are curved downwardly adjacent idler sprocket 19 to a point just above bottom tier 18 at the other end as can clearly be seen in FIG. 4.
The track rails forming tier 16 begin immediately above top tier 15 at the end of idler sprockets 20 and extend downwardly a little over 90 degrees at the end adjacent drive sprockets 23.
The track rails forming tier 17 begin immediately above tier 16 adjacent the end of drive sprockets 23 and extend downwardly slightly over 90 degrees slightly at the end adjacent idler sprockets 22.
Finally the track rails of tier 18 begin immediately above tier 17 adjacent the end of sprockets 22 and extend upwardly on the outside of the pusher bars 31 to a point adjacent upper tier 15 at the end adjacent idler sprockets 21, again all this can clearly be seen in FIG. 4.
The top 32 of the cooling system 10 is formed from sheet metal and is air tight. Air impervious side panels 33 are provided between the upright frames 11 and the horizontal frames 12. These side panels are removable for maintenance of the system but are otherwise left in place.
Ventilator panels 34 have fixed louvers 35 formed therein and are removably mounted immediately below side panels 33.
Air impervious end panels 35 are provided and are removably mounted for maintenance purposes.
The bottom 26 of the cooling system 10, along with side walls 37 and end walls 38 form a tank like structure. An internal wall or dam 39 runs longitudinally the length of the system thus forming sumps 40 and 41. Although only one wall or dam is shown forming only two sumps, it is to be understood that additional walls could be provided thus forming three or more sump areas in the lower portion of the system 10 of the present invention. The purpose of dividing the lower portion of the system into different sumps will hereinafter be discussed in greater detail.
At one end of the cooling system 10 of the present invention is provided a twist chute 42 which takes a can or other container 43 from an inlet conveyor 44 and orients it from vertical to horizontal prior to entering the system at tier 17 as can clearly been seen in FIG. 1.
Conversely an outlet twist chute 44 is provided adjacent upper tier 15 and is adapted to operatively carry the cooled product from the cooling system 10 and deposit the same in correct orientation on outlet conveyor 45.
Communicating through top 32 is an exhaust hood 46 operatively connected to exhaust stack 47 which includes a forced air drive means as indicated by dotted lines 48.
At least one pump means is provided for each of the sumps 40 and 41 and are designated at 49 and 50. These pumps are connected to their respective sumps by sump lines 51 and 52. Outlet lines 53 and 54 lead to headers 55 and 56 which are attached to spray tubes 57 and 58. These spray tubes operatively mount spray nozzles 59. These spray tubes and spray nozzles cover almost the entire area immediately below top 32.
A fresh water inlet line 60 comes from a standard water supply, passes through a controlling means 61 and into sump 40 as can be seen clearly in FIG. 7. A waste water line 62 is provided in sump 41 and leads to a disposal area such as the municipal sewer.
The various lanes formed between the track rails 14 within the cooling system 10 of the present invention are illustrated schematically in FIG. 5. The inlet indicated by arrow 66 comes into lane one, indicated by arrow 67 on tier 17. The cans are moved along such tier by pusher bars 31 and at the end of such tier move upwardly adjacent sprockets 23 between the curved track rails to tier 16. The cans continue to move as indicated by arrow 16' in FIG. 4 until they approach idler sprockets 20 where the track rails carry such cans up to tier 15. They continue to move as indicated by arrow 15' to the area adjacent idler sprockets 19 where such cans move downwardly between the track rails to the area adjacent idler sprockets 21. Here they enter tier 18 and continue to move as indicated by arrow 18'. The track rails forming the various lanes on tier 18 are offset one lane from the point the cans enter tier 18 to the point where they exit such tier. These shift lanes are indicated by broken lines 68 in the lane schematic shown in FIG. 5. Thus as the cans 43 move upwardly between the curved track rails adjacent idler sprockets 22, they will move into lane two 69 of tier 17.
The cans 43 continue to move through the system 10 of the present invention as described above, each time shifting one lane as they come pass tier 18, i.e., from one lane two 69, to lane three 70, to lane four 71, and finally to lane five 72. From lane five of upper tier 15 the cans automatically discharge as indicated by arrow 73.
Because of the multi-tiered, multi-laned track system of the present invention, a can will travel for, example, up to twelve hundred linear feet in a cooling system taking up only 30 linear feet. Thus a forty to one space reduction is achieved over conventional in-line cooling conveyors.
The cooling system 10 of the present invention includes the two sumps 40 and 41 described above which, through sump line 51 and pump 49, delivers water to header 55 and to spray tubes 57. It should be noted that these spray tubes are located directly over sump 40 while spray tubes 58 discharge water from sump 41 and are located directly thereabove.
Make-up water, which is supplied in limited amounts, can be controlled by any suitable means such as controller 61 which can be a float valve or other similar means. As make-up water is added, any overflow moves across dam 39 to sump 41 where the access is removed by discharge through overflow pipe 62. The reason for this arrangement is that sump 40, which receives the cool make-up water, sprays on the last two lanes 71 and 72 which are the coolest containers. Thus it can clearly be seen that water from each of the individual sumps removes the maximum amount of heat from the cans being processed under the respective spray tubes.
Although the spray tubes are only located at the top of the cooling system of the present invention, water therefrom moves down between the openings in the track rails 14 thereby cooling all of the tiers or levels of the conveying system.
The exhaust fan 48 located adjacent exhaust hood 46 on the top 32 of the cooler 10 draws outside air in through louvered panels 34 at the bottom of each cooler and sucks it through the water spray thus absorbing heat therefrom. As the heat saturated air leaves the cooler through the exhaust stack, a major part of the heat load is removed therewith. The balance of the heat load is removed through the water overflow in the sumps as hereinabove described.
It has been found that when the circulating pumps 49 and 50 use headers of 11/2 and 2 inch diameters, respectively, with the spray nozzles 59 being on eight inch centers in spray tubes 57, adequate cooling can be accomplished. The spray nozzles preferably have 13/64 inch orifices and the two headers deliver 1.1 gallons per minute at 10 psi in spray tubes 57 and 2.1 gallons per minute at 20 psi in spray tubes 58.
The pusher bars 31 are driven by a 11/2 horsepower motor 21 with a variable speed drive 28 which allows the drive chains 30 to move at any selected speed between twenty-five and seventy-five feet per minute.
Since the cans 43 propelled by the pusher bars 31 roll along the track rails 14, they will rotate or spin in one direction on one tier and will roll or spin in the opposite direction on the next tier thus changing direction some twenty times in a four tier, five lane systemdescribed herein. This spinning and changing of spin direction agitates the interior contents of the product being cooled thus greatly enhancing the efficiency of heat transfer from the product.
Although for simplicity in description, only a single inlet, single discharge system has been described, it is to be understood that additional lanes could be added with crossovers moving in opposite directions so that a dual or twin system could be operated from the same drive means.
Also the present invention is intended to be a modular system wherein additional sections of track rails can be added to extend the length of the cooler and thereby multiplying the travel distance for any given container to be cooled.
Finally mild vertical vibrations can be added when viscous products are being processed. Vibrations of two cycles per second at an amplitude one-fourth inch have been found to reduce the cooling time of light sauces and soups by approximately thirty per cent.
From the above it can be seen that the present invention has been developed to provide a very compact and yet highly efficient cooling system which can be extended or reduced in size as need dictates.
The present invention may, of course, be carried out in other specific ways than there herein set forth without departing from the spirit and essential characteristics of the invention. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, and all changes coming within the meaning and equivalency range of the appended claim are intended to be embraced therein. | This invention is a cooling device for cans and similar containers and is specifically designed for installation where floor space is either limited or at a premium. Additionally, there is a unique liquid circulation system which is extremely effective in cooling and yet low in energy consumption. | 5 |
This application is a divisional of copending application Ser. No. 07/688,299, filed on Apr. 22, 1991, the entire contents of which are hereby incorporated by reference
FIELD OF THE INVENTION
The present invention relates to a cephalosporin acetylhydrolase gene, a recombinant DNA molecule prepared by introducing said gene into a vector used in an Escherichia coli host-vector system, E. coli cells transformed with said recombinant DNA molecule, a protein having an amino acid sequence encoded by said gene, an enzyme comprising a multimer, preferably tetramer or octamer, of said protein, and a process for preparing said protein or enzyme.
PRIOR ART
Cephalosporins such as cephalosporin C and 7-aminocephalosporanic acid (hereafter referred to as 7-ACA) were hitherto derived by eliminating the acetyl group bonded to the hydroxymethyl group at their 3-position (hereafter referred to as deacetylation) to deacetylated compounds, such as deacetylcephalosporin C and deacetyl 7-ACA, which are useful as starting materials to synthesize a variety of cephalosporin antibiotics including those already on the market.
As a method for deacetylation of cephalosporins, there exist chemical and enzymatic methods. Of these methods, the latter is believed to be advantageous partly because it can be performed at an approximately neutral pH and at mild temperature and partly because it accompanies less side reaction. Several enzymatic methods have been already disclosed (for example, Japanese Patent Publication Nos. 108,790/1984, 132,294/1974 and 67,489/1986, and U.S. Pat. No. 3,304,236).
BRIEF DESCRIPTION OF THE INVENTION
The present inventors have found that a strain of Bacillus subtilis isolated from soil produces cephalosporin acetylhydrolase and efficiently produces deacetylcephalosporins by deacetylation of cephalosporins. This finding has led the inventors to the idea that the construction of a microorganism capable of preferentially producing the cephalosporin acetylhydrolase by recombinant DNA technology would be industrially very advantageous for preparing deacetylcephalosporins. Such a microorganism remarkably producing only cephalosporin acetylhydrolase is not known so far.
The present inventors have made an extensive study and succeeded in isolating a DNA fragment carrying a cephalosporin acetylhydrolase gene from B. subtills newly isolated from soil and in cloning of said DNA fragment in E. coli. They also found that E. coli transformed with a plasmid vector, into which said DNA fragment had been inserted, produced a remarkable amount of cephalosporin acetylhydrolase. The present invention has been completed on the basis of the above findings.
Thus, the present invention provides a cephalosporin acetylhydrolase gene, a recombinant DNA molecule containing said gene, E. coli cells transformed with said recombinant DNA molecule, a protein having an amino acid sequence encoded by said gene, an enzyme comprising a multimer of said protein, and a process for preparing said protein or enzyme.
The newly isolated strain, Bacillus subtilis SHS0133, from which the cephalosporin acetylhydrolase gene was obtained according to the present invention, was deposited at the Fermentation Research Institute, Agency of Industrial Science and Technology, 1-3, Higashi 1 chome, Tsukuba-shi, Ibaraki-ken, 305, Japan under Budapest Treaty with the accession number FERM BP-2755 (Date: Feb. 15, 1990).
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 depicts the amino acid sequence of cephalosporin acetylhydrolase (SEQ. ID. NO. 1).
FIGS. 2a and 2b depicts the base sequence of cephalosporin acetylhydrolase gene, (the lower row) (SEQ. ID. NO. 2) and the amino acid sequence deduced therefrom (the upper row) (SEQ. ID. NO. 2).
FIG. 3 depicts the partially determined amino acid sequence (34 amino acid residues) of cephalosporin acetylhydrolase (SEQ. ID. NO. 3).
FIG. 4 depicts four synthetic oligonucleotide probes including all of the genetically possible DNA base sequences deduced from the underlined amino acid sequence in FIG. 3.
FIG. 5 depicts the restriction enzyme cleavage map of recombinant plasmid pCAH01 and the position at which the DNA probe hybridizes.
FIG. 6 depicts the restriction enzyme cleavage map of recombinant plasmid pCAH03.
FIGS. 7a and 7b depicts the DNA sequence of the cloned cephalosporin acetylhydrolase gene and flanking regions (the upper row) (SEQ. ID. NO. 11) and the amino acid sequence deduced therefrom (the lower row) (SEQ. ID. NO. 11.
FIG. 8 depicts the construction of miniaturized plasmid pCAH10 which corresponds to plasmid pCAH03 but deletes a region downstream of cephalosporin acetylhydrolase gene.
FIG. 9 depicts the construction of expression plasmid pCAH21 used in E. coli.
FIG. 10 depicts the construction of expression plasmids pCAH211 and pCAH212 used in E. coli.
DETAILED DESCRIPTION OF THE INVENTION
Characteristics of B. subtilis SHS0133
1. G+C mole percent(%) of chromosomal DNA: 43.4
2. Morphological characteristics
The strain is a gram-positive, short rod-shaped bacterium of 0.7-0.8×1.8-2.6 μm in size, and is peritrichous. This strain grows well under an aerobic condition and also grows weakly in a natural medium containing glucose under an anaerobic condition. Spore, 0.8× 1.3-1.7 μm in size, is formed in the central part of the cell.
3. Cultural characteristics
(1) Meat extract agar plate culture (at 30° C., for 7 days)
Colony formation: 24 hours after inoculation
Shape: irregular
Surface: gilled
Margin: undulate
Elevation: convex
Color: cream
Luster: dull
Optical property: opaque
(2) Meat extract agar slant culture (at 30° C., for 7 days)
Growth: good
Shape: filiform
Surface: gilled
Color: cream
Luster: dull
Optical property: opaque
Consistency: butyrous
(3) Meat extract broth culture (at 30° C., for 7 days)
Growth on surface: thick film is formed
Clouding: slight
Odor: slightly aromatic
Sediment: visid
Amount of sediment: scanty
(4) Meat extract gelatin stab culture (at 24° C., for 30 days)
Growth: grows uniformly along the stab line
Line of puncture: filiform
Mode of liquefaction: liquefied on 7th day at 24° C. to form 0.5 mm of liquefied layer (stratiform)
(5) Litmus milk culture
Litmus is reduced. Casein is digested rapidly without coagulation.
4. Biochemical characteristics
(1) Reduction of nitrate: positive
(2) Denitrification: positive
(3) MR test: negative
(4) VP test: positive
(5) Formation of indole: negative
(6) Formation of H 2 S:
lead acetate paper: negative
TSI: negative
Krigler: negative
(7) Hydrolysis of starch: positive
(8) Utilization of citrate:
Koser: positive
Christensen: positive
(9) Utilization of inorganic nitrogen source:
nitrate: positive
ammonium: positive
(10) Formation of pigment: brown pigment was formed
(11) Urease test: positive
(12) Oxidase test: positive
(13) Catalase test: positive
(14) pH:
growth range: 1.5-8.8
optimum: 6.0-8.8
(15) Temperature:
growth range: 16.5° C.-50.5° C.
optimum: 26.0° C.-36.0° C.
(16) OF test:
D-glucose: produces acids fermentatively without generating gas
lactose: produces acids fermentatively without generating gas
(17) Formation of acids and gas from sugars:
i) produces acids and no gas from L-arabinose, D-xylose, D-glucose, D-mannose, D-fructose, maltose, sucrose, trehalose, D-mannitol, glycerol, and starch;
ii) produces neither acids nor gas from D-galactose, lactose, D-sorbitol, and inositol.
(18) Nutritional requirement: none
(19) Degradation of pectin: positive
(20) Degradation of hippuric acid: negative
(21) Formation of levan (from sucrose, raffinose): positive
(22) Arginine hydrolase: negative
(23) Lecithinase: negative
(24) Growth under anaerobic condition: grows weakly in natural medium containing D-glucose.
From the above results, the strain was identified to be one strain of B. subtilis on the basis of Bergey's Manual of Systematic Bacteriology, Vol. II, 1986, and designated as Bacillus subtilis SHS0133.
The present invention encompasses a process for preparing cephalosporin acetylhydrolase using a recombinant microorganism transformed with a recombinant DNA molecule prepared by introducing into a vector used in an E. coli host-vector system an isolated DNA base sequence encoding the amino acid sequence depicted in FIG. 1, preferably the DNA base sequence depicted in FIG. 2. This process may be realized by following the next seven steps which represent the history of the development of the present invention, although the process can be achieved by more simple procedure because of the reason that the DNA base sequence encoding the cephalosporin acetylhydrolase is revealed by this invention.
(1) Bacillus subtills (FERM BP-2755) is cultured in an appropriate medium and allowed to produce cephalosporin acetylhydrolase, and the produced cephalosporin acetylhydrolase is separated from the medium and purified. The purified enzyme is digested with an appropriate protease used in fragmentation of a protein, the resultant peptide fragments are separated, and then the amino acid sequence of one of the peptide fragments is determined from the amino terminus.
(2) Possible DNA base sequences corresponding to a part of the amino acid sequence determined are deduced, and a pool of oligonucleotides having the deduced base sequences are chemically synthesized, and the 5'-terminus of the oligonucleotides was labeled with 32 p. The labeled oligonucleotides are used as probes for gene cloning.
(3) Chromosomal DNA is extracted and purified from B. subtilis (FERM BP-2755), digested with various restriction enzymes, electrophoresed on agarose gel, and the separated DNA fragments are transferred onto nitrocellulose membrane from the gel. Southern hybridization is then conducted using the nitrocellulose membrane and the 32 p-labeled probes prepared in the above step (2) to select DNA fragments showing homology to the probes. Of the DNA fragments, a somewhat larger fragment as compared with the size of the desired gene expected from the molecular weight of cephalosporin acetylhydrolase protein is selected, relevant region on agarose gel containing the DNA fragment is excised, and the DNA is extracted.
(4) The DNA fragment from the above step (3) is inserted into an E. coli cloning vector and the resultant recombinant plasmid is introduced into E. coli cells by transformation. The transformants are plated on an agar medium to form colonies, and colony hybridization is conducted using the 32 P-labeled probes. The colony of E. coli showing homology with the probe is selected and isolated.
(5) The recombinant plasmid DNA is extracted from the selected E. coli cells and the restriction enzyme cleavage map is constructed. Subsequently, the region irrelevant to cephalosporin acetylhydrolase gene is eliminated. The base sequence of the B. subtilis-derived DNA fragment encoding the cephalosporin acetylhydrolase is determined. Amino acid sequence deduced from the determined DNA base sequence is then compared with the partial amino acid sequence, molecular weight, terminal amino acid analysis and amino acid composition analysis of cephalosporin acetylhydrolase, and the structural gene for the cephalosporin acetylhydrolase is determined.
(6) The DNA fragment containing cephalosporin acetylhydrolase gene is properly modified and then introduced into a gene expression vector for E. coli so that the structural gene is connected after a promoter derived from E. coli, to construct a recombinant plasmid for expression.
(7) The recombinant expression plasmid obtained above is introduced into an E. coli host by transformation to prepare a novel E. coli strain producing cephalosporin acetylhydrolase.
The procedures employed in the above steps are known to those skilled in the art and can be readily carried out according to an experimental protocol disclosed in standard text books, such as "Molecular Cloning", T. Maniatis et al., Cold Spring Harbor Laboratory (1982). All of the materials used, such as enzymes and reagents, are commercially available and may be used according to the supplier's instructions.
E. coli used as a host may be a strain of E. coli K-12 derivatives such as HB101, DH1, C600, JM103, JM105 and JM109. As an E. coli vector used in cloning, a plasmid vector such as pUC13, pBR322 and pAT153 as well as a phage vector such as λgt10 can be exemplified. The abovementioned hosts and vectors are commercially available and easily obtainable.
In the above step (1), the amino acid sequencing of a protein is known (for example, a commercially available automated amino acid sequencer may be used). In the above step (2), the synthesis of the oligonucleotides can be carried out using a commercially available DNA synthesizer according to the supplier's protocol. In the above step (5), the determination of the DNA base sequence can be performed according to the method by Sanger et al., Proc. Natl. Acad. Sci. U.S.A., 74, 5463-5467(1977), where a known M13 vector system is employed.
In the above step (6), the construction of a plasmid to direct efficient expression of the desired gene in E. coli may be carried out by inserting the DNA fragment containing the desired cephalosporin acetylhydrolase structural gene into an expression vector (pKK223-3, pBS, pDR540, pPL-lambda, etc.) containing a suitable promoter (Lac, Tac, Trc, Trp, P L , etc.) functional in a host and Shine-Dalgarno (SD) sequence, or into an ATG vector (pKK233-2, etc.) which additionally contains the translational initiation codon ATG. Introduction of the expression plasmid into a suitable host (for example, such a strain as E. coli JM103, JM109, HB101 and C600) yields a microorganism efficiently expressing cephalosporin acetylhydrolase.
The expressed cephalosporin acetylhydrolase may be purified according to a conventional purification method, for example, by combining centrifugation, column chromatography and the like.
The present invention is further illustrated by the following Example, but not limited thereto.
EXAMPLE 1
1. Separation and purification of cephalosporin acetylhydrolase and determination of partial amino acid sequence
(1) Separation and purification of cephalosporin acetylhydrolase
A medium (20 L) composed of 2.5% glucose, 0.75% corn steep liquor, 1.0% amino acids mixture, 0.3% KH 2 PO 4 , and 0.8 ppm MnSO 4 .4H 2 O, pH 7.0 was charged into a 30 L volume of jar-fermentor. After sterilization, B. subtilis (FERM BP-2755) which had been precultured in a medium composed of 0.5% glucose, 0.75% corn steep liquor, 0.5% amino acids mixture, and 0.02% KH 2 PO 4 , pH 7.0, was poured into the medium so as to obtain 6% of inoculum size. After 48 hours of cultivation at 28° C., activated charcoal was added to the cultured fluid to 1%, and stirred for 2 hours. Subsequent filtration gave a crude enzyme solution as filtrate. To the crude enzyme solution, DEAE Sephadex A-50 (Pharmacia) was added to 0.7%, and the mixture was adjusted to pH 8.0 using 2N NaOH and then stirred for one hour. After filtration, DEAE Sephadex A-50, on which cephalosporin acetylhydrolase activity was adsorbed, was washed with 50 mM Tris-HCl buffer (pH 8.0)(4 L) containing 0.1M NaCl, and the activity was then eluted with the same buffer containing 0.4M NaCl. After concentration and desalting by an ultrafiltration apparatus (Tosoh), the activity was adsorbed onto a column filled with DEAE Sepharose CL-6B (Pharmacia) which had been previously equilibrated with the same buffer. The column was washed with the same buffer and subsequently that containing 0.15M NaCl, and the activity was then eluted with the same buffer containing 0.2M NaCl. After concentration and desalting by ultrafiltration, purification with high performance liquid chromatography (hereafter referred to as HPLC) was performed. DEAE Toyopearlpak 650M (Tosoh) was used as the column. The activity was eluted by concentration gradient elution method where salt concentration was sequentially raised. Thus, starting with the same buffer containing 0.15M NaCl, the concentration of NaCl was sequentially raised to 0.5M. Fractions containing the eluted activity were collected, concentrated by ultrafiltration, and then purified by HPLC using a molecular sieve column. TSK-G3000 (Tosoh) was used as the column and 0.2M phosphate buffer (pH 7.0) was used as the mobile phase. The eluted active fractions were collected, concentrated by ultrafiltration, and then purified by HPLC using a reversed phase column. Microbondapak C 18 (Waters) was used as the column and the elution was carried out by concentration gradient elution method where acetonitrile concentration was sequentially raised. Thus, starting with aqueous system containing 0.1% trifluoroacetic acid, the acetonitrile concentration was raised to the final concentration of 98%. The fractions containing the eluted cephalosporin acetylhydrolase were concentrated under reduced pressure at 50° C. and the residue was dissolved in 0.5M Tris-HCl buffer (pH 8.0) containing 6M guanidine hydrochloride. To the solution, EDTA (ethylenediaminetetraacetic acid) was added to obtain 2 mM of concentration, and 200-fold mole amount of 2-mercaptoethanol relative to cephalosporin acetylhydrolase was added to the solution, and the reduction was performed at 37° C. for 4 hours under the nitrogen atmosphere. Subsequently, 190-fold mole amount of sodium iodoacetate relative to cephalosporin acetylhydrolase was added to the solution and reacted at 37° C. for 10 minutes in the dark to perform reductive carboxymethylation. Then, the purification by HPLC using a reversed phase column was conducted again according to the above method. The resulting cephalosporin acetylhydrolase fractions were analyzed by SDS-polyacrylamide gel electrophoresis (SDS-PAGE) according to the procedure of Laemmli, Nature, 227, 680-685(1970). Only a single band was detected at a position of molecular weight of 35 kD, implying that purification was achieved homogeneously. In addition, the facts that the purified cephalosporin acetylhydrolase solubilized in 0.1M Tris-HCl buffer (pH 8.0) containing 7M urea was reactivated by 10-fold dilution with 0.1M phosphate buffer (pH 7.0), and that the activity was eluted at a position of molecular weight of 280 kD by a molecular sieve column chromatography using the above-mentioned HPLC suggested that the cephalosporin acetylhydrolase in a natural form is the octamer consisting of homogeneous subunits.
On the other hand, the molecular weight determined using the procedure of Hedrick et al., Arch. Biochem. Biophys., 126, 155-164(1968) was about 150 kD and the activity was detected at the relevant position, which suggested that the tetramer is also active.
Amino acid terminal analysis of the purified cephalosporin acetylhydrolase by Edman degradation and hydrazine hydrolysis identified the amino terminus to be methionine and the carboxy terminus to be glycine.
(2) Determination of partial amino acid sequence of cephalosporin acetylhydrolase
The purified cephalosporin acetylhydrolase (1 mg) was solubilized in 0.1M Tris-HCl buffer (pH 8.8)(1.0 ml) containing 2M urea, and lysylendopeptidase (0.01 mg) was added to the solution and the mixture was reacted at 37° C. for 4 hours. The reaction mixture was then separated by HPLC. Microbondapak C 18 (Waters) was used as the column and the elution was carried out by concentration gradient elution method sequentially raising acetonitrile concentration. Thus, starting with aqueous system containing 0.1% trifluoroacetic acid, the acetonitrile concentration was raised to final concentration of 98%. The detection was carried out at 214 nm. Of the separated peaks, distinctive fractions having a long retention time were collected and again purified using the same reversed phase column, and the amino acid sequence of the peptide was analyzed using a gas phase automated amino acid sequencer (Applied Biosystems) to determine the amino acid sequence from amino terminus to 34th amino acid of the peptide fragment, as shown in FIG. 3.
2. Synthesis of DNA probes and labeling the 5'-termini
The sequence (SEQ. ID. No. 4) underlined in the amino acid sequence in FIG. 3 obtained by the above step 1 was selected and a pool of oligonucleotides corresponding to all of the genetically possible DNA base sequences (SEQ. ID. NOS. 5 and 6) deduced from this amino acid sequence were synthesized. As shown in FIG. 4, 4 groups of the oligonucleotides, which were designated as DNA probes CAH-RM1 (SEQ. ID. NO. 7), CAH-RM2 (SEQ. ID. NO. 8) CAH-RM3 (SEQ. ID. NO. 9) and CAH-RM4 (SEQ. ID. NO. 10), were synthesized. Synthesis of the oligonucleotides was conducted using automated DNA synthesizer ZEON-GENET A-II (Nihon Zeon).
5'-Termini of the resulting DNA probes were labeled using T4 polynucleotide kinase and [γ- 32 P]ATP according to the procedure of Wallace et al., Nucleic Acids Res., 6, 3543-3557(1979).
3. Extraction and purification of chromosomal DNA from B. subtilis and Southern hybridization
Cells of B. subtilis (FERM BP-2755) were treated with lysozyme followed by sodium N-lauroylsarcosinate, and the chromosomal DNA was extracted and purified from the resulting lysate by CsCl-ethidium bromide equilibrium density gradient ultracentrifugation according to the procedure of Harris-Warrick et al., Proc. Natl. Acad. Sci. U.S.A,, 72, 2207-2211(1975). The DNA (1 μg) was digested with various restriction enzymes (each about 10 units) under a suitable condition, and the reactants were electrophoresed on 0.8% agarose gel. After the analysis of restriction enzyme cleavage pattern, the gel was subjected to Southern hybridization according to the procedure of Southern et al., J. Mol. Biol., 98, 503-517(1975). The gel was treated with 1.5M NaCl solution containing 0.5N NaOH at room temperature for 1 hour to denature DNA, and then neutralized in 1M Tris-HCl buffer (pH 7.0) containing 1.5M NaCl at room temperature for 1 hour. A nitrocellulose membrane was then placed on the gel to transfer the DNA from the gel to the membrane. Using the DNA-transferred nitrocellulose membrane, the hybridization with the labeled probes was carried out. The hybridization was conducted at 38° C. overnight using 4-fold concentration of SSC (1×SSC: 0.15M NaCl, 0.015M sodium citrate, pH 7.0), 10-fold concentration of Denhardt's solution (1×Denhardt's solution: 0.02% Ficoll, 0.02% polyvinylpyrrolidone, 0.02% bovine serum albumin), and about 1×10 6 cpm/ml of the labelled probes. The membrane was washed several times with 4-fold concentration of SSC at room temperature, and then subjected to autoradiography. In addition, the washing temperature of the membrane was raised stepwise, and the membrane was provided for autoradiography repeatedly in each case. It was found that several DNA bands show positive signals even at the high washing temperatures such as 48° C. and 53° C., and that the sizes of the hybridizing bands differ each other depending on the restriction enzymes employed. Out of the DNA fragments showing positive signals 2.5-3 kb DraI digested and 4-4.5 kb HindIII digested fragments were preferable for gene cloning because their sizes were larger than the desired gene.
4. Cloning of cephalosporin acetylhydrolase gene
(1) Construction of gene library
To the chromosomal DNA (12 μg) from B. subtilis extracted and purified in the above step 3, restriction enzyme DraI (about 120 units) was added and incubated at 37° C. for 90 minutes. The reactant was then extracted with equal volume of phenol, and ethanol was added to the resulting aqueous layer to precipitate DNA. The resulting DNA was dissolved in TE buffer [10 mM Tris-HCl, 1 mM EDTA, pH 8.0](60 μl), the resultant solution was electrophoresed on 0.8% agarose gel, and a region of the gel corresponding to a size of 2-4 kb was excised. DNA fragments were eluted and recovered from the gel using a commercially available kit (Bio 101, GENECLEAN), and dissolved in TE buffer (30 μl).
On the other hand, pUC13 was used as a vector for constructing a gene library. pUC13 (10 μg) was mixed with restriction enzyme SmaI (about 100 units), incubated at 37° C. for 140 minutes, and then treated at 65° C. for 10 minutes. Alkaline phosphatase (BAP)(about 20 units) was added to the mixture and further reacted at 65° C. for 80 minutes. Phenol extraction followed by ethanol precipitation of DNA was carried out according to the above procedure and the DNA was finally dissolved in TE buffer (50 μl).
The solution containing the DraI digested fragments of B. subtilis chromosome (7.5 μl) and the solution containing the SmaI-BAP treated fragments of vector pUC13 (2.5 μl) were combined, and the mixture was incubated with T4 DNA ligase at 6° C. for 20 hours to ligate the fragments, forming a recombinant DNA. The resultant recombinant DNA was used to transform E. coli HB101 strain according to the procedure of Hanahan et al., J. Mol. BioS., .166, 557-580(1983). Subsequently, colonies were allowed to form on a nitrocellulose membrane placed on L-broth [1% bacto-tryptone, 0.5% yeast extract, 0.5% NaCl (pH 7.3)]agar medium containing 40 μg/ml ampicillin. These colonies were designated as the gene library of B. subtilis.
(2) Selection of cephalosporin acetylhydrolasepositive clone by colony hybridization
The colonies formed on the nitrocellulose membrane in the above step (1) were replicated on another nitrocellulose membrane. The replica membrane was placed on L-broth agar medium containing 40 μg/ml ampicillin and incubated at 37° C. for 3 hours. Then, the membrane was transferred on L-broth agar medium containing 250 μg/ml chloramphenicol and incubated at 37° C. overnight. Colony hybridization was then carried out substantially according to the procedure of Grunstein et al., Proc. Natl. Acad. Sci. U.S.A., 72, 3961-3965(1975). Thus, the membrane was treated with 0.5N NaOH (for 10-15 minutes) to effect lysis of colonies and denaturation of DNA. Subsequently, the membrane was neutralized with 1M Tris-HCl buffer (pH 7.2) for 5-10 minutes and further treated with 1M Tris-HCl buffer (pH 8.0) containing 1.5M NaCl for 10-15 minutes. After the membrane was baked under reduced pressure at 80° C. for 2 hours to immobilize DNA to the membrane, the immobilized DNA was hybridized with the labeled probe CAH-RM2. The reaction was carried out in a solution containing 4-fold concentration of SSC, 10-fold concentration of Denhardt's solution and about 2×10 6 cpm/ml of the labelled probe at 38° C. for 16 hours. Subsequently, the membrane was washed 3-4 times with 4-fold concentration of SSC at room temperature, then washed at 38° C. for 2 minutes, and subjected to autoradiography (exposure condition: -80° C., 3 hours). In order to examine the correlation between washing temperature and intensity of signal on the autoradiography, the washing temperature was further raised stepwise and the autoradiography was conducted in each case. The washing was carried out at 43° C., 48° C. and 53° C. each for 2 minutes.
As a result, it was found that 3 of about 30,000 colonies showed positive signals even at the high washing temperature. These colonies were liquid-cultured in L-broth (5ml) containing 40 μg/ml ampicillin at 37° C. overnight and recombinant plasmids were prepared [procedure of Birnboim et al., Nucleic Acids Res., 7, 1513-1523(1979)]. These plasmids were cleaved and fragmented with a restriction enzyme such as EcoRI, HindIII and PvuII for which the vector DNA (pUC13) has a cleavage site. Then, electrophoresis was carried out on agarose gel and Southern hybridization with the labeled probe was carried out. As a result, it was found that two of three recombinant plasmids contained a restriction enzyme digested fragment clearly hybridizing with the DNA probe. The size of the hybridizing fragments differed between the two positive plasmids, and therefore, the DNA fragments inserted into the vector DNA appeared different each other. Accordingly, respective recombinant plasmids were distinguished and designated as pCAH01 and pCAH02.
5. Identification of positive clone and determination of base sequence
(1) Identification of positive clone
In the course of attempts to prepare restriction enzyme cleavage maps for the recombinant plasmids pCAH01 and pCAH02 by cleaving them with various restriction enzymes, it was found that plasmid pCAH01 has two different DraI digested fragments and plasmid pCAH02 has at least three different DraI digested fragments inserted into the SmaI site on the vector DNA, and that the DNA probe hybridizes with one of these DraI fragments. Consequently, the recombinant plasmid pCAH01 was used in the subsequent procedures. The restriction enzyme cleavage map of plasmid pCAH01 was depicted in FIG. 5 together with the position at where the DNA probe hybridized.
Since plasmid pCAH01 contains two exogenous DraI fragments derived from the chromosomal DNA of B. subtilis (1.8 kb and 2.5 kb) and only the 2.5 kb fragment hybridizes with the DNA probe, the 1.8 kb DraI fragment was deleted from the plasmid. DraI-PstI fragment (2.6 kb) containing the 2.5 kb fragment was removed from plasmid pCAH01 and inserted into SmaI-PstI site of vector plasmid pUC13 to obtain a miniaturized recombinant plasmid pCAH03 (5.3 kb). The restriction enzyme cleavage map of the recombinant plasmid pCAH03 was shown in FIG. 6.
(2) Determination of base sequence
From the recombinant plasmid pCAH03, 0.24 kb EcoRI-HindIII fragment to which the DNA probe had hybridized was removed and its DNA base sequence was determined according to the procedure of Sanger et al., Proc. Natl. Acad. Sci. U.S.A., 74, 5463-5467(1977). As a result, a base sequence corresponding to the partial amino acid sequence cephalosporin acetylhydrolase obtained in the above step 1 was found in the EcoRI-HindIII fragment, revealing that the fragment contains a part of cephalosporin acetylhydrolase gene. By subsequent determination of the base sequence between DraI and HindIII sites (0.38 kb) as well as between ECORI and EcoRI sites (1.45 kb) on the basis of the restriction enzyme cleavage map of plasmid pCAH03, the base sequence of about 2 kb between DraI and EcoRI sites was revealed as shown in FIG. 7. This proved the presence of a base sequence encoding a protein composed of 318 amino acid residues containing methionine encoded by translational initiation codon ATG. In addition, the putative protein encoded by the above base sequence showed a good coincidence with the cephalosporin acetylhydrolase with respect to their molecular weight, amino-terminal and carboxy-terminal amino acids, as well as amino acid composition of lysylendopeptidase digested fragments and therefore, it was believed that this protein must be cephalosporin acetylhydrolase- Thus, it was proved that the structural gene of cephalosporin acetylhydrolase was entirely contained in the B. subtilis-derived DNA fragment on plasmid pCAH03.
6. Construction of expression plasmid
The cloned B. subtilis-derived DNA fragment on plasmid pCAH03 contains a region other than the cephalosporin acetylhydrolase gene, and therefore, the region considered to be irrelevant to phenotypic expression of the gene was deleted according to the process depicted in FIG. 8.
In order to drive high expression of a heterologous gene in E. coli, it is generally effective to construct an expression plasmid in which a desired structural gene is connected immediately after a sequence consisting of a promoter having a high expression efficiency, SD sequence and translational initiation codon ATG. Thus, in order to produce a large amount of cephalosporin acetylhydrolase in E. coli, an expression plasmid was constructed using a vector containing a promoter, SD sequence and ATG, according to the process depicted in FIG. 9. In the process of the construction, the cephalosporin acetylhydrolase structural gene can be prepared as follows. A region entirely containing the desired gene is cloned into a vector of M13 mp series to obtain a single-stranded DNA. According to a so-called primer extension method, using as a primer an oligonucleotide specifying several amino acids excluding methionine on the amino terminal sequence of cephalosporin acetylhydrolase, a DNA fragment in which only the cephalosporin acetylhydrolase structural gene moiety is double-stranded is obtained.
FIG. 10 shows the process for constructing a modified expression plasmid which shows increased copy number as compared with the expression plasmid prepared by the process in FIG. 9, and which bears tetracycline (Tc r ) resistance marker instead of ampicillin (Ap r ) resistance A marker.
The followings are the more detailed description of each step.
(1) Construction of miniaturized plasmid
In order to shorten a downstream region of the cephalosporin acetylhydrolase structural gene (abbreviated as CAH in FIG. 8), plasmid pCAH03 was cleaved with EcoRV and BanHI, about 4.1 kb DNA fragment obtained was purified, and then the 3' recessed termini created by BamHI digestion were filled using DNA polymerase Klenow fragment (FIG. 8). After further purification, ligation was carried out using T4 DNA ligase to construct miniaturized plasmid pCAH10 containing the cephalosporin acetylhydrolase gene.
(2) Preparation of single-stranded DNA for constructing expression plasmid
The miniaturized plasmid pCAH10 prepared in the above step (1) was cleaved with SacI and SalI and about 1.5 kb fragment obtained was purified and recovered as a SacI-SalI fragment. On the other hand, double-stranded phage M13 mpll DNA was cleaved with SacI and SalI. Then, to the latter was added the above SacI-SalI fragment and ligated with T4 DNA ligase to construct double-stranded phage M13-CAH DNA which contained the complete cephalosporin acetylhydrolase gene. Subsequently, its single-stranded DNA was prepared according to the procedure of Messing, Methods in Enzymology, 101, 20-78(1983).
(3) Primer extension
A region containing cephalosporin acetylhydrolase structural gene was prepared by eliminating a protein-noncoding region derived from B. subtilis, which locates upstream the initiation site (ATG) of cephalosporin acetylhydrolase, in substantial accordance with the procedure of Goeddel et al., Nucleic Acids Res., 8, 4057-4074(1980). An oligonucleotide having a base sequence corresponding to the 2nd amino acid glutamine to the 7th amino acid proline from amino terminus of cephalosporin acetylhydrolase was synthesized as a primer to be used in primer extension and designated as CAH-P1. The primer CAH-P1 (3 pmole) was then added to the single-stranded DNA (7.5 μg) of phage M13-CAH prepared in the above step (2), and the mixture was heated to 60° C. for 20 minutes and then allowed to stand to room temperature. Subsequently, to the mixture were added dATP, dCTP, dGTP and dTTP (each 0.25 mM) as well as DNA polymerase Klenow fragment (2 units), and the primer extension was carried out at 37° C. for 2 hours in a reaction mix (20 μl) of 7 mM Tris-HCl buffer (pH 7.5), 7 mM MgCl 2 , 0.1 mM EDTA, and 20 mM NaCl. After the reaction, phenol extraction and ethanol precipitation were conducted. The DNA was dissolved in a small amount of distilled water, to which S1 nuclease (4 units) was added and incubated at 37° C. for 30 minutes in a reaction mix (40 μl) of 30 mM sodium acetate (pH 4.6), 100 mM NaCl and 1 mM ZnSO 4 to digest remaining single-stranded DNA. The solution containing the double-stranded DNA fragment obtained was subjected to phenol extraction followed by ethanol precipitation, and the DNA was treated with DNA polymerase Klenow fragment according to the above procedure for repair reaction of the termini.
(4) Construction of expression plasmid
The vector pKK233-2 (ampicillin resistance) used in the present example for constructing an expression plasmid is commercially available from Pharmacia. The vector is a member of ATG vectors, which contains Trc promoter and can be cleaved immediately after initiation codon ATG by digestion with restriction enzyme NcoI and filling of the 3' recessed termini. As depicted in FIG. 9, the DNA fragment obtained in the above step (3), which contains the cephalosporin acetylhydrolase structural gene, was cleaved with PstI, and 1.27 kb DNA fragment was separated and purified. On the other hand, pKK233-2 containing Trc promoter was cleaved with NcoI and treated with DNA polymerase Klenow fragment. The resulting fragment was then cleaved with PstI to obtain about 4.6 kb DNA fragment. Subsequently, the above two fragments were mixed and ligated each other with T4 DNA ligase, the resultant mixture was used to transform E. coli JM103 strain, and colonies formed on L-broth agar medium containing 40 μg/ml ampicillin were selected. These colonies were liquid-cultured in L-broth overnight, cells were collected, plasmid DNA was extracted from the cells, and the base sequence near the junction of the ATG vector and the fragment containing cephalosporin acetylhydrolase gene was determined. As a result, an expression plasmid, in which the structural gene of cephalosporin acetylhydrolase excluding amino-terminal methionine had been inserted immediately after the ATG codon, was obtained and designated as pCAH21. Also, E. coli harboring the expression plasmid was designated as E. coli JM103/pCAH 21.
The replication system of the expression plasmid pCAH21 is derived from pBR322. Accordingly, in order to enhance the copy number of this plasmid to raise the expression level in E. coli, its replication region (ori) was changed to that derived from pAT153. Simultaneously, its drug resistance marker was changed from ampicillin resistance (Ap r ) to tetracycline resistance (Tc r ). A process for modifying the plasmid was depicted in FIG. 10. Plasmid pCAH21 was first cleaved with BamHI and treated with DNA polymerase Klenow fragment. Then, the resulting fragment was cleaved with ScaI to obtain about 2.4 kb DNA fragment containing Trc promoter, cephalosporin acetylhydrolase gene and T 1 T 2 terminator of 5S ribosomal RNA (5SrrnBT 1 T 2 ). Commercially available plasmid pAT153 was used as the vector plasmid. Plasmid pAT153 was cleaved with EcoRI, treated with DNA polymerase Klenow fragment, and then cleaved with DraI. Furthermore, in order to prevent selfligation of the vector, alkaline phosphatase treatment was conducted, and about 2.5 kb DNA fragment containing the replication region and tetracycline resistance gene from pAT153 was prepared. Then, the above two DNA fragments were mixed and ligated with T4 DNA ligase, the resultant mixture was used to transform E. coli JM103 strain, and colonies formed on L-broth agar medium containing 20 μg/ml tetracycline were selected. After these colonies were cultured in L-broth overnight, cells were collected, and the plasmid DNA was extracted from the cells and analyzed by restriction enzyme cleavage. As a result, two recombinant plasmids which differ in orientation of ligation were obtained. One plasmid in which the orientation of cephalosporin acetylhydrolase gene was identical with that of tetracycline resistance gene was designated as pCAH211 and another plasmid in which these genes were reversely inserted was designated as pCAH212. Also, E. coli strains harboring these recombinant expression plasmids were designated as E. coli JM103/pCAH211 and E. coli JM103/pCAH212, respectively.
7. Expression of cephalosporin acetylhydrolase gene in E. coli
(1) Expression of cephalosporin acetylhydrolase gene
E. coli JM103/pCAH211 or E. coli JM103/pCAH212 was inoculated on 2-fold concentration of L-broth (50 ml) containing 20 μg/ml tetracycline (in 0.5 L volume flask) and cultured at 37° C. for 24 hours with shaking. An aliquot (0.5 ml) of the cultured fluid was centrifuged to collect cells. The cells were suspended in 0.1M phosphate buffer (pH 7.0)(0.5ml) and disrupted with ultrasonicator. The supernatant obtained by centrifuging the solution was used as a sample solution containing the desired enzyme. On the other hand, the supernatant obtained by centrifuging the cultured fluid of B. subtilis (FERM BP-2755) obtained in the above step 1 was used as an enzyme solution for comparison. Cephalosporin acetylhydrolase acts not only on cephalosporin C and 7-ACA but also on p-nitrophenyl acetate (hereafter abbreviated to pNPA) to form colored substance, p-nitrophenol (hereafter abbreviated to pNP). The pNP is detectable spectrophotometrically, and therefore, the procedure in which pNPA is used as a substrate was adopted as a simple determination method for cephalosporin acetylhydrolase activity. Reaction was carried out in a mixture (3ml) containing 0.02% pNPA, 0.1M phosphate buffer (pH 6.8) and the above-mentioned enzyme solution at 30° C., and the enzyme activity was determined by measuring absorbance at 400nm using a spectrophotometer. The amount of the enzyme producing 1 μmole of pNP per minute under the condition of pH 6.8 and 30° C. of temperature was defined as one unit(U). As a result, it was found that the enzyme activities per cultured fluid of E. coli JM103/pCAH211 and E. coli JM103/pCAH212 were 9.9U/ml and 12.4U/ml, respectively. On the other hand, the enzyme activity of B. subtilis was 0.36 U/ml.
Furthermore, a plasmid was constructed in which Trc promoter and SD-ATG sequence of expression plasmid pCAH211 were replaced by Trp promoter and SD-ATG sequence derived from E. coli tryptophan operon. After the plasmid was introduced into E. coli JM109 by transformation, the resulting transformant was cultured in a similar manner as described above, and 75.5 U/ml of enzyme activity per cultured fluid was obtained.
The amount of cephalosporin acetylhydrolase produced can be increased by growing E. coli harboring these expression plasmids in a suitable medium under a suitable culture condition using a large scale culture apparatus such as jar-fermentor.
(2) Deacetylation of cephalosporin C and 7-ACA
Deacetylation by an enzyme solution from E. coli JM103/pCAH212 was carried out using cephalosporin C or7-ACA as a substrate. The reaction was conducted at 37° C. for 40 minutes after adding the enzyme solution (0.2ml) to 0.1M phosphate buffer (pH 7.0)(1.0ml) containing 10 mM of the substrate, and terminated by addition of 0.2M acetate buffer (pH 4.0)(1.2ml). The resulting solution was subjected to HPLC, and deacetylcephalosporin C or deacetyl-7-ACA was measured. Cosmosil 5C 8 (Nacalai tesque) was used as a column and the elution was carried out by concentration gradient elution method where methanol concentration was sequentially raised. Thus, using a solution containing 20 mM NaH 2 PO 4 , and 5 mM tetra-n-butylammonium hydroxide (TBAH), the methanol concentration was raised to 20%. Detection of the deacetylated products was carried out at 254nm. Activity of cephalosporin acetylhydrolase was defined as follows. Thus, the amount of the enzyme producing 1 μmole of the product per minute under the condition of pH 7.0 and 37° C. of temperature is defined as one unit(U). As a result, it was found that the activity per cultured fluid of the enzyme solution of [E. coli JM103/pCAH212 was 7.4 U/ml for both cephalosporin C and 7-ACA.
(3) Structure of recombinant cephalosporin acetylhydrolase
Determination of molecular weights of the active form and subunit of cephalosporin acetylhydrolase produced in E. coli gave the same results as obtained in the above step 1, suggesting that the recombinant cephalosporin acetylhydrolase also exists in an octamer form similar to the natural form.
Furthermore, the recombinant cephalosporin acetylhydrolase was purified by HPLC using a reversed phase column. Terminal analysis by Echnan degradation and hydrazine hydrolysis revealed that the amino and carboxy termini of the enzyme were methionine and glycine, respectively, and identical with those of natural form. In addition, determination of the amino terminal sequence using an automated amino acid sequencer revealed that the amino acid sequence to 25th amino acid was entirely identical with that deduced from the structural gene (FIG. 2).
Effects of the Invention
As described in the above Example in detail, the present inventors have confirmed that a great efficient production of cephalosporin acetylhydrolase is possible by cloning a gene encoding cephalosporin acetylhydrolase produced by B. subtilis and constructing a recombinant plasmid containing the gene by the use of a vector expressible in E. coli. This provides a premise for extensive application of this enzyme. In addition, the DNA fragment containing the cloned cephalosporin acetylhydrolase gene provides an extremely powerful means of advantageously utilizing the function of cephalosporin acetylhydrolase.
__________________________________________________________________________SEQUENCE LISTING(1) GENERAL INFORMATION:(iii) NUMBER OF SEQUENCES: 11(2) INFORMATION FOR SEQ ID NO:1:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 317 amino acids(B) TYPE: amino acid(D) TOPOLOGY: linear(ii) MOLECULE TYPE: peptide(xi) SEQUENCE DESCRIPTION: SEQ ID NO:1:GlnLeuPheAspLeuProL euAspGlnLeuGlnThrTyrLysProGlu151015LysThrAlaProLysAspPheSerGluPheTrpLysLeuSerLeuGlu2025 30GluLeuAlaLysValGlnAlaGluProAspLeuGlnProValAspTyr354045ProAlaAspGlyValLysValTyrArgLeuThrTyrLysSerPhe Gly505560AsnAlaArgIleThrGlyTrpTyrAlaValProAspLysGlnGlyPro65707580HisProAlaIle ValLysTyrHisGlyTyrAsnAlaSerTyrAspGly859095GluIleHisGluMetValAsnTrpAlaLeuHisGlyTyrAlaAlaPhe100 105110GlyMetLeuValArgGlyGlnGlnSerSerGluAspThrSerIleSer115120125LeuHisGlyHisAlaLeuGlyTrpMetThrLysGly IleLeuAspLys130135140AspThrTyrTyrTyrArgGlyValTyrLeuAspAlaValArgAlaLeu145150155160G luValIleSerSerPheAspGluValAspGluThrArgIleGlyVal165170175ThrGlyGlySerGlnGlyGlyGlyLeuThrIleAlaAlaAlaAlaLeu 180185190SerAspIleProLysAlaAlaValAlaAspTyrProTyrLeuSerAsn195200205PheGluArgAlaIleAspValAla LeuGluGlnProTyrLeuGluIle210215220AsnSerPhePheArgArgAsnGlySerProGluThrGluValGlnAla225230235 240MetLysThrLeuSerTyrPheAspIleMetAsnLeuAlaAspArgVal245250255LysValProValLeuMetSerIleGlyLeuIleAspLysValThr Pro260265270ProSerThrValPheAlaAlaTyrAsnHisLeuGluThrGluLysGlu275280285LeuLysValTyrA rgTyrPheGlyHisGluTyrIleProAlaPheGln290295300ThrGluLysLeuAlaPhePheLysGlnHisLeuLysGly305310315(2 ) INFORMATION FOR SEQ ID NO:2:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 957 base pairs(B) TYPE: nucleic acid(C) STRANDEDNESS: double(D) TOPOLOGY: linear(ii) MOLECULE TYPE: genomic DNA(xi) SEQUENCE DESCRIPTION: SEQ ID NO:2:ATGCAACTATTCGATCTGCCGCTCGACCAATTGCAAACATATAAGCCT48MetGln LeuPheAspLeuProLeuAspGlnLeuGlnThrTyrLysPro151015GAAAAAACAGCACCGAAAGATTTTTCTGAGTTTTGGAAATTGTCTTTG96GluLysThr AlaProLysAspPheSerGluPheTrpLysLeuSerLeu202530GAGGAACTTGCAAAAGTCCAAGCAGAACCTGATCTACAGCCGGTTGAC144GluGluLeuAlaLys ValGlnAlaGluProAspLeuGlnProValAsp354045TATCCTGCTGACGGAGTAAAAGTGTACCGTCTCACATATAAAAGCTTC192TyrProAlaAspGlyValLysVal TyrArgLeuThrTyrLysSerPhe505560GGAAACGCCCGCATTACCGGATGGTACGCGGTGCCTGACAAGCAAGGC240GlyAsnAlaArgIleThrGlyTrpTyrAlaValPro AspLysGlnGly65707580CCGCATCCGGCGATCGTGAAATATCATGGCTACAATGCAAGCTATGAT288ProHisProAlaIleValLysTyrHisGlyTyrAsn AlaSerTyrAsp859095GGTGAGATTCATGAAATGGTAAACTGGGCACTCCATGGCTACGCCGCA336GlyGluIleHisGluMetValAsnTrpAlaLeuHisGly TyrAlaAla100105110TTCGGCATGCTTGTCCGCGGCCAGCAGAGCAGCGAGGATACGAGTATT384PheGlyMetLeuValArgGlyGlnGlnSerSerGluAspThrSer Ile115120125TCACTGCACGGTCATGCTTTGGGCTGGATGACGAAAGGAATTCTTGAT432SerLeuHisGlyHisAlaLeuGlyTrpMetThrLysGlyIleLeuAsp1 30135140AAAGATACATACTATTACCGCGGTGTTTATTTGGACGCCGTCCGCGCG480LysAspThrTyrTyrTyrArgGlyValTyrLeuAspAlaValArgAla145 150155160CTTGAGGTCATCAGCAGCTTCGACGAGGTTGACGAAACAAGGATCGGT528LeuGluValIleSerSerPheAspGluValAspGluThrArgIleGly165 170175GTGACAGGAGGAAGCCAAGGCGGAGGTTTAACCATTGCCGCAGCAGCG576ValThrGlyGlySerGlnGlyGlyGlyLeuThrIleAlaAlaAlaAla180 185190CTGTCAGACATTCCAAAAGCCGCGGTTGCCGATTATCCTTATTTAAGC624LeuSerAspIleProLysAlaAlaValAlaAspTyrProTyrLeuSer1952 00205AACTTCGAACGGGCCATTGATGTGGCGCTTGAACAGCCGTACCTTGAA672AsnPheGluArgAlaIleAspValAlaLeuGluGlnProTyrLeuGlu210215 220ATCAATTCCTTCTTCAGAAGAAATGGCAGCCCGGAAACAGAAGTGCAG720IleAsnSerPhePheArgArgAsnGlySerProGluThrGluValGln225230235 240GCGATGAAGACACTTTCATATTTCGATATTATGAATCTCGCTGACCGA768AlaMetLysThrLeuSerTyrPheAspIleMetAsnLeuAlaAspArg245250 255GTGAAGGTGCCTGTCCTGATGTCAATCGGCCTGATTGACAAGGTCACG816ValLysValProValLeuMetSerIleGlyLeuIleAspLysValThr260265270 CCGCCGTCCACCGTGTTTGCCGCCTACAATCATTTGGAAACAGAGAAA864ProProSerThrValPheAlaAlaTyrAsnHisLeuGluThrGluLys275280285GAGCTGAA GGTGTACCGCTACTTCGGACATGAGTATATCCCTGCTTTT912GluLeuLysValTyrArgTyrPheGlyHisGluTyrIleProAlaPhe290295300CAAACGGAAAAACTTGCTT TCTTTAAGCAGCATCTTAAAGGCTGA957GlnThrGluLysLeuAlaPhePheLysGlnHisLeuLysGly305310315(2) INFORMATION FOR SEQ ID NO:3:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 34 amino acids (B) TYPE: amino acid(D) TOPOLOGY: linear(ii) MOLECULE TYPE: peptide(xi) SEQUENCE DESCRIPTION: SEQ ID NO:3:TyrHisGlyTyrAsnAlaSerTyrAspGlyGluIleHisGluMetVal151015AsnTrpAlaLeuH isGlyTyrAlaAlaPheGlyMetLeuValXaaGly202530GlnGln(2) INFORMATION FOR SEQ ID NO:4:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 6 amino acids(B) TYPE: amino acid(D) TOPOLOGY: linear(i i) MOLECULE TYPE: peptide(xi) SEQUENCE DESCRIPTION: SEQ ID NO:4:GluMetValAsnTrpAla15(2) INFORMATION FOR SEQ ID NO:5:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 17 base pairs(B) TYPE: nucleic acid(C) STRANDEDNESS: double(D) TOPOLOGY: linear(ii) MOLECULE TYPE: genomic DNA(xi) SEQUENCE DESCRIPTION: SEQ ID NO:5:G ARATGGTNAAYTGGGC17(2) INFORMATION FOR SEQ ID NO:6:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 17 base pairs(B) TYPE: nucleic acid(C) STRANDEDNESS: double(D) TOPOLOGY: linear(ii) MOLECULE TYPE: genomic DNA(xi) SEQUENCE DESCRIPTION: SEQ ID NO:6:GCCCARTTNACCATYTC17(2) INFORMATION FOR SEQ ID NO:7:(i) SEQUENCE CHARACTERISTICS: (A) LENGTH: 17 base pairs(B) TYPE: nucleic acid(C) STRANDEDNESS: single(D) TOPOLOGY: linear(ii) MOLECULE TYPE: other nucleic acid(A) DESCRIPTION: synthetic oligonucleotide probe(xi) SEQUENCE DESCRIPTION: SEQ ID NO:7:GCCCARTTAACCATYTC17(2) INFORMATION FOR SEQ ID NO:8:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 17 base pairs (B) TYPE: nucleic acid(C) STRANDEDNESS: single(D) TOPOLOGY: linear(ii) MOLECULE TYPE: other nucleic acid(A) DESCRIPTION: synthetic oligonucleotide probe(xi) SEQUENCE DESCRIPTION: SEQ ID NO:8:GCCCARTTTACCATYTC17(2) INFORMATION FOR SEQ ID NO:9:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 17 base pairs(B) TYPE: nucleic acid(C) STRANDEDNESS: single (D) TOPOLOGY: linear(ii) MOLECULE TYPE: other nucleic acid(A) DESCRIPTION: synthetic oligonucleotide probe(xi) SEQUENCE DESCRIPTION: SEQ ID NO:9:GCCCARTTGACCATYTC17(2) INFORMATION FOR SEQ ID NO:10:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 17 base pairs(B) TYPE: nucleic acid(C) STRANDEDNESS: single(D) TOPOLOGY: linear(ii) MOLECULE TYPE: other nucleic acid(A) DESCRIPTION: synthetic oligonucleotide probe(xi) SEQUENCE DESCRIPTION: SEQ ID NO:10:GCCCARTTCACCATYTC17(2) INFORMATION FOR SEQ ID NO:11:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 2046 base pairs(B) TYPE: nucleic acid(C) STRANDEDNESS: double(D) TOPOLOGY: linear(ii) MOLECULE TYPE: genomic DNA(xi) SEQUENCE DESCRIPTION: SEQ ID NO:11:AAAGAACCG CTATGTCAGTCTGACGGCCCAGGCCTTTATGGAACTAAGCCGGGAAAGTCT60TAAACAAACGTTTGATGAAGGCTGTCTGGGAAACAAAGATGAAAATATTTAGAAAACAAA120GACGAAACGTGGTAGTATAGGAATACAAACTAAATCTTATAAAACAAAGGGGAATAATCG 180GAAATGCAACTATTCGATCTGCCGCTCGACCAATTGCAAACATATAAG228MetGlnLeuPheAspLeuProLeuAspGlnLeuGlnThrTyrLys1510 15CCTGAAAAAACAGCACCGAAAGATTTTTCTGAGTTTTGGAAATTGTCT276ProGluLysThrAlaProLysAspPheSerGluPheTrpLysLeuSer2025 30TTGGAGGAACTTGCAAAAGTCCAAGCAGAACCTGATCTACAGCCGGTT324LeuGluGluLeuAlaLysValGlnAlaGluProAspLeuGlnProVal354045GA CTATCCTGCTGACGGAGTAAAAGTGTACCGTCTCACATATAAAAGC372AspTyrProAlaAspGlyValLysValTyrArgLeuThrTyrLysSer505560TTCGGAAACG CCCGCATTACCGGATGGTACGCGGTGCCTGACAAGCAA420PheGlyAsnAlaArgIleThrGlyTrpTyrAlaValProAspLysGln657075GGCCCGCATCCGGCGATCGTG AAATATCATGGCTACAATGCAAGCTAT468GlyProHisProAlaIleValLysTyrHisGlyTyrAsnAlaSerTyr80859095GATGGTGAGATTCATGAAATG GTAAACTGGGCACTCCATGGCTACGCC516AspGlyGluIleHisGluMetValAsnTrpAlaLeuHisGlyTyrAla100105110GCATTCGGCATGCTTGTCCGCG GCCAGCAGAGCAGCGAGGATACGAGT564AlaPheGlyMetLeuValArgGlyGlnGlnSerSerGluAspThrSer115120125ATTTCACTGCACGGTCATGCTTTGG GCTGGATGACGAAAGGAATTCTT612IleSerLeuHisGlyHisAlaLeuGlyTrpMetThrLysGlyIleLeu130135140GATAAAGATACATACTATTACCGCGGTGTTTAT TTGGACGCCGTCCGC660AspLysAspThrTyrTyrTyrArgGlyValTyrLeuAspAlaValArg145150155GCGCTTGAGGTCATCAGCAGCTTCGACGAGGTTGACGAAACAA GGATC708AlaLeuGluValIleSerSerPheAspGluValAspGluThrArgIle160165170175GGTGTGACAGGAGGAAGCCAAGGCGGAGGTTTAACCATTGCC GCAGCA756GlyValThrGlyGlySerGlnGlyGlyGlyLeuThrIleAlaAlaAla180185190GCGCTGTCAGACATTCCAAAAGCCGCGGTTGCCGATTATCCTT ATTTA804AlaLeuSerAspIleProLysAlaAlaValAlaAspTyrProTyrLeu195200205AGCAACTTCGAACGGGCCATTGATGTGGCGCTTGAACAGCCGTACCTT 852SerAsnPheGluArgAlaIleAspValAlaLeuGluGlnProTyrLeu210215220GAAATCAATTCCTTCTTCAGAAGAAATGGCAGCCCGGAAACAGAAGTG900Gl uIleAsnSerPhePheArgArgAsnGlySerProGluThrGluVal225230235CAGGCGATGAAGACACTTTCATATTTCGATATTATGAATCTCGCTGAC948GlnAlaMetLys ThrLeuSerTyrPheAspIleMetAsnLeuAlaAsp240245250255CGAGTGAAGGTGCCTGTCCTGATGTCAATCGGCCTGATTGACAAGGTC996ArgValLysVa lProValLeuMetSerIleGlyLeuIleAspLysVal260265270ACGCCGCCGTCCACCGTGTTTGCCGCCTACAATCATTTGGAAACAGAG1044ThrProProSer ThrValPheAlaAlaTyrAsnHisLeuGluThrGlu275280285AAAGAGCTGAAGGTGTACCGCTACTTCGGACATGAGTATATCCCTGCT1092LysGluLeuLysValTy rArgTyrPheGlyHisGluTyrIleProAla290295300TTTCAAACGGAAAAACTTGCTTTCTTTAAGCAGCATCTTAAAGGCTGA1140PheGlnThrGluLysLeuAlaPhe PheLysGlnHisLeuLysGly305310315TAAATGTGAAAAGCCGCCGCATATCATCAGGCGGTTTTTTTCTGCAAACTGCCGGAATGA1200GAACAGACTGGAGACGAATAGATATGAAACAAAGAATCATTAAT GAATTAAAACGGATCG1260AGCAGTCATACGGAGTCAAAATCGTGTATGCCGTCGAGTCAGGAAGCCGCGCATGGGGAT1320TTCCCTCGCAGGATAGTGATTACGACGTCCGCTTTATTTATGTGCCGAAAAAGGAGTGGT1380ACTTTTCAATTGAGCAGGAGCGTGATG TCATTGAGGAACCGATTCACGATTTGCTGGATA1440TCAGCGGCTGGGAGCTGAGAAAAACGCTTCGGCTTTTCAAAAAGTCAAACCCTCCGCTCC1500TCGAATGGCTGTCCTCAGACATTGTGTATTACGAAGCATTTACGACCGCAGAGCAGTTAA1560GAAAACTGCG CACGGAGGCATTTAAGCCTGAAGCAAGCGTGTATCACTATATCAATATGG1620CGAGAAGGAACGTCAAAGATTATCTACAAGGACAAGAGGTCAAAATTAAAAAGTACTTCT1680ACGTTCTTCGGCCTATTTTGGCTGCAATGGATTGAAAGCACGGAACCATACCGCCAATG G1740ACTTTACTGTTTTGATGAATGAACTTGTTGCTGAACCCGAGCTGAAGGCTGAAATGGAAA1800CCTTGCTTGAACGGAAAAGAAGAGGGGAAGAGATTGACCTCGAATCAAAGAACTGATGTA1860ATTCACCAATTCATTGAAACGGAAATCGAAAGAATCATGGA AGCACAAAAAGAACTGAAG1920GCAGAGAAAAAAGATATGACATCTGAATTGAACCGTTTACTTTTGAATACGGTTGAAGAA1980GTGTGGAAGGATGGAGGAAGCTGATGTTTTTTGTCGCTTCCTTTTCTCCTTTATTCGACA2040GAATTC 2046 | A cephalosporin acetylhydrolase gene, a recombinant DNA molecule prepared by introducing said gene into a vector used in an E. coli host-vector system, E. coli cells transfomed with said recombinant DNA molecule, a protein having the amino acid sequence encoded by said gene, an enzyme which is a multimer of said protein, and a process for preparing said protein or enzyme are provided, said cephalosporin acetylhydrolase being an enzyme useful for converting cephalosporins such as cephalosporin C and 7-ACA into deacetylated ones such as deacetylcephalosporin C and deacetyl 7-ACA which are useful as an intermediate for preparing a variety of derivatized cephalosporin antibiotics. | 2 |
BACKGROUND OF THE INVENTION
[0001] This application relates to an undercut rim used with a bladed rotor disk for a gas turbine engine section, wherein a plurality of rotor sections are held together by a tie shaft.
[0002] Gas turbine engines are known, and typically include a compressor section that compresses air to be delivered into a combustion section. Air is mixed with fuel in the combustion section and ignited. Products of this combustion pass downstream over turbine rotors, driving the turbine rotors to rotate.
[0003] Typically, the turbine rotors are arranged in several stages as are compressor rotors. It has typically been true that the rotor stages have been connected together by welded joints, bolted flanges, or other mechanical fasteners. This has required a good deal of additional weight and components.
[0004] More recently, a tie shaft arrangement has been proposed wherein the rotors all abut each other, and a tie shaft applies an axial force to hold them together and transmit torque, thus eliminating the need for weld joints, bolts, etc.
[0005] Some integrally bladed rotors have the abutment face in the proximity of the airfoil edge that will expose the airfoil to stresses generated by tie shaft preload and rotational forces.
SUMMARY OF THE INVENTION
[0006] An integrally bladed rotor is utilized in at least a stage of one of a compressor and turbine section. The rotors feature and inner hub and an outer rim that includes the platform the airflow path (platform). Airfoils extend radially outwardly from a platform, and there is an undercut in the rotor rim under the platform between the airfoil and the abutting face at a downstream edge of the airfoil.
[0007] These and other features of the present invention can be best understood from the following specification and drawings, the following of which is a brief description.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] FIG. 1 schematically shows a typical compressor section.
[0009] FIG. 2 shows a portion of the FIG. 1 section with an undercut.
[0010] FIG. 3 shows an enlarged portion of the FIG. 2 section.
[0011] FIG. 4 is a top view of an example rotor incorporated into the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0012] FIG. 1 shows a compressor rotor 32 that utilizes a tie shaft connection. As known, a tie shaft 30 joins together a compressor section 32 , comprising of a plurality of rotor stages 40 , 42 , and 44 . The sections 40 , 42 and 44 may all be “integrally bladed rotors,” or may have removable blades. As illustrated, rotor 44 has removable blades, as an example. Rotor stage 40 is an integrally bladed rotor, with a rotor hub that rotates about an axis of the shaft 30 , and which carries a plurality of secured rotor blades 50 .
[0013] As can be appreciated, an upstream end of the rotor 44 provides the stacking interface with a downstream end of the integrally bladed rotor 40 . Typically, these interfaces have been simply placed radially inward of the platform of the integrally bladed rotor, and abutting an end face of the neighboring rotor. As mentioned above, with such an arrangement, there has been a force or stress applied forcing the platform of the integrally bladed rotor radially outwardly.
[0014] As shown, a rear hub 37 biases the stages together. A left side a front hub 100 , shown schematically, provides the reaction for the rotors stack being compressed by the tie shaft 30 . In practice, there may be something closer to the rear hub 37 extending radially away from the tie shaft 30 at the left side in place of the schematically shown hub 100 . A nut 34 directs a force through the hub 37 into the several stages, holding them together. A force vector along the axis of a portion 101 of a section 102 , directs the force into the rotor stages.
[0015] As shown in FIGS. 2 and 3 , the axial component F is delivered from the downstream stage 44 into the integrally bladed rotor stage 40 . The integrally bladed rotor stage 40 has an upstream ear 52 fitting within a recess 53 on the next most upstream rotor section 42 . The rotor stage 44 has a pocket 72 having an outer ear 74 and an inner ear 70 . A bottom portion 68 of a platform 52 of the rim of the integrally bladed rotor 40 has a forward edge 66 abutting the face 72 . Thus, the force F is passed into the face 66 . A curved undercut 64 is cut away from the rim under the platform 52 , such that a trailing edge 62 of the airfoil 50 is not exposed to the force F. Instead, the undercut 64 limits the upper surface 69 of the rim at the area of the connecting surfaces 66 and 72 . This ensures there are no forces transmitted from the force F into the airfoil 50 , which is undesirable.
[0016] As can be appreciated from FIG. 4 , the rim of the rotor stage 40 receives a plurality of airfoils 50 with trailing edges 62 , which is separated from the ear 74 such that the abutting contact is radially inward of the lowermost end of the airfoil 50 .
[0017] With the disclosed embodiment, the forces are not transmitted into the airfoil, and the undercut ensures that the damage to the airfoil is limited or eliminated due to the force F. In addition, the stresses from the downstream rotor rim are also addressed with this arrangement.
[0018] Although an embodiment of this invention has been disclosed, a worker of ordinary skill in this art would recognize that certain modifications would come within the scope of this invention. For that reason, the following claims should be studied to determine the true scope and content of this invention. | An integrally bladed rotor is utilized in at least a stage of one of a compressor and turbine section. Airfoils extend radially outwardly from a platform, and there is an undercut inward from the platform at a downstream edge of the airfoil. | 5 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional of U.S. patent application Ser. No. 10/940,036, filed Sep. 13, 2004, which is a continuation-in-part of U.S. patent application Ser. No. 10/067,185, filed Feb. 1, 2002, now U.S. Pat. No. 6,808,917, which claims the benefit of U.S. Provisional Application No. 60/265,998, filed Feb. 2, 2001; the disclosures of which applications and patent are incorporated by reference as if fully set forth herein. The application also incorporates by reference the disclosure of U.S. Patent Application Publication No. US 2005-0096225 A1 as if fully set forth herein.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] The U.S. Government has a paid-up license in this invention and the right in limited circumstances to require the patent owner to license others on reasonable terms as provided for by the terms of Grant No. DMI-9901629 awarded by the National Science Foundation.
BACKGROUND OF THE INVENTION
[0003] This invention relates to a seed treated with a fungal/bacterial antagonist combination. In particular, the invention relates to a seed assembly comprising a fungal/bacterial antagonist combination for controlling plant pathogens.
[0004] Early and late season stalk and root rot are major causes of crop loss. A variety of plants are affected, including tomatoes, peppers, turf grass, soybeans, sunflower, wheat and corn. The pathogens that cause these symptoms include fungi of the genera Fusarium, Phythium, Phytophthora and Penicillium.
[0005] One approach to solving the problem of early season damping off of plants is treatment of seeds with fungicides, such as captan, metalaxyl and Maxim. Although these chemicals enhance seed germination and seedling stand by inhibiting the pathogenic ability of Phythium spp. (active in cool, wet soils), they have no activity against the pathogenic fungi that are responsible for late season root and stalk rot.
[0006] Fusarium and Penicillium are the pathogens responsible for late season root and stalk rot. These pathogens prefer the warm, dry conditions that occur late in the growing season. There is no chemical or biological fungicide available that addresses the problem of late season root and stalk rot in corn. Currently, the only way to deal with this problem is to periodically rotate to a non-susceptible crop to reduce pathogen numbers. Corn growers can also select hybrids that have better “standability,” but such hybrids usually have lower yields. Unfortunately, the corn varieties with the highest yields are usually those most susceptible to late season root and stalk rot.
[0007] Trichoderma is a genus of fungi that contains about 20 species. Synonyms for the genus name include Aleurisma and Sporoderma. Trichoderma virens , which is also called Gliocladium virens , is a member of the genus. The natural habitats of these fungi include soil and plant material. A member of the genus, Trichoderma harzianum KRL-AG2 (ATCC 20847) also known as strain T-22, is used as a biocontrol agent that is applied as a seed or soil treatment or on cuttings and transplants. Strains of the species, Trichoderma virens , have also been used for control of damping off diseases in plants. For example, Trichoderma ( Gliocladium ) virens Gl-21 is known and commercially available at a reasonable price, and is being marketed under the trademark SoilGuard® 12G (EPA Registration Number: 70051-3 and EPA Establishment Number: 067250-IL-001). It is manufactured by Thermo Trilogy Corporation of Columbia, Md. Other known and commercially available Trichoderma virens strains include those having the following ATCC accession numbers: 10043, 10044, 10045, 13213, 13362, 204067, 204443, 204444, 204445, 20903, 20904, 20906, 24290, 42955, 44327, 44734, 48179, 52045, 52199, 58676, 58677, 58678, 62399, 64271, 74180, 9645, MYA-297, MYA-298, MYA-649 and MYA-650.
[0008] Bacillus is a genus of rod-shaped, gram-positive, aerobic or (under some conditions) anaerobic bacteria. Bacillus species are widely found in soil and water and some have been used to control plant diseases, including root rot. Bacillus amyloliquefaciens is a spore-forming member of the genus. Bacillus amyloliquefaciens L.L. Campbell strain F (ATCC 23350) is the type strain for the species. Other known and commercially available Bacillus amyloliquefaciens strains include those having the following ATCC accession numbers: 23842, 23843, 23844, 23845, 31592, 49763, 53495 and BAA-390 (Int. J. Sys. Bacteriol. 37:69-71, 1987; J. Bacteriol. 94:1124-1130, 1967).
[0009] In the past, Bacillus amyloliquefaciens was also called Bacillus subtilis var. amyloliquefaciens by some investigators. A protease produced from Bacillus subtilis var. amyloliquefaciens is commonly used as a tenderized for raw meat products. According to the U.S. Environmental Protection Agency (EPA), Bacillus subtilis var. amyloliquefaciens strain FZB24 is a naturally-occurring microorganism and widespread in the environment. Bacillus subtilis var. amyloliquefaciens FZB24 (EPA Registration Number: 72098-5 and EPA Establishment Number: 73386-DEU-001) is known and commercially available at a reasonable price, being marketed under the trademark Taegro® by Earth Bioscience, Inc. of Fairfield, Conn.
[0010] Background art biocontrol products have comprised the bacterium Burkholderia cepacia , which is also known as Pseudomonas cepacia . This bacterium has been implicated as a human pathogen. Furthermore, it has little or no shelf life unless refrigerated at 4 degrees Centigrade at a minimum of 20 percent moisture.
[0011] The background art is characterized by U.S. Pat. Nos. 4,476,881; 4,489,161; 4,642,131; 4,668,512; 4,678,669; 4,713,342; 4,724,147; 4,748,021; 4,818,530; 4,828,600; 4,877,738; 4,915,944; 4,952,229; 5,047,239; 5,049,379; 5,071,462; 5,068,105; 5,084,272; 5,194,258; 5,238,690; 5,260,213; 5,266,316; 5,273,749; 5,300,127; 5,344,647; 5,401,655; 5,422,107; 5,455,028; 5,409,509; 5,552,138; 5,589,381; 5,614,188; 5,628,144; 5,632,987; 5,645,831; 5,665,354; 5,667,779; 5,695,982; 5,702,701; 5,753,222; 5,852,054; 5,869,042; 5,882,641; 5,882,915; 5,906,818; 5,916,029; 5,919,447; 5,922,603; 5,972,689; 5,974,734; 5,994,117; 5,998,196; 6,015,553; 6,017,525; 6,030,610; 6,033,659; 6,060,051; and 6,103,228.
[0012] No single reference and no combination of the references teach the invention disclosed herein. The background art does not teach combinations of microorganisms disclosed herein, combinations that provide a surprising consistency of performance in plant disease control.
BRIEF SUMMARY OF THE INVENTION
[0013] A purpose of the invention is to control the plant pathogens that cause early and late season root and stalk rot. Another purpose is to provide for season-long protection for plants from the pathogens that cause early and late season root and stalk rot. Another purpose is to provide consistent disease control for plants. Yet another purpose is to increase the yield of plants and plant seed production.
[0014] One advantage of the invention is that root and stalk rot can be controlled with a composition that is not toxic to humans. Another advantage of the invention is that root and stalk rot can be controlled more economically than with chemical fungicides. Yet another advantage of the invention is that it provides a biocontrol agent or bio-pesticide with extended shelf life. Thus, a seed can be treated with the biocontrol agent and stored for a period of months and still host a viable biocontrol agent that will colonize the root when the seed is placed in the ground, germinates and grows. Furthermore, the disclosed biocontrol agent is competitive with natural soil microbes that occur in the rhizosphere while providing pathogen protection for the plant. A further advantage of the invention is that the combination of a fungal/bacterial antagonist is more effective in controlling fungal pathogens in the plant rhizosphere than either a fungal antagonist or a bacterial antagonist alone. Thus, the invention provides an easy-to-use, effective means of controlling plant pathogens that have been only been controllable by rotation management. A further advantage of the invention is that its use produces more consistent results than the use of either a fungal antagonist or a bacterial antagonist alone, as shown by the Working Examples presented herein. In fact, use of the antagonist combinations disclosed herein is shown to be functional when use of its individual constituent antagonists is not.
[0015] The compositions disclosed herein may be integrated into Integrated Pest Management (IPM) programs, the inventive compositions may be used in combination with other management systems. As an alternative to synthetic agents, biocontrol agents (bio-pesticides) offer the advantage of containing naturally derived constituents that are safe to both humans and the environment. Specifically, bio-pesticides offer such advantages as being inherently less toxic than conventional pesticides, generally affecting only the target pest and closely related organisms, and are often effective in very small quantities. For these reasons, bio-pesticides often decompose quickly and, therefore, are ideal for use as a component of Integrated Pest Management (IPM) programs.
[0016] The applicant has shown through a variety of laboratory and field trials that Bacillus subtilis var. amyloliquefaciens TJ 1000 and Trichoderma virens G1-3 are compatible with one another and that they act synergistically to consistently produce increased yield in plants. These results were presented in the parent application referenced above.
[0017] Field trials were conducted as part of the applicant's continuing research effort that tested other known Bacillus subtilis var. amyloliquefaciens ( Bacillus amyloliquefaciens ) strains and other known Trichoderma virens isolates. The purpose of testing was to determine whether the surprising synergism between a Bacillus subtilis var. amyloliquefaciens bacterium and a Trichoderma virens fungus disclosed in the parent application would be present between other strains and isolates of the same genus and species.
[0018] This testing by the applicant did result in the discovery of a synergistic activity between other isolates and strains of Trichoderma virens and Bacillus subtilis var. amyloliquefaciens . These results are presented in the final three working examples at the end of this document. The results show that other isolates of Trichoderma virens and other strains of Bacillus subtilis var. amyloliquefaciens do have synergistic properties. The applicant's research has also confirmed that the combination of T. virens G1-3 and Bacillus subtilis var. amyloliquefaciens TJ 1000 is superior to combinations comprising any other tested strains, but that synergies among other combinations do exist. These synergies have led the applicant to the conclusion that his patent rights should include combinations of all Trichoderma virens isolates and all Bacillus subtilis var. amyloliquefaciens strains.
[0019] The invention is an inoculum, a seed coated with the inoculum, a plant protected with the inoculum, a method of producing the inoculum and a method of protecting a seed or a plant with the inoculum. A further embodiment of the inoculum comprises a combination of a fungus and a bacterium. Preferably, the fungus is a species of Trichoderma and the bacterium is a species of Bacillus , preferably a spore-forming strain of Bacillus . More preferably, the fungus is Trichoderma virens and the bacterium is Bacillus subtilis var. amyloliquefaciens , although other combinations are also envisioned. Even more preferably, the fungus is Trichoderma virens G1-3 (ATCC 58678) or Trichoderma virens Gl-21 (an isolate that is commercially available from Thermo Trilogy Corporation) and the bacterium is Bacillus subtilis var. amyloliquefaciens TJ1000 or 1BE (ATCC BAA-390) or Bacillus subtilis var. amyloliquefaciens FZB24 (a strain that is commercially available from Earth Biosciences, Inc.).
[0020] Further embodiments of the invention comprise combining of a Trichoderma virens fungus and a Bacillus amyloliquefaciens bacterium and placing this combination on a seed or in the vicinity of the seed or seedling. A person having ordinary skill in the art would understand that the names Trichoderma virens and Gliocladium virens are synonymous. The ATCC listing of this organism under ATCC Accession No. 58678 confirms its prior classification as Gliocladium virens.
[0021] In a further embodiment, the inoculum is produced by adding an essentially pure culture, a substantially pure culture, an axenic culture or a biologically pure culture of Trichoderma virens to a bioreactor containing molasses-yeast extract growth medium using a standard inoculation technique. The medium is agitated and aerated and its temperature is maintained at about 28 degrees Centigrade. After the Trichoderma virens is grown in the medium for about eight hours, an essentially pure culture, a substantially pure culture, an axenic culture or a biologically pure culture of Bacillus amyloliquefaciens is added to the medium using a standard inoculation technique. The combined, competitive culture is grown under the aforementioned conditions and produces maximum cell and spore counts in approximately seven days. The combined culture is then used as an inoculum and is applied each seed at a rate of no less than about 1,000 spore counts per seed.
[0022] In a further embodiment, a solution containing an essentially pure culture, a substantially pure culture, an axenic culture or a biologically pure culture of the fungal antagonist Trichoderma virens is combined with a solution containing an essentially pure culture, a substantially pure culture, an axenic culture or a biologically pure culture of Bacillus amyloliquefaciens in a 50/50 mixture by volume and is applied to a seed at a rate of no less than about 10,000 spore counts per seed.
[0023] In a preferred embodiment, the invention is an agricultural inoculum suitable for inoculating plant seeds comprising a Trichoderma virens fungal antagonist selected from the group consisting of isolate ATCC 58678, isolate Gl-21 and mutants thereof; a Bacillus subtilis var. amyloliquefaciens bacterial antagonist selected from the group consisting of strain ATCC BAA-390, strain FZB24 and mutants thereof, and a suitable carrier that is non-phytotoxic, non-bacteriostatic, and non-bactericidal. Suitable carriers include wettable clay based powders, dextrose granules or powders, sucrose granules or powders and maltose-dextrose granules or powders.
[0024] A further embodiment of the invention is a composition of matter comprising a plant seed inoculated with a combination comprising a Trichoderma virens antagonist selected from the group consisting of isolate ATCC 58678, isolate Gl-21 and mutants thereof and a Bacillus amyloliquefaciens antagonist selected from the group consisting of strain ATCC BAA-390, strain FZB24 and mutants thereof, wherein said combination suppresses growth of plant pathogenic fungi.
[0025] Yet a further embodiment of the invention is a seed or plant inoculated with a combination selected from the group consisting of: a Trichoderma virens antagonist selected from the group consisting of isolate Gl-21 and mutants thereof and a Bacillus amyloliquefaciens antagonist selected from the group consisting of strain FZB24 and mutants thereof; a Trichoderma virens antagonist selected from the group consisting of isolate ATCC 58678 and mutants thereof and a Bacillus amyloliquefaciens antagonist selected from the group consisting of strain FZB24 and mutants thereof, and a Trichoderma virens antagonist selected from the group consisting of isolate ATCC 58678 and mutants thereof and a Bacillus amyloliquefaciens antagonist selected from the group consisting of strain FZB24 and mutants thereof, wherein the combination suppresses growth of plant pathogenic fungi.
[0026] In another preferred embodiment, the invention is a method of protecting a plant from disease caused by a plant pathogenic fungus comprising inoculating seeds from said plant with a combination comprising a Trichoderma virens fungal antagonist selected from the group consisting of isolate ATCC 58678, isolate Gl-21 and mutants thereof and a Bacillus amyloliquefaciens bacterial antagonist selected from the group consisting of strain ATCC BAA-390, strain FZB24 and mutants thereof, wherein said combination suppresses growth of plant pathogenic fungi.
[0027] A further embodiment of the invention is a method of protecting a seed or a plant from disease caused by a plant pathogenic fungus comprising inoculating seeds from said plant with a composition comprising a Trichoderma virens fungal antagonist and a Bacillus amyloliquefaciens bacterial antagonist. Preferably, the fungal antagonist is selected from the group consisting of isolate ATCC 58678, isolate Gl-21 and mutants thereof and the bacterial antagonist is selected from the group consisting of strain ATCC BAA-390, strain FZB24 and mutants thereof.
[0028] A further embodiment of the invention is a method of protecting a seed or a plant from disease caused by a plant pathogenic fungus comprising inoculating seeds from said plant with a composition comprising a fungal antagonist and a bacterial antagonist, wherein said combination suppresses growth of plant pathogenic fungi. A further embodiment is capable of control of the plant pathogen fungi Fusarium, Phythium, Phytophthora and Penicillium.
[0029] A further embodiment of the invention is a method of protecting a plant from disease caused by a plant pathogenic fungus comprising inoculating seeds from said plant with a composition selected from the group: a composition comprising a Trichoderma virens fungal antagonist selected from the group consisting of isolate ATCC 58678 and mutants thereof and a Bacillus amyloliquefaciens bacterial antagonist selected from the group consisting of strain ATCC BAA-390 and mutants thereof, and a composition comprising a Trichoderma virens fungal antagonist selected from the group consisting of isolate Gl-21 and mutants thereof and a Bacillus amyloliquefaciens bacterial antagonist selected from the group consisting of strain FZB24 and mutants thereof, wherein said combination suppresses growth of plant pathogenic fungi.
[0030] Yet a further embodiment of the invention is a method for biologically controlling or inhibiting stalk rot or root rot comprising coating seeds with an effective amount of a composition comprising a Trichoderma virens isolate Gl-21 and mutants thereof and a Bacillus amyloliquefaciens strain FZB24.
[0031] A further embodiment of the invention is process for making a composition comprising introducing an essentially pure culture of Bacillus amyloliquefaciens (strain FZB24) to a growth medium about eight hours after an essentially pure culture of Trichoderma virens (isolate Gl-21) is introduced to the growth medium and growing the culture as a competitive culture.
[0032] A further embodiment of the invention is a process comprising making a composition by combining an essentially pure culture of Trichoderma virens G1-3 (isolate Gl-21) with an essentially pure culture of Bacillus amyloliquefaciens (strain FZB24) in a 50:50 mixture and applying said composition to a seed at a rate of at least 100,000 spores per seed.
[0033] In one embodiment of the invention disclosed herein, the spore count applied per seed ranges from about 1,000 to about 1,000,000, regardless of seed size. In another embodiment of the invention, the spore count per seed is from about 1,000 to about 10,000. In a further embodiment of the invention, the spore count per seed is from about 10,000 to about 100,000. In a yet further embodiment of the invention, the spore count per seed is from about 100,000 to about 1,000,000. In a yet another embodiment of the invention, the spore count per seed is from about 1,000,000 to about 2,000,000.
[0034] A further embodiment of the invention is a method for protecting plants in a growing medium from damping off and root rot fungal plant disease comprising placing in the growing medium in the immediate vicinity of the plant to be protected an effective quantity of one of the fungal/bacterial combinations disclosed herein.
[0035] Yet a further embodiment of the invention is a method for protecting plants from fungal plant disease comprising adding one of the fungal/bacterial combinations disclosed herein in an effective quantity to a substrate such as pelletized calcium sulfate or pelletized lime and placing the pellet in the immediate vicinity of the plant to be protected. The pellet may or may not contain other nutrients.
[0036] A further embodiment of the invention is a method for protecting plants from fungal plant disease comprising adding one of the fungal/bacterial combinations disclosed herein in an effective quantity to a liquid solution such as water and applying the liquid solution in the immediate vicinity of the plant to be protected. The liquid may or may not contain additional nutrients and may include a chemical fungicide applied to the seed such as, for example, Maxim or captan. The disclosed combination may also be added to a plant nutrient (nitrogen-phosphorus-potassium (NPK)) plus plant micro-nutrient solution that is compatible with the combination and applied as an in-furrow treatment.
[0037] A further embodiment of the invention is a method for biologically controlling a plant disease caused by a plant-colonizing fungus, the method comprising inoculating a seed of the plant with an effective amount of a microbial inoculant comprising a combination of microorganisms having all of the identifying characteristics of Trichoderma virens and Bacillus amyloliquefaciens , said inoculation resulting in the control of said plant disease. The invention is also a method according to the above further embodiment wherein said inoculation results in the control of more than one plant disease.
[0038] Yet a further embodiment of the invention involves combining a Trichoderma virens fungal antagonist and a Bacillus amyloliquefaciens bacterial antagonist to enhance ease of use and longevity of shelf life both as a stored product and when applied to a seed. In a further embodiment, the invention involves applying the disclosed Trichoderma microorganism and the Bacillus microorganism to a wettable powder, in which form it is applied.
[0039] A further embodiment of the invention is composition of matter made by combining: a composition made by combing a plurality of antagonists selected from the group consisting of a Trichoderma virens antagonist selected from the group consisting of isolate Gl-21 and mutants thereof and a Bacillus amyloliquefaciens antagonist selected from the group consisting of strain FZB24 and mutants thereof; a Trichoderma virens antagonist selected from the group consisting of isolate ATCC 58678 and mutants thereof and a Bacillus amyloliquefaciens antagonist selected from the group consisting of strain FZB24 and mutants thereof; and a Trichoderma virens antagonist selected from the group consisting of isolate ATCC 58678 and mutants thereof and a Bacillus amyloliquefaciens antagonist selected from the group consisting of strain FZB24 and mutants thereof; and a suitable carrier that is non-phytotoxic, non-bacteriostatic, and non-bactericidal.
[0040] A further embodiment of the invention is an antagonist for controlling plant pathogens made by combining effective amounts of: a fungal antagonist selected from the group of Trichoderma virens isolate (isolate Gl-21) and mutants thereof; a bacterial antagonist selected from the group of Bacillus amyloliquefaciens (strain FZB24) and mutants thereof; and a suitable carrier that is non-phytotoxic, non-bacteriostatic, and non-bactericidal. Preferably, the antagonist made by further combining with the antagonist an effective amount of another bacterial strain.
[0041] Yet a further embodiment of the invention is a seed assembly made by combining a plant seed with effective amounts of a Trichoderma virens fungal antagonist and a Bacillus subtilis var. amyloliquefaciens bacterial antagonist. In a further embodiment, the seed is a seed of a plant selected from the group of a monocot, and a dicot. In a further embodiment, the seed is a seed of a plant selected from the group of a legume plant, and a non-legume plant. In a further embodiment, the seed is a seed of a plant selected from the group of corn, sunflower, soybean, field pea, and wheat.
[0042] A further embodiment of the invention is method for culturing a plant comprising: applying an antagonist disclosed herein to a seed or to the seedbed of the plant; planting the seed in the seedbed; growing the plant to yield a crop; and harvesting the crop; wherein said applying step increases the yield of the crop. In a further embodiment, the antagonist is applied to the seed or to the seedbed of a plant selected from the group of a monocot, and a dicot. In a further embodiment, the antagonist is applied to the seed or to the seedbed of a plant selected from the group of a legume plant, and a non-legume plant. In a further embodiment, the antagonist is applied to the seed or to the seedbed of a plant selected from the group of corn, sunflower, soybean, field pea, and wheat.
[0043] Plant species that may be treated with the disclosed invention include commercial crops species, e.g., barley, oat, millet, alfalfa. The disclosed invention may also be used to treat leguminous plants (e.g., soybeans, alfalfa, and peas) and non-leguminous plants (e.g., corn, wheat, and cotton). The disclosed invention may also be used to treat angiosperms and cereals.
[0044] Yet a further embodiment is a process comprising: making a composition by combining an essentially pure culture of Trichoderma virens (isolate Gl-21) with an essentially pure culture of Bacillus amyloliquefaciens (strain FZB24) in a mixture; and applying said composition to a seed; wherein said mixture ranges in composition from 10 to 90 percent Trichoderma virens (isolate Gl-21) by volume and from 90 to 10 percent Bacillus amyloliquefaciens (strain FZB24) by volume.
[0045] Yet a further embodiment of the invention is a process comprising: making a composition by combining an essentially pure culture of Trichoderma virens (isolate Gl-21) with a plurality of essentially pure cultures of bacteria in a mixture; and applying said composition to a seed; wherein said mixture ranges in composition from 10 to 90 percent Trichoderma virens (isolate Gl-21) by culture volume.
[0046] In one embodiment of the invention the mixture ranges in composition from 10 to 90 percent Trichoderma virens by volume and from 90 to 10 percent Bacillus amyloliquefaciens by volume. In another embodiment of the invention, the mixture comprises about 20 percent Trichoderma virens by volume 80 percent Bacillus amyloliquefaciens by volume. In a further embodiment of the invention, the mixture comprises about 30 percent Trichoderma virens by volume 70 percent Bacillus amyloliquefaciens by volume. In a yet further embodiment of the invention, the mixture comprises about 40 percent Trichoderma virens by volume 60 percent Bacillus amyloliquefaciens by volume.
[0047] A further embodiment of the invention is an antagonist for controlling plant pathogens made by combining effective amounts of: a fungal antagonist selected from the group of an isolate of Trichoderma virens and mutants thereof; a bacterial antagonist selected from the group a strain of Bacillus amyloliquefaciens and mutants thereof; and a suitable carrier that is non-phytotoxic, non-bacteriostatic, and non-bactericidal. Preferably, the isolate is Trichoderma virens (isolate Gl-21), which is presently EPA registered.
[0048] In a further embodiment, the invention is an antagonist for controlling plant pathogens made by combining effective amounts of: a fungal antagonist selected from the group of Trichoderma virens (isolate Gl-21) and mutants thereof; a plurality of bacterial antagonists; and a suitable carrier that is non-phytotoxic, non-bacteriostatic, and non-bactericidal. Preferably, the plurality of bacterial antagonists comprises a strain of Bacillus lentimorbus.
[0049] In a preferred embodiment, the invention is a method comprising: combining a spore-forming fungal strain and a spore-forming bacterial strain to produce a product comprising a composition of matter disclosed herein; and applying the product to a plant or to a part of the plant; whereby application of the product produces yield enhancement in the plant.
[0050] In another preferred embodiment, the invention is a method comprising: applying a Trichoderma spp. microorganism and a Bacillus spp. microorganism to a wettable powder to produce a combination comprising an antagonist disclosed herein; and applying the combination to a seed; whereby application of the combination produces a positive yield response in a plant growing from the seed.
[0051] In yet another preferred embodiment, the invention is a process comprising: making a composition of matter disclosed herein; and applying said composition of matter to a seed; wherein said composition of matter ranges in composition from 1 to 99 percent Trichoderma virens by culture volume and from 99 to 1 percent Bacillus amyloliquefaciens by culture volume.
[0052] In another preferred embodiment, the invention is a composition of matter comprising: a plant seed inoculated with an agricultural inoculum disclosed herein; wherein said combination increases the yield of the plant. In another preferred embodiment, the invention is a method for increasing the yield of a plant, the method comprising: coating a seed of the plant with an effective amount of an agricultural inoculum disclosed herein; and culturing the plant.
[0053] In another preferred embodiment, the invention is a composition made by combining effective amounts of: a spore-forming fungal antagonist; and a spore-forming bacterial antagonist; wherein the spore-forming fungal antagonist does not produce a substance that substantially inhibits the growth of the spore-forming bacterial antagonist and the spore-forming bacterial antagonist does not produce a substance that substantially inhibits the growth of the spore-forming fungal antagonist; and wherein the composition is effective at increasing the yield of a plant grown from a seed to which the composition has been applied. Preferably, the composition is effective at increasing the manganese content of the plant
[0054] The compositions of the present invention can be used for controlling fungal infestations by applying an effective amount of the composition or a formulation thereof, either at one point in time or throughout the plant/crop cycle via multiple applications. The formulation may be applied to the locus to be protected for example by spraying, atomizing, vaporizing, scattering, dusting, coating, watering, squirting, sprinkling, pouring, fumigating, and the like. The dosage of the bioagent(s) applied may be dependant upon factors such as the type of fungal pest, the carrier used, the method of application (e.g., seed, plant application or soil delivery) and climate conditions for application (e.g., indoors, arid, humid, windy, cold, hot, controlled), or the type of formulation (e.g., aerosol, liquid, or solid).
[0055] Biocontrol agents comprising the disclosed compositions may be applied in agricultural, horticultural and seedling nursery environments. This generally includes application of agents to soil, seeds, whole plants, or plant parts (including, but not limited to, roots, tubers, stems, flowers and leaves). Bio-pesticide or microbial combinations may be used alone, however, they may additionally be formulated into conventional products such as dust, granule, microgranule, pellet, wettable powder, flowable powder, emulsion, microcapsule, oil, or aerosol. To improve or stabilize the effects of the bio-pesticide, the agent may be blended with suitable adjuvants and then used as such or after dilution if necessary.
[0056] A worker skilled in the art would recognize that the bioagent(s) may be formulated for seed treatment either as a pre-treatment for storage or sowing. The seed may form part of a pelleted composition or, alternatively, may be soaked, sprayed, dusted or fumigated with the inventive compositions. Additionally, the inventive compositions may be applied to the soil or turf, a plant, crop, or a plantation. Some areas may additionally require that the invention provide for slow-release materials such that the agent is designed to have an extended release period.
[0057] In use, the invention disclosed herein may comprise the application of an aqueous or a non-aqueous spray composition to the crop. For example, the inventive composition may be applied to the soil, or to a plant part (e.g., stalk, root or leaf), or both, as an aqueous spray containing spray adjuvants such as surfactants and emulsified agricultural crop oils which insure that the agent is deposited as a droplet which wets the stalk or leaf and is retained on the plant so that agent can be absorbed.
[0058] The skilled artisan would realize that the inventive compositions may be applied in combination with nutrients (fertilizers) or herbicides or both, or may form part of a formulation comprising the inventive composition in combination with a fertilizer or herbicide or both. Such a formulation may be manufactured in the form of a liquid, a coating, a pellet or in any format known in the art.
[0059] The skilled artisan would realize that the inventive compositions may be applied to seeds as part of stratification, desiccation, hormonal treatment, or a mechanical process to encourage germination or to terminate dormancy. Treatments including the inventive agents in combination with hormones, PEG, or varying temperature, or in combination with mechanical manipulation of the seed (i.e. piercing), are contemplated.
[0060] Further aspects of the invention will become apparent from consideration of the drawings and the ensuing description of further embodiments of the invention. A person skilled in the art will realize that other embodiments of the invention are possible and that the details of the invention can be modified in a number of respects, all without departing from the inventive concept. Thus, the following drawings and description are to be regarded as illustrative in nature and not restrictive.
BRIEF DESCRIPTION OF THE DRAWINGS
[0061] The features of the invention will be better understood by reference to the accompanying drawings which illustrate presently further embodiments of the invention. In the drawings:
[0062] FIG. 1 is a plot that compares the incidence of stalk rot in TJ1300-treated plots versus the incidence of stalk rot in control plots.
[0063] FIG. 2 is a plot that compares final plant populations in TJ1300-treated plots versus final plant populations in control plots.
DETAILED DESCRIPTION OF THE INVENTION
[0064] A preferred embodiment of the invention comprises the fungus Trichoderma virens isolate G1-3 (ATCC 58678) or other isolates. These microorganisms may be obtained from the American Type Culture Collection (ATCC), 12301 Parklawn Drive, Rockville, Md., 20852-1776 and other culture collections or isolated from nature.
[0065] Another preferred embodiment of the invention comprises Trichoderma ( Gliocladium ) virens isolate Gl-21 which is being marketed under the trademark SoilGuard® 12G by Thermo Trilogy Corporation, 9145 Guilford Road, Suite 175, Columbia, Md. 21046.
[0066] A further embodiment of the invention also comprises the bacterium Bacillus lentimorbus TJ 1000, which is renamed herein Bacillus amyloliquefaciens TJ1000 or 1BE, based on a more accurate determination of the name of Bacillus species that occurred before the parent patent application was filed. This microorganism was deposited with the ATTC on Oct. 31, 2001, and was assigned accession number ATCC BAA-390. Alternative embodiments of the invention comprise other strains which can be isolated from nature or obtained from ATCC or other culture collections.
[0067] Another preferred embodiment of the invention is comprised of Bacillus subtilis var. amyloliquefaciens strain FZB24 which is being marketed under the trademark Taegro® by Earth Bioscience, Inc., 26 Sherman Court, PO Box 764, Fairfield, Conn. 06430.
[0068] A further embodiment of the invention involves combining an essentially pure culture of Trichoderma virens and an essentially pure culture of Bacillus amyloliquefaciens in a competitive culture process. The competitive culture process involves adding the Bacillus amyloliquefaciens to a growth medium about eight hours after the Trichoderma virens was added to the medium. The combined culture is then applied to a seed, for example, a corn seed. The combination grown in a competitive culture provides protection for seeds and plants and is especially effective in a high-stress, high-fungal pathogen environment during the early stages of plant development.
[0069] A further embodiment of the invention involves growing an essentially pure culture of Trichoderma virens and an essentially pure culture of Bacillus amyloliquefaciens TJ1000 separately for five days. After the cultures are grown separately, the compositions that contain them are combined in a 50/50 combination by volume and then the combination is applied to a seed, for example, a corn seed. The combined cultures are applied to a seed provides protection for seeds and plants from fungal pathogens. This combination is especially effective under conditions that are less stressful to the plant.
[0070] A further step in the process involves applying either of the above combinations to a seed involves adding an aqueous solution comprising 30 grams/liter of molasses to the solution containing the combination to produce an appropriate spore count in the resulting composition. The resulting composition is then applied to the seed as a liquid mist to achieve optimum application rates per seed using the molasses as an adhesive to adhere the spores to the seed.
[0071] In a further embodiment, the bioreactor used to culture the microorganism cultures is a New Brunswick Bioflow III bioreactor. For optimal results, the agitation setting of the bioreactor is set at about 350 rpm, the aeration setting of the bioreactor is set at about 3.0 with an aeration air pressure of about 15 pounds per square inch and the temperature setting is set at about 28 degrees Centigrade. The further growth medium for each of the individual cultures and the combined competitive culture comprises about 30 grams per liter of molasses and about 5 grams per liter of yeast extract and is referred to as a MYE medium. In A further embodiment, the medium contains about 5 milliliters of antifoam. In a further embodiment, spore production is measured by counting spores using a hemacytometer manufactured by Hausser Scientific.
[0072] A variety of seed treatments or no seed treatment may be practiced before the seed is inoculated with the disclosed inoculum. In some further embodiments, seed treatments include osmotic priming and pre-germination of the seed. Because Trichoderma virens and Bacillus amyloliquefaciens are spore formers, the disclosed inoculum does not require high moisture levels for survival and, therefore, can be applied to seed and other materials without a sticker, such as those sold under the trade names Pelgel (LipaTech), Keltrol (Xanthan) Cellprill or Bond.
[0073] In a further embodiment, the invention involves combining of a spore forming fungal strain and a spore forming bacterial strain to enhance ease of use and longevity of shelf life both as a stored product and when applied to a seed. In A further embodiment, the invention involves applying the disclosed Trichoderma microorganism and the disclosed Bacillus microorganism to a wettable powder, and marketing the wettable powder.
FIRST GREENHOUSE WORKING EXAMPLE
[0074] Greenhouse testing was conducted to determine the effectiveness of the disclosed biocontrol agents. Treated and untreated corn seeds were grown in soil infested with seven percent Fusarium infested wheat seed. In this testing, the following treatment codes were used:
[0075] CONTROL—Nothing on the seed
[0076] TJ 1000— Bacillus amyloliquefaciens TJ 1000 or 1 BE
[0077] TJ 0300— Trichoderma virens G1-3
[0078] TJ 1300—50/50 combination of Trichoderma virens G1-3 and Bacillus amyloliquefaciens TJ 1000 or 1 BE
[0079] TJ 1310—competitive culture of Trichoderma virens G1-3 and Bacillus amyloliquefaciens TJ 1000 or 1 BE, resulting in a 70/30 ratio of Trichoderma to Bacillus
[0080] The results of greenhouse testing are presented in Table 0. The rating scale used was 9=worst plant protection and 1=best plant protection. Seed treated with biocontrol organisms grown in competitive culture showed an increase in plant protection over seed treatments with the same biological control organisms grown in non-competitive culture. The biocontrol agents were applied to the seed without a sticker.
[0000]
TABLE 0
Greenhouse Testing Results
Treatment
Replication 1
Replication 2
Replication 3
Average
Control
9
7
6
7.3
TJ 0300
6
5
5
5.3
TJ 1000
7
6
5
6
TJ 1300
6
5
6
5.6
TJ 1310
1
3
3
2.3
FIELD TRIALS WORKING EXAMPLE
[0081] In a subsequent experiment, field trials were conducted at seven locations throughout the U.S. Site locations included Arizona, Colorado, Kansas, Montana, North Dakota and two South Dakota locations. At each location, the trial contained a CONTROL that was treated with the industry-standard chemical treatment, MAXIM. All cultures used in the trial were grown in MYE broth for five days. Bacillus amyloliquefaciens TJ 1000 or 1 BE was cultured individually (non-competitive) and with Trichoderma virens G1-3 (competitive culture). Trichoderma virens G1-3 and Bacillus amyloliquefaciens TJ 1000 or 1BE were also grown in non-competitive culture were also applied to the same seed to test the effectiveness of non-competitive culture versus competitive culture. Corn seeds were treated to give a final concentration of 1,000,000,000 bacterial/fungal spores per acre. Seed treatment was done with a Gustafson benchtop seed treater, Model BLT.
[0082] The plot location in Kansas was severely damaged by early dry conditions and the plot was terminated prior to harvest. The Colorado location was damaged due to machine damage prior to harvest. Colorado yield data were collected but were extremely variable and were not included in the analyzed data set. The Colorado stalk rot data were included in the data set.
[0083] The value of the Stalk Rot variable was determined by counting ten plants in a row, determining the number of root rot/stalk rot infected plants and expressing that number as a percentage. As illustrated in FIG. 1 , in six trials, the average infection rate in the control was 55.13 percent versus 38.62 percent in the entries treated with the fungal/bacterial combination, TJ1300. The data revealed an average reduction of disease incidence of 30 percent with the Colorado location showing a reduction of over 60 percent.
[0084] The value of the Final Population variable was determined by a conducting a physical count of the plants in a measured area and converting to a per acre count. As illustrated in FIG. 2 , the average increase in final plant population was 3,742 plants per acre or an increase of 12.2 percent. This increased population was the result of controlling the disease early and having less plant death throughout the season.
[0085] Use of TJ1300 resulted in an average yield benefit of 5.35 bushels per acre. Average yield was determined from eight trials: 4 in South Dakota, 1 in North Dakota, 2 in Arizona, and 1 in Montana.
SECOND GREENHOUSE WORKING EXAMPLE
[0086] Greenhouse Methods: All test cultures were grown in MYE (three percent Molasses, 0.5 percent Yeast Extract) broth for five days. Bacteria were grown up individually (non-competitive) and with T. virens G1-3 (competitive culture). T. virens G1-3 was also grown in a non-competitive culture for testing. T. virens G1-3 and test bacteria grown in non-competitive culture were also applied to the same seed to test the effectiveness of non-competitive culture versus competitive culture. Corn seeds were treated to give a final concentration of 1×10 9 bacteria/fungal spores (may also be referred to a Colony Forming Units or CFU) per acre. Seed treatment was done with a Gustafson Benchtop Seed Treater, Model BLT. Seeds were grown in soil infested with seven percent Fusarium -infested wheat seed. After four weeks, plant heights were taken as well as plant biomass. Plant heights were taken by measuring from the soil line to the tallest leaf, biomass of the plants was taken by cutting the plants at the soil line and then weighing plants on analytical scale. The treatment matrix was as follows:
[0087] Control—No pathogen added to soil.
[0088] Control—With pathogen added to soil.
[0089] TJ1000— Bacillus amyloliquefaciens TJ1000 or 1BE
[0090] TJ0300— Trichoderma virens G1-3
[0091] TJ2000— Erwinia carotovora
[0092] TJ1300— B. amyloliquefaciens TJ1000 or 1BE and T. virens G1-3 (non-competitive)
[0093] TJ2300— E. carotovora and T. virens G1-3 (non-competitive)
[0094] TJ1310— B. amyloliquefaciens TJ1000 or 1 BE and T. virens G1-3 (competitive)
[0095] TJ1-2310— B. amyloliquefaciens TJ1000 or 1BE, E. carotovora and T. virens G1-3 (competitive)
[0096] TJ2310— E. carotovora and T. virens G1-3 (competitive)
[0097] Determination of CFU (Colony Forming Units) concentrations in competitive cultures: Competitive cultures grown for five days. CFU counts of each organism were performed using a hemacytometer (Hausser Scientific) under light microscopy 5000× magnification. This method was used to determine the CFU counts in the greenhouse and field trials.
[0098] Enumeration through plate counts: Competitive cultures were grown for five days in submerged culture then 200 milliliters (ml) of the culture was harvested and aliquoted into four 50 ml centrifuge tubes. After centrifugation at 10,000 revolutions per minute (rpm) for 10 minutes resulting pellets were washed twice in equal volumes of D 2 H 2 0. Pellets were then re-suspended in 25 ml of saline. One ml samples were diluted 10 −1 to 10 −8 and plated onto potato dextrose agar (PDA) plates. Colonies are then counted and correlated with the dilution rates to determine CFU per ml of culture broth.
[0099] Results: All of the biocontrol agents in this experiment produced significant plant biomass increases over the pathogen-treated control and all of the treatments were numerically greater than the control plants in soil that contained no pathogen. The effects of bacterial/fungal combination TJ 1310 and the bacterial treatment TJ 1000 were significantly greater than both controls in the experiment.
[0000]
TABLE 1
Demonstration of the Effectiveness of Biological Combinations
and Individual Bacteria and Individual Fungal Treatments on
Increasing the Biomass of Greenhouse-Grown Corn Seedlings in
Pathogen-Treated Soil vs. the Untreated Control
Treatment
Ratio
Rank
Biomass (grams)
Control Path
0/0
10
3.62 a
Control No Path
0/0
9
7.25 ab
TJ 1300
50/50
8
8.67 b
TJ 2310
30/70
7
9.04 b
TJ 2000
100/0
6
10.73 b
TJ 1-2310
20/20/60
5
11.37 b
TJ 2300
50/50
4
11.41 b
TJ 0300
0/100
3
11.53 b
TJ 1310
30/70
2
12.24 bc
TJ 1000
100/0
1
12.89 bc
CV %
33.9
LSD (0.05)
4.55
COMBINATIONS FIELD TRIAL WORKING EXAMPLE
[0100] Materials and Methods: A field trial was conducted using the corn variety NK 3030Bt using the following biological treatments of the seed at a rate of approximately 10 6 CFU per seed. The seed was planted at a seeding rate of 25,000 seeds per acre in 30-inch rows in a randomized, replicated block. Each entry was replicated four times. The pathogen levels were natural populations at a location near Groton, S. Dak. The entries were as follows:
[0101] Control: Maxim Seed treatment (Maxim is a trademark of Syngenta Crop Protection)
[0102] TJ 1000— Bacillus amyloliquefaciens TJ 1000 or 1BE
[0103] TJ 0300— Trichoderma virens G1-3
[0104] TJ 1300—50/50 combination of B. amyloliquefaciens TJ1000 or 1BE and T. virens G1-3
[0105] TJ 1310—Coculture 30/70 combination of B. amyloliquefaciens TJ 1000 or 1BE and T. virens G1-3
[0106] TJ 66/300—50/50 combination of Bacillus lentimorbus and T. virens G1-3
[0107] Results: The trial produced significant yield response over the control with the entries TJ 0300, TJ 1300, and TJ 1310. The combinations TJ 1300 and TJ 1310 produced a yield response numerically greater than that of TJ 0300. The effects of bacterial/fungal combination TJ 66/300 and the bacterial treatment TJ 1000 were numerically greater than the control but not significantly greater. The results are presented in Table 2.
[0108] Conclusion: The bacterial/fungal combinations of entries TJ 1300 and TJ 1310 are the most effective biocontrol treatments in the trial for increasing the yield of corn.
[0000]
TABLE 2
Effect of Biological Seed Treatment on Yield of Corn Variety N3030
Bt under Field Conditions.
Treatment
Ratio
Rank
Location
Trial
Yield
Control Maxim
0/0
6
Groton, SD
Seed Treat
164.8 a
TJ 1000
100/0
4
Groton, SD
Seed Treat
175.1 ab
TJ 0300
0/100
3
Groton, SD
Seed Treat
179.5 bc
TJ 1300
50/50
2
Groton, SD
Seed Treat
183.3 bc
TJ 1310
30/70
1
Groton, SD
Seed Treat
189.8 c
TJ 66/300
50/50
5
Groton, SD
Seed Treat
173.2 ab
CV %
13.54
LSD (0.05)
12.5
50/50 COMBINATION FIELD TRIAL WORKING EXAMPLE
[0109] Materials and Methods: A field trial was conducted using the corn variety NK 3030Bt using the following biological treatments of the seed at a rate of approximately 10 6 CFU per seed. The seed was planted at a seeding rate of 25,000 seeds per acre in 30-inch rows in a randomized replicated block. Each entry was replicated four times. The pathogen levels were natural populations at a location near Groton, S. Dak. The entries were as follows:
[0110] Control: Maxim Seed treatment (Maxim is a trademark of Syngenta Crop Protection)
[0111] TJ 1300-50/50 combination of B. amyloliquefaciens TJ1000 or 1BE and T. virens G1-3
[0112] Results: As indicated in Table 3, the trial produced a significant response in the yield of the seed treated with the biocontrol agent TJ 1300 (described above) as compared with the untreated control.
[0000]
TABLE 3
Effect of Biological Seed Treatment on Yield of Corn Variety
NK 3030Bt under Field Conditions.
Treatment
Ratio
Rep
Location
Yield
Control
0/0
1
Groton, SD
156.8
Control
0/0
2
Groton, SD
163.3
Control
0/0
3
Groton, SD
151.0
Average
0/0
Groton, SD
157.03 a
1300
50/50
1
Groton, SD
184.3
1300
50/50
2
Groton, SD
179.1
1300
50/50
3
Groton, SD
177.3
Average
50/50
Groton, SD
180.21 b
CV %
5.65
LSD (0.05%)
9.04
APPLICATION RATE FIELD TRIAL WORKING EXAMPLE
[0113] Materials and Methods: A field trial was conducted using the corn variety NK2555 using the TJ 1300 (50/50 combination of B. amyloliquefaciens TJ1000 or 1BE and T. virens G1-3) biological treatments of the seed at variable rates. The purpose of the trial was to identify the most effective application rate for the bacterial/fungal combination of TJ 1300. The 1× rate was approximately 1×10 6 CFU per seed. The seed was planted at a seeding rate of 25,000 seeds per acre in 30-inch rows in a randomized, replicated block. Each entry was replicated four times. The pathogen levels were natural populations at a location near Groton, S. Dak. The entries were as follows:
[0114] Control—Maxim (Maxim is a trademark of Syngenta Crop Protection)
[0115] 0.5× rate
[0116] 1× rate
[0117] 1.5× rate
[0118] 2× rate
[0119] Results: All of the biocontrol treatments in this experiment resulted in significant yield response over the control with the 1.5× rate producing significantly better results than the 2× rate. The results of this trial, presented in Table 4, indicated that the most efficacious application rate of the biocontrol agent TJ 1300 was approximately 1.5×10 6 per seed.
[0000]
TABLE 4
Effect of TJ1300 Biological Seed Treatment on Yield of Corn Variety
N2555 at Variable Rates
Treatment
Ratio
Rank
Location
Trial
Yield
Control
0/0
5
Groton, SD
Rate
140.2 a
0.5x rate
50/50
3
Groton, SD
Rate
153.6 bc
1x rate
50/50
2
Groton, SD
Rate
156.2 bc
1.5x rate
50/50
1
Groton, SD
Rate
161.1 c
2x rate
50/50
4
Groton, SD
Rate
152.07 b
CV %
5.31
LSD (0.05%)
8.61
LIQUID BIOCONTROL PREPARATIONS WORKING EXAMPLE
[0120] Materials and Methods: Field trials were conducted using the corn varieties NK 3030 and NK 3030Bt at a location in Brookings, S. Dak. and NK 3030Bt and NK2555 at a location in Groton, S. Dak. The purpose of the trial was to compare pathogen control of liquid biocontrol preparations to a control treated with only water. The results of the trial were quantified in yield of corn in bushels per acre. The water was applied to the control at a 10 gallon per acre rate. Biocontrol treatments were prepared by adding 1×1 8 CFU per gram of a wettable powder (Mycotech, Inc.). Two and one half grams of the wettable powder was added per one gallon of water and soil applied in the seed furrow at a rate of 10 gallons per acre. The seed was Maxim (Maxim is a trademark of Syngenta Crop Protection) treated and was planted at a seeding rate of 25,000 seeds per acre in 30-inch rows in a randomized, replicated block. Each entry was replicated four times. The pathogen levels were natural populations at each location. The entries were as follows:
[0121] Control—Water
[0122] TJ 1000— Bacillus amyloliquefaciens TJ 1000 or 1 BE
[0123] TJ 0300— Trichoderma virens G1-3
[0124] TJ 1300—50/50 combination of B. amyloliquefaciens TJ1000 or 1BE and T. virens G1-3
[0125] TJ 1310—Coculture 30/70 combination of B. amyloliquefaciens TJ 1000 or 1BE and T. virens G1-3
[0126] TJ 66/300—50/50 combination of Bacillus lentimorbus and T. virens G1-3
[0127] Results: Table 5 shows a significant yield increase to the biocontrol treatments of TJ 1000, TJ1300, and TJ 66/300. All of the biocontrol treatments showed a numerical yield increase.
[0128] Table 6 shows a significant yield increase to the biocontrol treatments of TJ 1000, TJ0300, and TJ1300. Again, all of the biocontrol treatments showed a numerical yield increase.
[0129] Table 7 shows no significance in the yield between the treatments and the control, however, the yield of TJ0300 was numerically less than the control by over 10 bushels per acre and is significantly less than the yields of the TJ 1000 and TJ 1310 bacterial/fungal combination. This table demonstrates the strength of the disclosed bacterial/fungal combinations over the fungal control alone.
[0130] Table 8 shows the treatments of TJ 1000 and TJ 66/300 with significantly less yield than the control while the treatments of TJ0300, TJ1300, and TJ1310 having no significant difference. In this trial, it was the bacterial entry of TJ1000 alone that shows weakness in pathogen control. This table demonstrates the strength of disclosed bacterial/fungal combinations over the bacterial treatment alone.
[0131] Conclusion: The bacterial/fungal combination of entries TJ 1300 and TJ 1310 produce consistent pathogen control and/or yield response, while the bacteria entry of TJ 1000 alone and fungal entry of TJ 0300 alone produce inconsistent pathogen control and/or yield response.
[0000]
TABLE 5
Liquid Drench Treatment on Corn Variety NK3030 at Brookings,
SD Location
Treatment
Variety
Ratio
Rank
Location
Trial
Yield
Control
NK3030
0/0
6
Brookings,
Liquid
162.2 a
SD
TJ1000
NK3030
100/0
1
Brookings,
Liquid
179.7 b
SD
TJ0300
NK3030
0/100
5
Brookings,
Liquid
170.7ab
SD
TJ1300
NK3030
50/50
2
Brookings,
Liquid
177.9 b
SD
TJ1310
NK3030
30/70
4
Brookings,
Liquid
172.8ab
SD
TJ66/300
NK3030
50/50
3
Brookings,
Liquid
175.0 b
SD
CV %
7.38
LSD (0..20%)
12.36
[0000]
TABLE 6
Liquid Drench Treatment on Corn Variety NK2555 at Groton,
SD Location
Treatment
Variety
Ratio
Rank
Location
Trial
Yield
Control
NK2555
0/0
6
Groton,
Liquid
136.2 a
SD
TJ1000
NK2555
100/0
1
Groton,
Liquid
147.7 c
SD
TJ0300
NK2555
0/100
2
Groton,
Liquid
145.0bc
SD
TJ1300
NK2555
50/50
3
Groton,
Liquid
142.5bc
SD
TJ1310
NK2555
30/70
4
Groton,
Liquid
141.5abc
SD
TJ66/300
NK2555
50/50
5
Groton,
Liquid
138.5abc
SD
CV %
10.92
LSD (0.20%)
8.42
[0000]
TABLE 7
Liquid Drench Treatment on Corn Variety NK 3030Bt at Brookings,
SD Location
Treatment
Variety
Ratio
Rank
Location
Trial
Yield
Control
NK3030Bt
0/0
4
Brookings,
Liquid
181.5
SD
ab
TJ1000
NK3030Bt
100/0
2
Brookings,
Liquid
185.5 b
SD
TJ0300
NK3030Bt
0/100
6
Brookings,
Liquid
171.3 a
SD
TJ1300
NK3030Bt
50/50
5
Brookings,
Liquid
180.7ab
SD
TJ1310
NK3030Bt
30/70
1
Brookings,
Liquid
185.8 b
SD
TJ66/300
NK3030Bt
50/50
3
Brookings,
Liquid
181.6
SD
ab
CV %
6.32
LSD (0.20%)
11.40
[0000]
TABLE 8
Liquid Drench Treatment on Corn Variety 3030Bt at Groton,
SD Location
Treatment
Variety
Ratio
Rank
Location
Trial
Yield
Control
NK3030Bt
0/0
2
Groton,
Liquid
173.9 c
SD
TJ1000
NK3030Bt
100/0
6
Groton,
Liquid
164.1 a
SD
TJ0300
NK3030Bt
0/100
4
Groton,
Liquid
171.3abc
SD
TJ1300
NK3030Bt
50/50
3
Groton,
Liquid
171.5abc
SD
TJ1310
NK3030Bt
30/70
1
Groton,
Liquid
176.3 c
SD
TJ66/300
NK3030Bt
50/50
5
Groton,
Liquid
164.4 ab
SD
CV %
10.92
LSD (0.20%)
8.42
COMPATIBILITY WITH DRY GRANULE MICRO-NUTRIENT FERTILIZER WORKING EXAMPLE
[0132] Materials and Methods: A field trial was conducted using the corn variety NK 3030Bt at a location in Groton, S. Dak. The purpose of the trial was to compare the compatibility and yield benefit of the biocontrol preparation TJ1300 in combination with a dry granule micro-nutrient fertilizer vs. the micro-nutrient fertilizer alone vs. a control with no micro-nutrient fertilizer. The micro-nutrient fertilizer is sold commercially by the applicant under the trademark TJ Micromix™. Biocontrol treatments were prepared by adding 1×10 6 CFU per seed. The control seed was Maxim (Maxim is a trademark of Syngenta Crop Protection) treated with the biocontrol treatments applied in addition to the Maxim. The seed was planted at a seeding rate of 25,000 seeds per acre in 30-inch rows in a randomized, replicated block. TJ Micromix™ was applied at a rate of 20 pounds per acre. Each entry was replicated four times. The pathogen levels were natural populations at each location. The entries were as follows:
[0133] Control: Maxim
[0134] TJ Micromix
[0135] TJ Micromix+TJ 1300-50/50 combination of B. amyloliquefaciens TJ1000 or 1BE and T. virens G1-3
[0136] Results: In this trial, as shown in Table 9, the Granular TJ Micromix produced a non-significant yield increase compared to the control. When the seed-applied biocontrol treatment TJ1300 was applied in combination with the TJ Micromix, the treatment resulted in a significant increase in yield.
[0137] Conclusion: The trial shows that TJ 1300 is compatible with micro-nutrient applications and the combination produces a significant yield response.
[0000]
TABLE 9
Effect of TJ Micromix and TJ Micromix + TJ 1300 on Corn
Variety NK 3030Bt
Treatment
Variety
Rank
Location
Trial
Yield
Control
NK3030Bt
3
Groton, SD
Fertilizer
157.0 a
TJ Micromix
NK3030Bt
2
Groton, SD
Fertilizer
163.3 ab
TJ Micromix +
NK3030Bt
1
Groton, SD
Fertilizer
175.5 b
TJ 1300
CV %
9.04
LSD (0.05%)
5.64
COMPATIBILITY WITH LIQUID CHELATE MICRO-NUTRIENT FERTILIZER WORKING EXAMPLE
[0138] Materials and Methods: A field trial was conducted using the corn variety NK 3030Bt at a location in Groton, S. Dak. The purpose of the trial was to compare the compatibility and yield benefit of the biocontrol preparation TJ1300 in combination with a liquid chelate micro-nutrient fertilizer vs. the liquid chelate micro-nutrient fertilizer alone. The liquid chelate micro-nutrient fertilizer is sold commercially under the Trademark TJ Micromix™—Cornmix. Biocontrol treatments were prepared by adding 1×10 6 CFU per seed. The control seed was Maxim (Maxim is a trademark of Syngenta Crop Protection) treated with the biocontrol treatments applied in addition to the Maxim. The seed was planted at a seeding rate of 25,000 seeds per acre in 30-inch rows in a randomized, replicated block. TJ Micromix™—Cornmix was applied at a rate of 1.5 quarts per acre. Each entry was replicated four times. The pathogen levels were natural populations at the location. The entries were as follows:
[0139] Control: Maxim+Liquid Chelate TJ Micromix
[0140] TJ Micro+TJ1000: Liquid Chelate TJ Micromix plus TJ 1000— B. amyloliquefaciens TJ1000 or 1BE
[0141] TJ Micro+TJ0300: Liquid Chelate TJ Micromix plus TJ 0300— T. virens G1-3
[0142] TJ Micro+TJ1300: Liquid Chelate TJ Micromix+TJ 1300—50/50 combination of B. amyloliquefaciens TJ 1000 or 1 BE and T. virens G1-3
[0143] TJ Micro+TJ1310: Liquid Chelate TJ Micromix+TJ 1310—Coculture 30/70 combination of B. amyloliquefaciens TJ 1000 or 1BE and T. virens G1-3
[0144] TJ Micro+TJ66/300: Liquid Chelate TJ Micromix+TJ 66/300—50/50 combination of Bacillus lentimorbus and T. virens G1-3
[0145] Results: As shown in Table 10, the biocontrol treatments TJ1000, 66/300, and 1300 combined with the liquid chelate TJ Micromix resulted in a significant increase in yield over the control of TJ Micromix alone. The other biocontrol entries showed numerical but non-significant increases in yield. The conclusion was that the biocontrol agents used in this study are compatible with liquid chelate micro-nutrient applications. This biocontrol/liquid chelate micro-nutrient fertilizer combination is a viable means to significantly increase the yield of corn.
[0000]
TABLE 10
Effect of TJ Micromix Liquid Chelate and TJ Micromix Liquid
Chelate + TJ 1300 on Yield of Corn Variety NK3030Bt
Loca-
Treatment
Variety
Ratio
Rank
tion
Trial
Yield
Control
NK3030Bt
0/0
6
Groton,
Liquid TJ
161.0 a
SD
Micromix
TJ Micro +
NK3030Bt
100/0
3
Groton,
Liquid TJ
173.0
TJ 1000
SD
Micromix
bc
TJ Micro +
NK3030Bt
0/100
5
Groton,
Liquid TJ
163.0
TJ 0300
SD
Micromix
ab
TJ Micro +
NK3030Bt
50/50
1
Groton,
Liquid TJ
183.7 c
TJ1300
SD
Micromix
TJ Micro +
NK3030Bt
30/70
4
Groton,
Liquid TJ
172.0
TJ 1310
SD
Micromix
ab
TJ Micro +
NK3030Bt
50/50
2
Groton,
Liquid TJ
173.2
TJ 66/300
SD
Micromix
bc
CV %
11.2
LSD (0.05%)
12.36
SUNFLOWER DRY GRANULE MICRO-NUTRIENT FERTILIZER WORKING EXAMPLE
[0146] Materials and Methods: A field trial was conducted using the sunflower variety Pioneer 63M80 NuSun at a location in Hazelton, N. Dak. The purpose of the trial was to compare the compatibility and yield benefit of the biocontrol preparation TJ1300 in combination with a dry granule micro-nutrient fertilizer vs. the micro-nutrient fertilizer alone vs. a control with no micro-nutrient fertilizer. Analyzing yield of sunflower is a function of seed yield in pounds per acre and the amount of oil in the seed which is expressed as a percentage. The micro-nutrient fertilizer is sold commercially under the Trademark TJ Micromix™. Biocontrol treatments were prepared by adding 1×10 6 CFU per seed. The control seed was Maxim (Maxim is a trademark of Syngenta Crop Protection) treated with the biocontrol treatments applied in addition to the Maxim. The seed was planted at a seeding rate of 22,000 seeds per acre in 30-inch rows in a randomized, replicated block. TJ Micromix™ was applied at a rate of 20 pounds per acre. Each entry was replicated four times. The pathogen levels were natural populations at the location. The entries were as follows:
[0147] Control: Maxim
[0148] TJ Micromix
[0149] TJ 1300—50/50 combination of B. amyloliquefaciens TJ1000 or 1BE and T. virens G1-3
[0150] TJ Micromix+TJ 1300—50/50 combination of B. amyloliquefaciens TJ1000 or 1BE and T. virens G1-3
[0151] Results: As shown in Table 11, in this trial, the Granular TJ Micromix produced a significant yield increase and a significant oil percentage increase compared to the control. When the seed-applied biocontrol treatment TJ 1300 was applied in combination with the TJ Micromix, the treatment resulted in a significant increase in yield as compared to the control but not significantly different from the TJ Micromix application alone. The yield of the TJ 1300+TJ Micromix was numerically higher in yield. The conclusion was that TJ 1300 is compatible with micro-nutrient applications and may be a viable tool to increase the yield of sunflower.
[0000]
TABLE 11
Effect of TJ1300 Liquid Biological Treatment Plus Dry Granular
TJ Micromix on Yield of Nu-sun Sunflower Variety 63M80
Treatment
Rank
Location
Trial
Yield
Oil
Control
Hazelton, ND
TJ Micro
1709.7 a
44.8 a
TJ Micromix
Hazelton, ND
TJ Micro
1857.3 bc
47.2 b
TJ 1300
Hazelton, ND
TJ Micro
1734.7ab
45.5 a
TJ 1300 + TJ
Hazelton, ND
MM
1864.7 bc
44.9 a
Micromix
CV %
7.48
4.67
LSD (0.20)
132.8
1.5
SUNFLOWER LIQUID CHELATE MICRO-NUTRIENT WORKING EXAMPLE
[0152] Materials and Methods: Field trial was conducted using the sunflower variety Pioneer 63M80 NuSun at 3 locations: Hazelton, N. Dak.; Kensal, N. Dak.; and Selby, S. Dak. The purpose of each trial was to compare the compatibility and yield benefit of the biocontrol preparation TJ1300 in combination with a liquid chelate micro-nutrient fertilizer vs. an untreated control. Analyzing yield of sunflower is a function of seed yield in pounds per acre and the amount of oil in the seed which is expressed as a percentage. The liquid chelate micro-nutrient fertilizer is sold commercially under the Trademark TJ Micromix™. Biocontrol treatments were prepared by adding 1×10 8 CFU per gram to a wettable powder (Mycotech, Inc). 25 grams of the wettable powder was then added to 1.5 quarts of liquid chelate TJ Micromix and the combination applied in the seed furrow at a rate of 1.5 quarts per acre. The control seed was Maxim (Maxim is a trademark of Syngenta Crop Protection) treated with the biocontrol treatments applied in addition to the Maxim. The seed was planted at a seeding rate of 22,000 seeds per acre in 30-inch rows in a randomized, replicated block. Each entry was replicated four times. The pathogen levels were natural populations at each location. The entries were as follows:
[0153] Control—no treatment
[0154] TJ 1300—50/50 combination of B. amyloliquefaciens G1-3 and T. virens G1-3
[0155] TJ1300+TJ Micromix—Liquid chelate TJ Micromix+50/50 combination of B. amyloliquefaciens and T. virens
[0156] Result: As shown in Table 12, TJ Micromix liquid and the combination of TJ Micromix plus TJ 1300 both gave sunflower a significant increase in yield. TJ 1300+TJ Micromix produced an additional numerical increase in yield over the TJ Micromix alone.
[0157] Conclusion: TJ 1300+TJ Micromix is a viable means of biocontrol delivery on sunflower and is a viable means of increasing the seed yield of sunflower.
[0000]
TABLE 12
Effect of TJ1300 Biological Liquid Plus Liquid TJ Micromix
Fertilizer on Yield of Nu-sun Sunflower Variety 63M80
Treatment
Ratio
Location
Trial
Yield
Oil
Control
0/0
Hazelton, ND
Liquid TJ
1709.7
44.8
Micro
TJ 1300
50/50
Hazelton, ND
Liquid TJ
1765.0
45.5
Micro
TJ1300 + TJ
50/50
Hazelton, ND
Liquid TJ
1992.3
45.9
Micromix
Micro
Control
0/0
Kensal, ND
Liquid TJ
2000.3
N/a
Micro
TJ1300
50/50
Kensal, ND
Liquid TJ
2159.0
N/a
Micro
TJ1300 + TJ
50/50
Kensal, ND
Liquid TJ
2329.0
N/a
Micromix
Micro
Control
0/0
Selby, SD
Liquid TJ
2225.0
43.2
Micro
TJ 1300
50/50
Selby, SD
Liquid TJ
2324.0
44
Micro
TJ1300 + TJ
50/50
Selby, SD
Liquid TJ
2228.5
44
Micromix
Micro
Control
1978.3 a
44 a
Average
TJ 1300
2082.8 b
44.75 a
TJ 1300 + TJ
2173.3 b
45.5 a
Micromix
CV %
10.58
4.67
LSD (0.05)
104.1
NS
SOYBEAN LIQUID CHELATE MICRO-NUTRIENT FERTILIZER WORKING EXAMPLE
[0158] Materials and Methods: A field trial was conducted using the soybean variety Pioneer 91B52 a location near Groton, S. Dak. The purpose of the trial was to compare the compatibility and yield benefit of the biocontrol preparation TJ1300 in combination with a liquid chelate micro-nutrient fertilizer vs. the liquid chelate alone vs. an untreated control. Yield in bushels per acre was used as the measure of the treatment response. The liquid chelate micro-nutrient fertilizer is sold commercially under the Trademark TJ Micromix™. Biocontrol treatments were prepared by adding 1×10 8 CFU per gram to a wettable powder (Mycotech, Inc). Twenty-five grams of the wettable powder was then added to 10 gallons of water and applied in the seed furrow at a rate of 10 gallons per acre to establish treatment TJ1300. Twenty-five grams of the wettable powder was added to 1.5 quarts of liquid chelate TJ Micromix and the combination added to water to form a 10 gallon solution and applied in the seed furrow at a rate of 10 gallons per acre. The seed was planted at a seeding rate of 175,000 seeds per acre in 30-inch rows in a randomized, replicated block. Each entry was replicated four times. The pathogen levels were natural populations at the location. The entries were as follows:
[0159] Control—no treatment
[0160] TJ 1300—50/50 combination of B. amyloliquefaciens TJ1000 or 1BE and T. virens G1-3
[0161] TJ1300+TJ Micromix—Liquid chelate TJ Micromix+50/50 combination of B. amyloliquefaciens TJ1000 or 1BE and T. virens G1-3
[0162] Result: As shown in Table 13, TJ Micromix liquid and the combination of TJ Micromix plus TJ 1300 both gave soybean a significant increase in yield. TJ 1300+TJ Micromix produced an additional numerical but non significant increase in yield over the TJ Micromix alone.
[0163] Conclusion: TJ 1300+TJ Micromix is a viable means of biocontrol deliver on soybean and is a viable means of increasing the yield of soybean.
[0000]
TABLE 13
Effect of TJ1300 Liquid Biological Treatment Plus Liquid
TJ Micromix Fertilizer on Yield of Soybean Variety 91B52
Treatment
Ratio
Location
Trial
Yield
Control
0/0
Groton, SD
Liquid TJ
54.2 a
Micromix
TJ 1300
50/50
Groton, SD
Liquid TJ
60.8 b
Micromix
TJ1300 + TJ
50/50
Groton, SD
Liquid TJ
61.8 b
Micromix
Micromix
CV %
8.92
LSD (0.05)
4.19
SOYBEAN DRY GRANULE MICRO-NUTRIENT WORKING EXAMPLE
[0164] Materials and Methods: A field trial was conducted using the soybean variety Pioneer 91B52 at a location near Groton, S. Dak. The purpose of the trial was to compare the compatibility and yield benefit of the biocontrol preparation TJ1300 in combination with a dry granule micro-nutrient fertilizer vs. the micro-nutrient fertilizer alone vs. a control with no micro-nutrient fertilizer. Soybean yield in bushels per acre was used to measure the treatment response. The micro-nutrient fertilizer is sold commercially under the Trademark TJ Micromix™. Biocontrol treatments were prepared by adding 1×10 5 CFU per seed. The seed was planted at a seeding rate of 175,000 seeds per acre in 30-inch rows in a randomized, replicated block. TJ Micromix™ was applied at a rate of 20 pounds per acre. Each entry was replicated four times. The pathogen levels were natural populations at each location. The entries were as follows:
[0165] Control: Maxim
[0166] TJ Micromix
[0167] TJ 1300—50/50 combination of B. amyloliquefaciens TJ1000 or 1BE and T. virens G1-3
[0168] TJ Micromix+TJ 1300-50/50 combination of B. amyloliquefaciens TJ1000 or 1BE and T. virens G1-3
[0169] Results: As shown in Table 14, in this trial, the Granular TJ Micromix produced a significant yield increase compared to the control. When the seed-applied biocontrol treatment TJ1300 was applied in combination with the TJ Micromix, the treatment resulted in a significant increase in yield as compared to the control but not significantly different from the TJ Micromix application alone. The yield of the TJ 1300+TJ Micromix was numerically higher.
[0170] Conclusion: TJ 1300 is compatible with micro-nutrient applications and is a viable tool to increase the yield of soybean.
[0000]
TABLE 14
Effect of TJ1300 Biological Seed Treatment Plus Dry Granule
TJ Micromix Fertilizer on Yield of Soybean Variety 91B52
Treatment
Ratio
Location
Trial
Yield
Control
0/0
Groton, SD
TJ Micro
54.2 a
TJ Micromix
0/0
Groton, SD
TJ Micro
61.6 b
Granule
TJ 1300
50/50
Groton, SD
TJ Micro
62.5 b
TJ 1300 + TJ
50/50
Groton, SD
TJ Micro
63.3 b
Micromix
CV %
8.92
LSD (0.05)
4.19
SPRING WHEAT WORKING EXAMPLE
[0171] Materials and Methods: A field trial was conducted using Russ Spring wheat at a location near Kensal, N. Dak. The purpose of the trial was to test biocontrol TJ 1300 on spring wheat against an untreated control. The biocontrol TJ 1300 was applied to the seed so as to achieve an application rate of 2.5×10 9 CFU per acre. The plot was planted in a randomized, replicated block design with each entry replicated three times.
[0172] Result: As shown in Table 15, the entry TJ 1300 produced a non-significant yield increase. The conclusion was that TJ 1300 may be of value as a seed treatment on wheat.
[0000]
TABLE 15
Effect of TJ1300 Biological Seed Treatment Plus Fertilizer on
Russ Spring Wheat
Treatment
Ratio
Location
Trial
Yield
Control
0/0
Kensal,
MM
43.8
ND
1300
50/50
Kensal,
MM
44.0
ND
CV %
7.52
LSD (0.05)
NS
FIELD PEAS WORKING EXAMPLE
[0173] Materials and Methods: A field trial was conducted to compare the biocontrol treatment TJ 1300 to a non-treated control on field peas. The seed was treated with the biocontrol agent to achieve an application of 2.5×10 9 CFU per acre. Yield response was measured as pounds per acre.
[0174] Results: As shown in Table 16, the entry TJ 1300 produced a non-significant yield increase in field peas. The conclusion was that TJ 1300 may be an effective tool to increase the yield of field peas.
[0000]
TABLE 16
Effect of TJ1300 Biological Seed Treatment on Yield of
Integra Field Pea
Test
Treatment
Ratio
Rep
Location
Trial
Yield
weight
Control
0/0
Ave of 3
Carrington,
Pea
3590.0
62.9
ND
1300
50/50
Ave of 3
Carrington,
Pea
3613.0
63.5
ND
CV %
7
0.5
LSD (0.05)
ns
Ns
INCREASED MANGANESE UPTAKE WORKING EXAMPLE
[0175] A surprising aspect of the subject invention is that plants that grow from seeds treated with the disclosed combination experience increased uptake of manganese. The protective nature of increased manganese uptake is documented in Project S-269: Biological Control and Management of Soilborne Plant Pathogens for Sustainable Crop Production, 5 th International Conference on the Biogeochemistry of Trace Elements. Jul. 11-15 1999. Vienna, Austria, p. 1086-1087. Dr. Don Huber of Purdue University has documented the connection between an imbalance in the ratio of nitrogen to manganese and the incidence of stalk rot in corn. (Huber D. 2000. “Hidden Hunger” threatens many crops. Purdue News. Online at WWW URL purdue.edu/UNS/html4ever/0012.Huber.deficiency.html or news.uns.purdue.edu/UNS/html4ever/0012.Huber.deficiency.html
[0176] The disclosed combination of Trichoderma virens and Bacillus amyloliquefaciens for the purpose of plant pathogen control and increased plant yield thus has unexpected characteristics. The first is the fact that the combination produces an increase in yield, not just plant protection from the pathogen. Plant tissue analysis from test plots presented in Tables 17 and 18 below show an unexpected trend toward higher nutrient intake of a nutrient, manganese.
[0177] The treatments that produced the surprising results shown in Table 17 are defined as follows:
[0178] bs-unt-bt=Brookings, S. Dak. location—no treatment on the seed—Bt variety of corn
[0179] bs-max-bt=Brookings, S. Dak. location—chemical fungicide Maxim on the seed—Bt variety of corn
[0180] bs-1000-bt=Brookings, S. Dak. location— Bacillus amyloliquefaciens TJ 1000 on the seed-Bt variety
[0181] bs-0300-bt=Brookings, S. Dak. location— Trichoderma virens G1-3 on the seed—Bt variety of corn
[0182] bs-1300-bt=Brookings, S. Dak. location— B. amyloliquefaciens TJ 1000 and T. virens G1-3 (1 to 1 ratio) on the seed—Bt variety of corn
[0183] bs-1310-bt=Brookings, S. Dak. location— B. amyloliquefaciens TJ 1000 and T. virens G1-3 (7 to 3 ratio) on the seed—Bt variety of corn
[0184] bs-66/300-bt=Brookings, S. Dak. location— B. lentimorbus and T. virens G1-3 (1 to 1 ratio) on the seed—Bt variety of corn
[0000] The term “Bt” is defined as: A corn hybrid that has been genetically modified by the insertion of a gene from the bacteria Bacillus thuringiensis . The inserted gene produces a protein that will kill European corn bore that feed on the plant tissue.
[0000]
TABLE 17
Effects of Treatments on Plant Mineral Content on Bt Variety of Corn at Brookings
SD Location
Concentration
Treatment
N
P
K
Mg
Ca
S
Na
Fe
Mn
B
Cu
Zn
bs-unt-bt
3.43
0.39
1.65
0.66
1.11
0.29
0.003
110
105
17
18
32
bs-max-bt
3.42
0.43
2.10
0.56
0.91
0.27
0.005
117
91
14
18
29
bs-1000-bt
3.44
0.40
2.10
0.52
0.86
0.24
0.004
96
91
12
13
25
bs-300-bt
3.38
0.41
2.02
0.58
1.00
0.27
0.004
97
98
12
14
25
bs-1300-bt
3.36
0.43
1.89
0.66
1.11
0.27
0.004
118
134
13
16
28
bs-1310-bt
3.45
0.41
1.69
0.59
1.02
0.25
0.004
182
106
16
15
27
bs-66/300-bt
3.30
0.42
2.19
0.58
1.04
0.27
0.004
112
107
16
15
29
[0185] The treatments that produced the surprising results in Table 18 are defined as follows:
[0186] bl-unt-non=Brookings location—no treatment on the seed—non Bt variety of corn (non Bt can also be described as: non genetically modified)
[0187] bl-max-non=Brookings location—chemical fungicide Maxim on the seed—non Bt variety of corn
[0188] bl-1000-non=Brookings location— Bacillus amyloliquefaciens TJ 1000 on the seed—non Bt variety of corn
[0189] bl-300-non=Brookings location— Trichoderma virens G1-3 on the seed—non Bt variety of corn
[0190] bl-1300-non=Brookings location— B. amyloliquefaciens TJ 1000 and T. virens G1-3 on the seed (1 to 1 ratio)—non Bt variety of corn (one of the claimed combinations)
[0191] bl-1310-non=Brookings location— B. amyloliquefaciens TJ 1000 and T. virens G 1-3 on the seed (7 to 3 ratio)—non Bt variety of corn
[0192] bl-66/300-non=Brookings location— B. lentimorbus and T. virens G1-3 on the seed (1 to 1 ratio)—non Bt variety of corn
[0000]
TABLE 18
Effects of Treatments on Plant Mineral Content on Non Bt Variety of Corn at
Brookings SD Location
Concentration
Treatment
N
P
K
Mg
Ca
S
Na
Fe
Mn
B
Cu
Zn
bl-unt-non
3.33
0.39
1.93
0.55
0.85
0.21
0.005
76
103
12
13
24
bl-max-non
3.28
0.48
2.39
0.62
0.92
0.24
0.007
101
116
12
15
28
bl-1000-non
3.14
0.51
2.39
0.64
0.95
0.25
0.008
103
115
12
15
26
bl-300-non
3.19
0.48
2.21
0.65
0.93
0.24
0.009
95
99
15
15
24
bl-1300-non
3.38
0.48
2.43
0.60
0.96
0.25
0.006
111
137
13
15
26
bl-1310-non
3.21
0.46
2.18
0.68
1.03
0.26
0.007
108
117
18
16
25
bl-66/300-non
3.23
0.43
1.96
0.61
0.86
0.23
0.009
93
95
11
13
25
[0193] Manganese is known in the art as a disease prevention micronutrient. However, if manganese is added to fertilizer and applied to corn, the expected result is a decrease in yield. The significance of the subject invention is that it increases the manganese content of the corn plant while increasing yield. Furthermore, the increase in the manganese content in the plant does not occur with either organism alone or when the Trichoderma virens is combined with a different organism (e.g., treatment 66/300) or the formulation of the mixture is altered (e.g., treatment 1310). This increase in manganese content of the plant tissue is documented in tables 1 and 2 above on Bt (genetically modified) corn and conventional (non-genetically modified) corn. Tissue analysis of the corn in the charts above was done after the silking and pollination of the corn, documenting that this increase in manganese continues into the late stages of growth. Late season intake is significant because the lack of manganese in the plant is implicated in mid to late season stalk rot.
[0194] Data from disclosed combinations of the Trichoderma with other bacteria strains show that other combinations tested did not increase the manganese levels to the level of the present invention. It is surprising that neither organism alone increased the manganese level in the tissue of the corn. Only seed treatment with the claimed combination of the T. virens G1-3 fungus and the B. amyloliquefaciens bacterium increase the manganese level in the tissue of both the Bt and non-Bt corn.
CONSISTENCY OF INCREASED YIELD WORKING EXAMPLE
[0195] Another surprising aspect of the subject invention is unexpected consistency of increased yield: (1) consistency compared to either organism alone, in that our field trial results show the claimed combination to be significantly higher in yield over the control in both individual locations and multiple location and either organism alone did not produce a significant yield response over the control; (2) consistency across geography, in that the field trial results show the combination to be effective in a number of geographies from North Dakota to Arizona; and (3) consistency of higher yield in a more than one crop, in that the field data collected on corn, soybeans, sunflowers and wheat show significant increased in yield with the claimed combination. Field trial results are presented in the above working examples. The results of those field trials produced a surprisingly consistent yield response, and consistency is what is commercially important.
[0196] The disclosed combination of microorganisms gives more consistent yield response than either microorganism alone. The claimed combination produces a consistent increase in yield over a range of conditions while alone the microorganisms do not. The data in the patent application show this, but the data presented in Table 19 below that was produced at the experiment station in Carrington, N. Dak. show this effect.
[0000] TABLE 19 Consistency of Yield Response 2000 2001 2002 3 YR Control 96.9 146 87.7 110.2 Bacillus 93.3 150 94.9 112.7 T. virens 94.7 162 88.5 115.1 QuickRoot 105.6 156 90.4 117.3 1310 89.5 151 88.5 109.6
In Table 19, the treatments are defined as follows:
[0197] Control=chemical fungicide Maxim
[0198] Bacillus=B. amyloliquefaciens alone
[0199] T. virens=T. virens G1-3 alone
[0200] Quick Root=QuickRoots™ is the product name of the claimed combination of T. virens G1-3 and B. amyloliquefaciens
[0201] 1310= T. virens G1-3 and B. amyloliquefaciens at a 7:3 ratio.
[0202] The column headings in Table 19 denote the year of the trial with “3YR” indicating the average treatment response for the combined three years. Note that in 2000, seed treatment with the individual organisms alone (the individual components of the claimed combination) produced yields that were less than control. In 2001, seed treatment with individual organisms both produced yields that were greater than the control as did the claimed combination. In 2002, seed treatment with the individual organisms produced yields that were greater than the control and again the claimed combination increased yield as well.
[0203] The North Dakota data presented in Table 19 document consistency in two of ways. First, in reviewing year 2000 data, neither the Bacillus bacteria (1000) seed treatment nor the Trichoderma fungi (G1-3) seed treatment by themselves produced a positive yield response; but the claimed combination did produce a positive response. Two negative responses added together do not produce a positive. Synergism is what creates positive response from two negatives. In years 2001 and 2002, the performance of treatments with the bacteria and the fungi traded places as the top seat while the performance of the claimed combination performed between treatments with the individual components. Overall, the consistent performance of the claimed combination gave the largest yield advantage because of consistency of response. These data are from the same location; only weather changed from season to season. The Bacillus alone seed treatment did not perform well at all in the average and the Trichoderma alone seed treatment only averaged well because it had one great performance out of three.
[0204] Presented in Table 20 is a compilation of data from three years of field trials, 63 entries, at 12 locations. The test plots were located at North Dakota State University, University of Arizona, and Colorado State University. This compilation clearly shows the 50/50 combination of B. amyloliquefaciens+T. virens (one of the claimed combinations) produces a significantly higher yield than the control and than either organism alone. It should be noted that while the individual components show a numerical increase in yield, it is a non-significant increase at a 0.05 rejection level while the claimed combination is significant at a 0.05 rejection level.
[0000]
TABLE 20
QuickRoots ™ Effect on Corn Yield in Replicated Field Trials.
3 Year Average Evaluating QuickRoots ™/Maxim vs. Maxim
Treatment
Moisture
Yield
Pricing
Advantage
Control
17.5
154.77
$300.25
B. amyloliquefaciens alone
17.5
158.7
$307.88
$7.62
T. virens alone
17.4
158.81
$308.57
$8.31
B. amyloliquefaciens +
17.5
161.62
$313.54
$13.29
T. virens combined 50/50
Mean
17.5
158.88
$307.56
CV (%)
23.3
21.7
LSD (0.05)
.19(NS)
5.05
CORN VARIETY NK 2555 TREATMENT WITH OTHER STRAINS WORKING EXAMPLE
[0205] Materials and Methods: For these studies Trichoderma virens Gl-21 (an isolate that is commercially available from Thermo Trilogy Corporation) and Bacillus subtilis var. amyloliquefaciens FZB24 (a strain that is commercially available from Earth Biosciences, Inc.) were selected. The plot entries (treatments) were as follows:
[0206] Treatment A—Control (MAXIM, industry standard fungicide seed treatment)
[0207] Treatment B—T virens G1-3+ Bacillus subtilis var. amyloliquefaciens TJ 1000
[0208] Treatment C— T. virens Gl-21+ Bacillus subtilis var. amyloliquefaciens TJ 1000
[0209] Treatment D— T. virens G1-3+ Bacillus subtilis var. amyloliquefaciens FZB24
[0210] Treatment E— T. virens Gl-21+ Bacillus subtilis var. amyloliquefaciens FZB24
[0211] The treatments were applied to corn seed (NK 2555) at equal rates of at least 1×10 6 fungal spores and 1×10 6 bacterial spores per seed. Previous field trials had confirmed that Treatment B produced an unexpected synergism that consistently and significantly increased yield in plants. The follow up field trials were conducted with the same test protocol as the initial trials and set up as a randomized-replicated block.
[0212] Results: Presented in Table 21 are the results of this trial. In this trial, all of the T. virens—Bacillus subtilis var. amyloliquefaciens combinations produced a numerically positive response. These results gave strong indication that combinations of T. virens and Bacillus subtilis var. amyloliquefaciens produce a synergistic effect that is similar to that discovered when Trichoderma virens G1-3 and Bacillus subtilis var. amyloliquefaciens TJ 1000 were combined and placed in the vicinity of the seed.
[0000]
TABLE 21
Treatment of Corn Variety NK 2555 with Other Strains and Isolates
Treatment
Test Weight
Moisture
Yield
A
55.9
21.8
173.6
B
56.9
20.4
177.2
C
56.9
20.3
183.2
D
56.3
20.9
181.1
E
55.7
20.6
182.2
C.V.
5.4
LSD .05
16.3
CORN VARIETY NK 3030 BT TREATMENT WITH OTHER STRAINS WORKING EXAMPLE
[0213] This trial compared the treatment of Trichoderma virens G1-3 and Bacillus subtilis var. amyloliquefaciens TJ 1000 vs. Trichoderma virens GL-21 and Bacillus subtilis var. amyloliquefaciens FZB24 vs. a control (Maxim, industry standard fungicide seed treatment). Plot entries were as follows:
[0214] Treatment A—Control (MAXIM, industry standard fungicide seed treatment)
[0215] Treatment B— T. virens G1-3 and Bacillus subtilis var. amyloliquefaciens TJ 1000
[0216] Treatment C— T. virens Gl-21 and Bacillus subtilis var. amyloliquefaciens FZB24
[0217] Materials and Methods: Corn seed (NK 3030 Bt) was treated at the same rate of Bacillus and Trichoderma as in the previous working example and the seed was planted in a randomized-replicated block design.
[0218] Results: Presented in Table 22 are the results of this trial. In this trial, the yields of Treatments B and C were significantly greater than the control. Treatment B was numerically superior to Treatment C but not significantly. The results of this trial also indicated that other combinations of T. virens and Bacillus subtilis var. amyloliquefaciens can be expected to show a synergistic response.
[0000]
TABLE 22
Treatment of Corn Variety NK 3030 Bt with Other Strains
and Isolates
Treatment
Test Weight
Moisture
Yield
A
52.5
21.5
172.1
B
54.6
21.5
210.0
C
55.3
21.6
192.8
C.V.
8.09
LSD .05
19.43
COMBINED TRIALS WITH OTHER STRAINS WORKING EXAMPLE
[0219] This example compared the same treatments as the previous working example, which were as follows: Trichoderma virens G1-3 and Bacillus subtilis var. amyloliquefaciens TJ 1000 vs. Trichoderma virens Gl-21 and Bacillus subtilis var. amyloliquefaciens FZB24 vs. a control (MAXIM). This trial differed from the previous working example because it compared 43 entries from 12 locations and 6 different corn hybrids. Plot entries were as follows:
[0220] Treatment A—Control (MAXIM, industry standard fungicide seed treatment)
[0221] Treatment B— T. virens G1-3 and Bacillus subtilis var. amyloliquefaciens TJ 1000
[0222] Treatment C— T. virens Gl-21 and Bacillus subtilis var. amyloliquefaciens FZB24
[0223] Materials and Methods: Seed was treated the same as in the previous two trials and each location was randomized and replicated.
[0224] Results: Presented in Table 23 are the results of this trial. This trial used a larger data set and revealed that the yield increase with the originally discovered combination of Treatment B ( Trichoderma virens G1-3 and Bacillus subtilis var. amyloliquefaciens TJ 1000) is significantly greater than the control while the yield increase with Treatment C ( T. virens Gl-21 and Bacillus subtilis var. amyloliquefaciens FZB24) is not significantly greater, even at the 0.20 rejection level. However, Treatment C did not show a numerical yield decrease nor did it show a significant yield decrease compared to the control. A yield decrease compared to the control would most likely have occurred if the microorganisms in the combination were antagonistic to each other. This result clearly showed that the original discovery (Treatment B) was superior to the Treatment C. The result also showed that Treatment C is a potentially beneficial treatment.
[0000]
TABLE 23
Treatment with Other Strains and Isolates
Treatment
Yield in Bushels per Acre
A
153.84
B
160.63
C
156.36
C.V.
3.42
LSD .20
4.4
[0225] Many variations of the invention will occur to those skilled in the art. Some variations include non-competitive culturing of the biocontrol organisms. Other variations call for competitive culturing. All such variations are intended to be within the scope and spirit of the invention. | A seed treated with a fungal/bacterial antagonist combination and a seed assembly comprising a seed and a fungal/bacterial antagonist combination. The fungal/bacterial antagonist combination comprises a Trichoderma virens fungal antagonist and a Bacillus amyloliquefaciens bacterial antagonist for controlling plant pathogens as a biocontrol agent, bio-pesticide or bio-fungicide. In preferred embodiments, the invention produces an increase in plant yield. Control of early and late season stalk and root rot caused by fungi such as Fusarium, Phythium, Phytophthora and Penicillium in tomatoes, peppers, turf grass, soybeans, sunflower, wheat and corn is achieved. | 0 |
This application is a continuation of application Ser. No. 07/197,004, filed May 20, 1988 now abandoned.
BACKGROUND OF THE INVENTION
This invention relates to programmable controllers and to integrated circuits for interfacing peripheral devices to computers.
There are a number of peripheral interface controller chips known in the art. Such devices typically include a data bus for receiving data or commands from a host CPU, and an address bus for receiving an address from the host CPU. The received data (or command) is placed in an appropriate register selected in response to the received address. The controller then sends appropriate commands or data to the peripheral device in response to the data or command received from the host CPU. Such controllers can control peripheral I/O devices so that the host CPU need not spend time performing peripheral device control tasks.
As peripheral devices become faster, it is necessary to provide controllers capable of great speed and efficiency. Accordingly, it is an object of the present invention to provide a controller capable of performing a number of tasks in parallel to enhance controller speed and efficiency.
SUMMARY
A controller constructed in accordance with my invention controls a peripheral device and facilitates communication of data and commands between the peripheral device and a host CPU. The controller includes a CPU, a memory for providing instructions to the CPU, and a sequencer for providing addresses to the memory. The memory output words include three fields: a first field for providing instructions and branch addresses to the sequencer, a second field for providing instructions to the CPU, and a third field which provides data or instructions to the peripheral device. The controller also includes an I/O port for permitting the host CPU to provide data to the peripheral device, and an address counter for permitting the controller to provide sequential addresses to the peripheral device (e.g. to facilitate DMA operations). Thus, the architecture of the controller permits a number of functions to be performed simultaneously, quickly, and efficiently.
The host CPU communicates with the controller asychronously by storing data and instructions in a FIFO memory. In one embodiment, each data word stored in the FIFO memory has two fields: an address field and a command/data field. A first bit within the address field indicates whether the information in the command/data field is a command or data. If the information in the command/data field is a command it is used as a vector branch address by the sequencer. If it is data, it is stored in one of a plurality of registers selected by the address in the address field. Thus, because of the unique FIFO interface circuit, a single word of data loaded into the FIFO memory in one write cycle contains either a command or data. The controller does not need to fetch an additional word of information from the FIFO to determine whether it is a command or data, and if it is data, the controller does not need to fetch an additional word of information to determine where that data is to be stored. Thus, the interface circuit of the present invention is extremely efficient.
My invention is better understood with reference to the detailed description below.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates a programmable controller 100 for controlling a peripheral device 104.
FIG. 2 illustrates a sequencer used to address an EPROM in the controller of FIG. 1.
FIG. 3 illustrates data flow paths of operand and resultant data received and provided by CPU 110 of FIG. 1.
DETAILED DESCRIPTION
FIG. 1 is a block diagram of a programmable controller 100 constructed in accordance with my invention. Referring to FIG. 1, controller 100 receives commands and data from a host computer 102, and in response thereto, controls a peripheral device 104. Peripheral device 104 can be any conventional type of I/O device.
The main blocks of controller 100 include a CPU 110, an EPROM 112 for providing instructions to CPU 110, and a sequencer 114 for addressing EPROM 112.
During operation, an instruction counter 113 within sequencer 114 provides sequential addresses to EPROM 112, which provides a 64 bit output word in response thereto. A first group of bits from the output word are communicated as an instruction or data to CPU 110 via a pipeline register 115, and a 28 bit bus 116. A second group of bits from the EPROM output word are communicated back to sequencer 114 via pipeline register 115, a 20 bit bus 120, and a multiplexer 121. The data on bus 120 can include a branch address to be loaded into sequencer 114 under appropriate conditions (described below) or can comprise other instructions to be executed by sequencer 114 (e.g. a call instruction, a conditional branch, etc., as discussed below).
A third group of bits is communicated from EPROM 112 to a 16 bit output bus F via pipeline register 115. Output bus F can be used for providing user programmable instructions to peripheral device 104. (Various lines of bus F can also be coupled to provide user-programmable signals to host processor 102.)
In one embodiment, EPROM 112 is programmed using a circuit described in copending U.S. patent application Ser. No. 07/197,008, filed on May 20, 1988 by De Hieu Nguyen, entitled "Structure for Programming an EPROM", now abandoned, incorporated herein by reference.
Also illustrated in FIG. 1 is an I/O port 124 coupled to an 8-bit I/O bus 126 which facilitates exchange of data and commands between CPU 110 and peripheral device 104.
Data and instructions are exchanged between host CPU 102 and controller 100 via a 16 bit data bus HD, a 6 bit address bus HAD, and a host interface circuit 106. Host interface circuit 106 also receives a chip select signal CS, a write enable signal WR, and a read enable signal RD to control data flow between microprocessor 102 and controller 100.
Host interface circuit 106 loads the signals from buses HD and HAD into 8 word by 22 bit FIFO memory 108. In response to an instruction from EPROM 112, a word stored in FIFO memory 108 can be read by controller 100.
Five of the six bits of data originating from bus HAD which are read from FIFO memory 108 are used to select one of 32 registers 136 within CPU 110 where data originating from bus HD is to be stored. The sixth bit from bus HAD read from FIFO memory 108 determines whether the sixteen 16 bits of data received from bus HD are a command or are data. If the sixth bit (HAD-B) is a zero, the data from FIFO memory 108 originating from bus HD is stored in the register within registers 136 selected by the 5 lowest bits of bus HAD for future use as an operand. If bit HAD-5 is a one, the sixteen bits of data which originated from bus HD are communicated to sequencer 114 and are used as a branch address. Thus, host CPU 102 can command sequencer 114 to branch to an address where desired instructions are stored.
Host processor 102 can also read various registers within controller 100 via interface circuit 106. Table I below lists the various registers that can be read from or written to by host process 102.
TABLE I__________________________________________________________________________ ##STR1## ##STR2## ##STR3## HAD-5 HAD-0 to HAD-4 HD Operation__________________________________________________________________________0 1 0 0 Register Address Data Write data to FIFO 1080 1 0 1 Don't care Command Write command to FIFO 108. Data originating from bus HD serves as branch address.0 0 1 0 00000 Read contents of I/O Port 124 (Contents of port 124 loaded onto bus HD)0 0 1 0 00100 Reset controller 1000 0 1 0 00010 Read the contents of instruction counter 113 within sequencer 114.0 0 1 0 00001 Read Status register 139 (within interface circuit 106)__________________________________________________________________________
The status register 139 comprises a FIFO input ready signal FIIR (i.e. a flag indicating that FIFO memory 108 is ready to accept data) and bits HAD-5 of each of the 8 words in FIFO memory 108.
Address Counter and Block Counter
Programmable controller 100 includes an address counter 128 which can be loaded by CPU 110, and enabled or disabled by writing appropriate data to the ACEN bit of a configuration register 140. Counter 128 can be configured to operate as either a 16 bit counter or a 22 bit counter, depending on the state of the AC22 bit (bit 9) of an I/O configuration register 141. (Configuration register 140 and I/O configuration register 141 are loaded with data from EPROM 112 in a manner described below.) When enabled, address counter 128 increments every instruction cycle of CPU 110. When counter 128 is a 16 bit counter, the contents of address counter 128 can be presented on a 16 bit address bus ADD via multiplexer 142. When address counter 128 is in the 22 bit mode, only the higher 16 bits of counter 128 are presented on bus ADD, while the lower 6 bits can be used to drive bus HAD. (Multiplexer 142 drives bus ADD with either the contents of address counter 128 or an address register 144, depending on the state of the ASEL bit of configuration register 140.)
Bus ADD is typically connected to peripheral device 104. Address counter 128 can be used to provide sequential addresses to peripheral device 104, e.g. to perform DMA operations. Address counter 128 can also serve as an event counter. When the contents of address counter 128 are all ones, a flag signal ACO is generated.
Controller 100 also includes a block counter 146 which can be loaded with data by CPU 110 or read by CPU 110. Block counter 146 is a 16 bit down counter which decrements every instruction cycle of CPU 110 when enabled by bit BCEN of configuration register 140. Block counter 146 generates a flag BCZ when its contents reach zero. Block counter 146 can be used in DMA operations, e.g. by causing controller 100 to branch to a routine which disables address counter 128 after address counter 128 generates a predetermined number of addresses.
Program Control
As mentioned above, sequencer 114 includes program counter 113 for providing sequential addresses to EPROM 112. Also provided in sequencer 114 is a 15 level stack 204 (FIG. 2) for storing return addresses for subroutine calls or interrupt service routines. When stack 204 is one level away from being full, an interrupt, if enabled, will occur.
Sequencer 114 also includes a loop counter 205, i.e. a 10-bit programmable counter which decrements after each instruction. Loop counter 205 can be used to execute loops, e.g. to execute a set of instructions a predetermined number of times. Loop counter 205 can also be used as a source of addresses to be presented to EPROM 112.
The functions performed by sequencer 114 are controlled by 20 bit bus 120, which is driven by pipeline register 115. Bus 120 is divided into a group of 10 data lines 120a, 4 instruction lines 120b, and 6 condition code select lines 120c. Instructions on instruction lines 120b are decoded by instruction decoder 208, which causes sequencer 114 to execute one of 16 instructions. The instruction set for sequencer 114 is similar to the instruction set of device number Am2910, manufactured by Advanced Micro Devices, and described at pages 2-88 to 2-100 of "The Am2900 Family Data Book" published by Advanced Micro Devices, Inc in 1978, incorporated herein by reference.
The instructions executed by sequencer 114 include conditional jump and conditional call statements which are executed in response to condition signal CC and condition enable signal CCEN. These signals are used by instruction decoder 208 in a manner discussed in the above mentioned Am2900 Family Data Book. Signals CC and CCEN are generated by condition code logic 210 in response to a set of flag signals, interrupt signals, and condition code signals. The interrupt signals are provided on lines INT0 to INT4 from sources external to controller 100, e.g. host CPU 102 or peripheral device 104. The condition code signals are provided on condition code leads CC0 to CC7, also by sources external to controller 100. Condition code logic 210 also receives other flags generated by controller 100 (discussed below), as well as the signals on condition code select lines 120c from EPROM 112. The signals on lines 120c are used to select a condition code signal, interrupt signal, or flag which is in turn used to generate signals CC and CCEN. Signals CC and CCEN are tested by instruction decoder 208 for conditional branching.
The flag signals received by condition code logic 210 generated by controller 100 are as follows:
______________________________________Flag Interpretation______________________________________ACO Address counter 128 is all onesSTKF Stack 204 fullFIIR FIFO input ready (i.e. space available in FIFO 108)DOR I/O port 124 has been readINT An interrupt has occurredBCZ Block counter 146 all zerosFIOR FIFO 108 has at least one messageFICD FIFO 108 top message is a commandS Most significant bit as a result of last operation of CPU 110 was a 1O Most recent operation of CPU 110 caused an overflowZ Most recent operation of CPU 110 generated a zeroCY Most recent operation of CPU 110 generated a carry signal or a borrow signal______________________________________
Sequencer 114 includes a zero detect circuit 209 which generates a signal on a lead R which indicates that the contents of loop counter 205 are zero. Decoder 208 responds to the signal on lead R in a manner described in "The Am2900 Family Data Book".
Sequencer 114 includes a breakpoint register 214 which can be loaded with data from data lines 120a. (Breakpoint register 214 is loaded with data from lines 120a when the value on condition code select lines 120c is a predetermined value not used by condition code logic 210.) When the contents of breakpoint register 214 equals the contents of program counter 113, an interrupt, if enabled, will occur.
As mentioned above, controller 100 includes four interrupt leads INT0 to INT4 for receiving interrupt signals. Leads INT0 to INT4 are coupled as input leads to interrupt logic 212. In addition, other conditions within controller 100 can generate interrupt signals which are received by interrupt logic 212. Each interrupt, when enabled, causes interrupt logic 212 to load a branch address into program counter 113, thereby causing sequencer 114 to branch to a selected address in EPROM 112 as indicated in Table II below.
______________________________________BranchAddress Priority Source______________________________________0000 lowest External reset low0008 External interrupt signal INT00009 External interrupt signal INT1000A External interrupt signal INT2000B External interrupt signal INT3000C Always active unless masked000D FIFO 108 full000E Contents of Breakpoint register 214 equals program counter 113000F highest Stack 204 full, Address counter 128 all ones, or FIFO 108 input ready.______________________________________
During an interrupt, the previous contents of program counter 113 are saved in stack 204. Of importance, the above interrupts can be masked by writing appropriate data to an interrupt mask register 143.
It is noted that controller 100 contains a number of registers, including mask register 143, configuration register 140, I/O configuration register 141, and an I/O special function register 145. These registers are loaded with data from lines 120a in response to predetermined values on lines 120c not used by condition code logic 210. The functions performed by these registers are discussed below.
The data from lines 120a can also be stored in one of registers 136.
CPU 110
As mentioned above, CPU 110 receives 28 signals from EPROM 112 as follows: a five bit A address bus 300 (FIG. 3), a five bit B address bus 301, a 9 bit instruction word I, 2 bits of carry-in data T, and 7 bits 302 which define the source of data supplied to CPU 110 and the destination of output data provided by CPU 110.
The 9 bit instruction word I is interpreted by CPU 110 in the same manner as the instruction bus I of device number Am2901, manufactured by Advanced Micro Devices, Inc., and described at pages 2-2 to 2-25 of the above-incorporated "Am2900 Family Data Book". The structure of CPU 110 is similar to that of the Am2901, except that CPU 110 is a 16 bit device, whereas the Am2901 is a 4 bit device.
The five bit A address bus 300 and B address bus 301 each select a register within registers 136 as a source of operand data on an A operand input bus 110a and a B operand input bus 110b. The data on the A operand input bus 110a and B operand input bus 110b is used in the same manner as the A and B data buses described in the "Am2900 Family Data Book".
CPU 110 includes a D input bus 302 (which functions in the same manner as the Am2901 D bus) which can receive input data from a multiplexer 308. Multiplexer 308 can provide data from the following sources:
1. I/O port 124;
2. An address input register 304;
3. The high and low order bits of address counter 128;
4. A data input register 106a;
5. A swap register 306;
6. FIFO register 108; and
7. Lines 120a from EPROM 112.
The output data from CPU 110 can be stored in any of the following destinations:
1. I/O port 124;
2. Address register 144;
3. The low and high order bits of address counter 128;
4. Block Counter 146; and
5. A data output register 106b.
Of importance, the source of operand data for D input bus 302 and the destination of output data is selected by seven output lines 116a which are part of EPROM output lines 116.
Address input register 304 is coupled to 16 bit bus ADD. When the output drivers which are used by controller 100 to drive bus ADD are disabled (e.g. by writing a zero to the ADOE bit of configuration register 140) bus ADD can be used as an address input bus, and data from bus ADD is clocked into address input register 304 each instruction cycle. Address input register 304 can be used as D operand data by CPU 110 as described above.
Also listed as a source of operand data is a data input register 106a within interface circuit 106. When line CS is tied high, FIFO 108 is disabled, and when data is written via 16 bit bus HD to interface circuit 106, it is stored in data input register 106a instead of FIFO memory 108.
Swap register 306 receives output data from CPU 110 every instruction cycle (and is thus always enabled as an output data destination) and swaps the upper and lower order bytes. Swap register 306 can be selected as a source of D operand data.
Data output register 106b is part of interface circuit 106b. Data from output register 106b is provided on leads HD by interface circuit 106 when signal CS is high and signal RD is low.
I/O PORT 124
I/O port 124 can serve as a general purpose input port or a general purpose output port, depending on the data in an I/O configuration register 141, and an I/O special function register 145. I/O configuration register 141 governs whether the individual pins of I/O port 124 are input pins or output pins.
Pins 0 to 7 of port 124 are also controlled by special function register 145 as follows:
______________________________________ Special Function Reg-I/O Pin ister 145 As input pin As output pin______________________________________I07 0 Simple input Simple output 1 Simple input Signal FIIR (FIFO input ready)I06 1 Simple input Simple output 0 AOE (output enable Not Allowed for bus ADD)I05 1 Simple input Simple output 0 ADOE (output enable Not Allowed for bus HAD)I04 1 Simple input Simple output 0 DOE (output enable Not Allowed for bus HD)I03 0 Simple input Simple output 1 QO Shift register Q15 Serial serial input OutputI02 0 Simple input Simple output 1 Q15 Serial input QO Serial OutputI01 1 Simple input Simple output 0 ACEN Not AllowedI00 1 Simple input Simple output 0 BCEN Reserved______________________________________
Bits ADOE, DOE, ACEN and BCEN are also control bits within configuration register 140. However, when bit 6 of special function register 145 is a zero, I/O port 124 bit 6 controls the output enable for bus ADD. Similar, bits 0, 1, 4 and 5 can be programmed to override corresponding bits in register 140.
Bits 3 and 2 can be programmed as the Q shift register input/out leads. The Q shift register (not shown) is part CPU 110, and performs the same function as a corresponding Q shift register in the Am2901.
Configuration Register 140
Controller 100 includes a 10 bit configuration register 140, the contents of which are as follows:
______________________________________BIT NAME FUNCTION______________________________________0 ACEN enables or disables address counter 1281 BCEN enables or disables block counter 1462 DOE sets lines HD as controller output lines3 ADOE sets lines HAD as output lines4 AOE Sets lines ADD as output lines5,6 DSEL0,DSEL1 Gives source of data when RD is asserted by host as follows:00 None01 Status register 13910 Microprocessor data output register 106b11 Program Counter 1137 DIREN Causes data from bus HD to go to address register 106a8 AIREN Causes data from HD bus to go to address register 1149 ASEL Causes lines ADD to provide contents of address counter 138. Otherwise contents of address register 144 are provided on bus ADD______________________________________
I/O Configuration Register 141
The I/O configuration register is a 10 bit register. Bits 0 to 7 determine whether corresponding bits of I/O port 128 are input leads or output leads. Bit 9 is not assigned. Bit 10 is signal AC22, which determines whether address counter 128 is a 16 or 22 bit counter.
Special Function Register 145
The special function register bits are as follows:
______________________________________Bit______________________________________0 1NTR Enables/disables all interrupts. When interrupts are disabled, they can be tested by condition code logic 210.1 Not Available2 BCENI When BCENI is set, the block counter enable signal BCEN is connected to I/O port 124 pin 0. Otherwise, BCEN signal is generated by control register 140.3 ACEBI When ACEBI is set, address counter 128 enable bit ACEN is connected to pin 1 of I/O port 124. Otherwise, ACEN Bit is generated by control register 140.4 SIO EN When SIO EN is set, pins 2 and 3 of I/O port 124 are connected to ALU Q register least and most significant bits, respectively, so that pins 2 and 3 can serve as serial I/O pins. Otherwise, pins 2 and 3 of I/O port 124 are used as general purpose I/O pins.5 DOEI When set, pin 4 of I/O port 124 serves as the output enable pin for HD bus.6 ADOEI When set, pin 5 of I/O port 124 serves as the output enable for HAD bus.7 AOEI When set, I/O port 124 bit 6 serves as the output enable for ADD bus.8 FIFOIR When set, FIFO input ready signal appears on pin 7 of I/O port 124.9 FIRST FIFO reset bit.______________________________________
While the invention has been described with regard to specific embodiments, those skilled in the art will appreciate that changes can be made in form and detail without departing from the spirit and scope of the invention. For example, controller 110 can be used as a standalone controller which does not receive instructions from host processor 102. Accordingly, all such changes come within the present invention. | A programmable controller includes an interface circuit for communicating with a host CPU. The interface circuit includes a FIFO memory having a plurality of locations, each location receiving address and data information. The data information can either be an operand or a command. Whether the data information is an operand or a command is determined by one of the bits of the address. If the data information is an operand, it is stored at a location determined by the address. Accordingly, in a single host CPU cycle, the host CPU can write one word to the controller which comprises either a command or data and the address where the data can be stored. Multiple cycles are not required to provide a single instruction or data to the controller. Further, because a FIFO memory is used, a plurality of instructions are loaded into the controller and the controller and the host CPU can operate asynchronously. The controller also includes an EPROM for providing instructions to an internal CPU and a sequencer for providing addresses to the EPROM. The EPROM provides an output word including a bit field containing instructions for the sequencer, a bit field containing instructions for the CPU, and a bit field including instructions which are sent directly to the peripheral device. Accordingly, the controller can perform a plurality of instructions in parallel. | 6 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention pertains to power transmission, and more particularly to apparatus for driving tracked carriages.
2. Description of the Prior Art
Mobile storage systems for storing books, supplies, and files are well known. Such systems provide high density storage, and therefore they save valuable space in offices, schools, and libraries.
Typical mobile storage systems include two or more parallel rails embedded in or attached to a building floor. One or more relatively long and narrow carriages span the rails. The carriages may be as long as thirty feet, and the number and spacing of the rails are chosen to suit the particular carriage length. The carriages are usually supported by a pair of wheels rolling along each of the rails.
The carriages may be designed to move along the rails under manual power. For that purpose, a hand wheel is usually mounted to a carriage end panel. The hand wheel is connected by various drive components to a shaft that in turn is connected with at least one of the carriage wheels. Manually rotating the hand wheel causes the drive wheels to rotate and move the carriage. Electrically powered carriages are also in wide-spread use. With that design, a suitable electric motor is substituted for the manual hand wheel. The motor shaft is mechanically connected through a suitable mechanism to the carriage drive wheels.
It has been a common practice to design mobile carriages such that the drive wheels are located on the two ends of the carriages. That is, the carriages are driven by a wheel supported on each of the two outermost rails, and the center regions of the carriages are supported on the interior rails by non-driving wheels. In some designs, there is a driving wheel on each of the rails. Those designs require multiple locations of the drive wheels, which is undesirably expensive. Further, the prior design requires a long shaft for connecting the drive wheels on the carriage ends. The long shafts are awkward to assemble and service. In addition, the long shafts may undergo torsional wind-up when used with heavy carriages, such that the drive wheels at the carriage end remote from the electric motor or hand wheel do not rotate in synchronization with the drive wheels at the carriage hand wheel or motor end. Consequently, despite flanges on the drive wheels, the carriages can tend to skew as they are driven along the rails.
Thus, a need exists for improved driving mechanisms for mobile storage carriages.
SUMMARY OF THE INVENTION
In accordance with the present invention, an economical center drive is provided that improves the performance of mobile storage system carriages. This is accomplished by apparatus that includes components that drive the mobile carriages solely from near the centers of the respective carriages.
Each carriage of the mobile storage system is supported by conventional non-driving wheels on all the system rails except the center rail. Synchronized transversely spaced drive wheels engage the center rail or mid rail. Preferably, the drive wheels have central flanges that fit within and are guided by a longitudinal groove in the rail top surface.
To drive the carriage drive wheels in synchronization, they are provided with respective sprockets. A chain is trained around the sprockets. The chain is driven by a driver sprocket that is journaled in the carriage frame. The driver sprocket is fixed to the shaft of an electric motor or to the output shaft of a speed reducer mounted to the carriage frame proximate the drive wheels. To provide tension adjustment to the drive wheel chain, the driver sprocket bearings are received within slots in the carriage frame. Varying the position of the driver sprocket bearings within the carriage frame slots also varies the driver sprocket position and the drive wheel chain tension. In an alternate construction, the motor may be stationarily mounted to the carriage frame, with an idler sprocket movably mounted within the frame to adjust chain tension. By locating the electric motor and drive wheels at the center of the carriage, the previously required long drive shaft between the two carriage ends is eliminated. In addition, the synchronized drive wheels on the single center rail improve carriage tracking and performance.
The center drive carriage of the present invention may also be used with manually powered carriages. In that instance, a relatively short shaft is used to join the portions of the drive mechanism associated with the hand wheel to the wheel driving chain at the center of the carriage. A driver sprocket is fixed to the shaft end at the carriage center for driving the chain trained over the drive wheel sprockets. Like the electrically powered carriage, the manually driven driver sprocket is journaled in bearings that are received in slots in the carriage frame. The driver sprocket is thus adjustable to a location that produces proper tension for the drive wheels chain. In an alternate design, the driver sprocket bearings are fixedly mounted to the carriage frame, and an adjustable idler sprocket is provided to set the proper chain tension.
Other benefits and features of the present invention will become apparent to those skilled in the art upon reading the disclosure.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a simplified side view of a mobile storage carriage that advantageously employs the present invention;
FIG. 2 is a cross sectional view taken along lines 2--2 of FIG. 1 and rotated 90° counterclockwise;
FIG. 3 is an enlarged cross sectional and partially broken view taken along lines 3--3 of FIG. 2;
FIG. 4 is a cross sectional view taken along lines 4--4 of FIG. 3;
FIG. 5 is an exploded partially broken perspective view of an electrically powered drive mechanism according to the present invention;
FIG. 6 is a view similar to FIG. 2, but showing a manually powered mobile carriage according to the present invention;
FIG. 7 is a view generally similar to FIG. 3, but showing the design of the manually operated carriage of FIG. 6;
FIG. 8 is an exploded partially broken perspective view of the drive mechanism of the manually powered mobile carriage;
FIG. 9 is a view similar to FIG. 3, but showing an alternate construction of the present invention;
FIG. 10 is a partially broken perspective view of the carriage drive of FIG. 9;
FIG. 11 is a view generally similar to FIG. 9, but showing an alternate design of a manually powered mobile carriage according to the present invention; and
FIG. 12 is an exploded partially broken perspective view of the manually powered carriage drive of FIG. 11.
DETAILED DESCRIPTION OF THE INVENTION
Although the disclosure hereof is detailed and exact to enable those skilled in the art to practice the invention, the physical embodiments herein disclosed merely exemplify the invention which may be embodied in other specific structure. The scope of the invention is defined in the claims appended hereto.
Referring to FIG. 1, a mobile storage carriage 1 is illustrated that includes the present invention. The mobile carriage 1 is typically part of a mobile storage system that includes additional mobile carriages, as well as one or more stationary units, not shown, as are known in the art.
The mobile carriage 1 travels along two or more parallel rails 7 spaced longitudinally along the carriage length and embedded in or attached to a building floor 9. The carriage is supported on the rails 7 by respective pairs of wheels 11. Power for moving the carriage along the rails may be supplied manually. In that case, the ends of the carriage are usually furnished with a hand wheel 13. Alternately, the carriage may be designed with an electrically powered system. In that situation, the hand wheel 13 is eliminated, and a suitable electrical control, schematically represented at reference numeral 15, is substituted.
In accordance with the present invention, electrically and manually powered mobile carriages are driven along the rails 7 through synchronized wheels that engage a single mid rail. Looking also at FIG. 2, a typical mobile storage system is depicted that has five rails. The center rail is designated as reference numeral 7a. The frame 17 of a carriage 1 is designed with longitudinal beams 19 and with a cross brace 21 over each of the rails except the mid rail 7a. At least two wheels 11 are suitably journaled in each cross brace 21 for supporting the carriage on the associated rail. The mounting of the wheels to the cross braces may be by conventional components that form no part of the present invention.
To drive the carriage 1 along the rails 7 and 7a, the carriage frame 17 comprises a pair of drive wheels 23. Referring also to FIGS. 3-5, the drive wheels 23 are rotatably mounted, as by bearings 24, on respective axles 25. The axles 25 are supported between channels 27 and 28 that span the frame longitudinal beams 19. To each drive wheel is attached a sprocket 29, as by plug welds 30. Trained over the sprockets 29 is a chain 31. The chain 31 is driven by a driver sprocket 33 that is fastened to the output shaft 35 of a combination electrical motor and speed reducer 41. The motor and speed reducer 41 is mounted to the channel 27 by conventional fasteners 54 passing through vertical slots 43 in the channel.
To provide adjustability to the chain 31, adjusting screw 45 coacts between the flange 47 of the channel 27 and the motor housing 41. The adjusting screw 45 assists positioning the motor and thus the motor output shaft 35 within the channel hole 44 for applying proper tension to the chain. When the shaft 35 is in the proper location, the fasteners 54 are tightened to the channel. Actuation of the control 15 energizes the motor 41 to rotate the drive wheels 23 in synchronization and move the carriage 1 along the rails 7 and 7a.
To guide the carriage 1 on the rails 7 and 7a, each drive wheel 23 is formed with an annular flange 49 that extends concentrically from the wheel peripheral bearing surface 50. The drive wheel flanges 49 interfit within grooves 51 formed in the top surface of the rail 7a. In FIGS. 3 and 4, reference numerals 52 represent decorative or safety floor panels placed between the rails, as is known in the art.
Turning to FIGS. 6-8, a manually powered version of the present invention is illustrated. As with the electrically powered version described previously in connection with FIGS. 1-5, the manual version includes one or more carriages 52, each having a frame 17' comprised of longitudinal beams 19' and cross braces 21'. Support wheels 11' are journaled to the cross braces 21' for supporting the carriage 52 on the rails 7. The center rail 7a is grooved at 51 to accept the flanges 49' of the drive wheels 23'. To each drive wheel 23' is fixed a sprocket 29'. A chain 31' is trained over the sprockets 29'. To drive the chain 31', a driver sprocket 53 is fixed to one end of a shaft 55, and the chain 31' is also trained over the sprocket 53. The shaft 55 is journaled in the carriage channel 27' by means of a flangette bearing 57 that is movably secured to the carriage frame 17' by conventional fasteners 58 passing through channel slots 59. The drive for the manual mobile carriage 52 further comprises an idler sprocket 56 for the chain. The idler sprocket 56 is mounted for rotation on suitable bearings supported by a stub shaft 62 that is fixed to the channel 27'. The flangette bearing 57 is adjustably positionable relative to channel hole 60. Adjusting screw 45' coacts between the channel 27' and the flangette bearing to aid adjusting the flangette bearing and thus the shaft 55 to provide variable tension to the chain 31'.
The manually powered carriage 52 is driven through a hand wheel 13, which is connected to the second end 63 of the shaft 55 by any suitable means, such as a chain and sprocket mechanism 61. In that manner, the manual center drive carriage can be operated with a drive shaft that is only approximately one-half as long as previously required.
Now looking at FIGS. 9 and 10, an alternate construction of an electrically powered mobile carriage is illustrated. The speed reducer 41 is fixedly mounted to the carriage channel 64 by screws 54'. A hole 65 is provided in the channel 64 for passage of the driver sprocket 33, but there are no adjustment slots for the screws 54'. To adjust the tension of the drive chain 31', an idler sprocket 67 is slidably mounted to the channel 64. The idler sprocket 67 is supported on a short shaft 69 by a conventional bearing, not shown. The shaft 69 passes through a vertical slot 71 in the channel 64. The shaft 69 may be fixed to one leg 73 of a right angle plate 75 by a collar 77. An adjustment screw 79 is threaded through the longitudinal flange 81 of the channel 64 to contact the second leg 83 of the plate 75. By turning the screw 79 within the channel flange 81, the plate 75 forces the sprocket shaft 69 and the idler sprocket 67 to slide within the channel slot 71, thereby altering the tension of the chain 31'. The remaining components of the design of FIGS. 9 and 10, including the drive wheels 23 and sprockets 29, are the same as for the design described previously with respect to FIGS. 2-5.
The manually powered mobile carriage as previously described in connection with FIGS. 6-8 may also have an alternate construction. In FIGS. 11 and 12, the flangette bearing 57' is fixedly secured to the carriage frame channel 85 by fasteners 58'. An opening 86 is cut in the channel 85 for the driver sprocket 53'. Tension adjustment of the drive chain 87 is achieved by an idler sprocket 89 mounted for rotation on a short shaft 91. The shaft 91 passes through a slot 93 in the channel 85 and is fastened to a right angle plate 95 as with a collar 97. The plate 95 and shaft 91 are slidably captured to the channel 85. An adjustment screw 99 threaded into the flange 101 of the channel 85 bears against a leg 103 of the right angle plate 95. Turning the screw 99 against the plate leg 103 adjusts the tension of the chain 87 by causing the idler sprocket and shaft 91 to slide in the channel slot 93. The remainder of the alternately constructed manually powered mobile carriage is substantially similar to that described previously in conjunction with FIGS. 6-8.
Thus, it is apparent that there has been provided, in accordance with the invention, a center drive mobile carriage that fully satisfies the aims and advantages set forth above. While the invention has been described in conjunction with specific embodiments thereof, it is evident that many alternatives, modifications, and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, it is intended to embrace all such alternatives, modifications and variations as fall within the spirit and broad scope of the appended claims. | A mobile storage system includes mobile carriages that roll on rails embedded in a building floor. The carriages are driven along the rails by at least two flanged wheels that engage a grooved rail. The flanged wheels are preferably mounted in parallel channels located at the center of the carriages. The flanged wheels are driven in synchronization by a sprocket and chain drive. Either electric or manual power may be provided. In both cases, the sproket and chain drive is adjustable to provide proper chain tension to the wheels to improve tracking. Chain adjustment may be accomplished by an idler sprocket movably mounted to a carriage channel. | 1 |
FIELD OF THE INVENTION
The present invention is directed to fabric filter media for commercial and industrial applications, and more particularly, to a stiffened, pleated filter medium for high-temperature gaseous filtration applications.
BACKGROUND OF THE INVENTION
Over the last several decades, there has been an increased awareness and emphasis on environmental issues, including air and water quality. Increasingly strenuous governmental controls and limits have been imposed to preserve these natural resources and prevent associated health hazards.
Numerous advances have been made in effectively controlling air pollution by removing undesirable particular matter from gaseous processing streams and exhausts. One particular type of air filtration technique has been the employment of particulate collectors known as “baghouses”. Baghouses operate much like a household vacuum cleaner. Dirty air is drawn into a chamber, or plenum, where a filter medium is positioned. The air passes through the filter into a clean air plenum, depositing the particulate matter, dust, etc. on the filter surfaces as it passes into the clean air plenum. Because of the high volumes of air being processed in industrial applications, these baghouses must be equently cleaned. Cleaning is typically conducted by reversing the flow of air or gas through from the clean air plenum into the dirty air plenum, dislodging the dust and particulate matter that has accumulated on the surfaces of the filter. In some industrial applications, these cleaning cycles must be repeated hundreds of times each day. As will be appreciated, the filters very quickly become structurally fatigued, tearing in short periods, thus requiring frequent, costly replacement.
The cleaning problems and failures of baghouse filters, including cartridge filters, are further exacerbated when the filters are installed in high temperature applications where the gaseous discharges exceed 450 degrees Fahrenheit. Fabric filter media very quickly deform and deteriorate, rapidly losing their structural rigidity and filtration efficiency. As a result, filtering high temperature gaseous discharges to meet regulatory requirements in a cost-effective manner, has been problematic.
SUMMARY OF THE INVENTION
The present invention is directed to a fabric filter material and a pleated filter formed therefrom that address the problems of filtering gaseous streams in high temperature applications; i.e., at temperatures between about 450 and 550 degrees Fahrenheit.
A preferred embodiment of the present invention provides a fabric material to which a stiffener is applied for maintaining the form (rigidity) of the fabric in the spectrum of high temperature applications. A fibrous fabric material that is capable of being stiffened and formed is selected. In this embodiment, the fibrous fabric is woven entirely from yarns of fiberglass, preferably type ECDE (continuous filament electrical grade) yarns in which a portion of both the fill and warp yarns are air-jet texturized. It has been found that using texturized yarns substantially increases the wet pickup of the fabric and facilitates the more precise forming (shaping) of the fabric. “Wet pickup” refers to the amount of a liquid finish, expressed as a percentage, that a finished fabric will absorb. The greater the wet pickup, the more effective the stiffener is in maintaining the form of the woven fabric during its anticipated high temperature service. It has also been found that fiberglass, as a filter material, retains superior durability after frequent and numerous fatigue cycles, and is quite adaptable to stiffening and forming.
The preferred stiffener is comprised of a resorcinol-formaldehyde resin solution, an acrylic resin emulsion, ammonia, hexamethylenetetramine, and water. The stiffener may be applied using any of the conventional methods known in the art for applying finishiners such as dipping, spraying, etc. Once the stiffener is applied, the treated fabric is heated until dry, but at a temperature and duration that will not exceed B-stage curing of the treated fabric. This allows the treated fabric to be later formed and set in a desired shape.
In a preferred embodiment, the stiffening system of the present invention includes three discrete layers that are sequentially applied to the woven fiberglass fabric, that is, two additional layers that complement the stiffener. An initial, or inner, layer serves as a lubricant for the subsequently applied stiffening layer and consists of water, a lubricant (desirably a silicon such as a phenyl silicone polymer because of its high temperature stability), and a polytetrafluorethylene (PTFE) dispersion. After the lubrication layer is applied, it is heated within a specified temperature range for a specified duration until dry. The stiffening layer is next applied. This layer is comprised of a resorcinol-formaldehyde resin solution, an acrylic resin emulsion, ammonia, hexamethylenetetramine, and water. The treated fabric is again heated until dry, but at a temperature and duration that will not exceed B-stage curing of the treated fabric. This allows the treated fabric to be later formed and set in a desired shape. Lastly, a protective layer is applied to the treated fabric, the protective layer consisting of a PTFE dispersion and water. The treated fabric is heated until dry, but again at a limited temperature and duration combination so that the fabric will not cure beyond the B-stage. The finished treated fabric may be immediately shaped and set, or may be stored in the B-stage for later forming.
In a preferred embodiment, the treated fabric is pleated as it is well known in the filtration arts that pleated filters provide substantially more (2 to 3 tires) filtration surface area for a selected filter size. Any of the known commercial pleating machines may be used to pleat the fabric. Sufficient heat and duration are required to set the pleats, fully curing and setting the treated fabric. An oven or infrared lights downstream of the pleating operation are employed to provide this curing, setting heat.
A further embodiment of the present invention is a filter device, such as a pleated cartridge filter, for high temperature filtration applications. Such a cartridge filter is easily adapted to the baghouse filter systems described above. The filter device is comprised of a perforated liner, a generally circular pleated portion of treated, stiffened fabric, at least one retainer, and end flanges. The perforated liner is preferably a metallic cylinder with open ends and perforations formed through and spaced about the cylinder walls. The perforations are sized and spaced to optimize the flow of air into the clean air plenum after passing through the pleated filter. The most important function served by the liner, however, is structural support for the surrounding fabric filter. Completely surrounding the outer wall surface of the cylindrical liner is the pleated fabric filter material. At least one retainer, such as a band, strap, wire, etc. holds the filter material in place around the cylindrical liner. This especially provides additional rigidity and support to the filter material during the frequent cleaning cycles which force air in a reverse flow through the liner and back across the filter material to dislodge trapped particulate. Finally, to secure the upper and lower free ends, or edges, of the pleated filter, caps or flanges are fitted around the ends or edges and adhered to the fabric with a conventional potting compound known in the art and adapted for high temperature applications.
The fabric filter material treated and formed as described hereinabove and in accordance with the detailed description that follows, is capable of achieving a filtration efficiency of greater than 99% for particulate matter of 10 microns or greater. Further, when pleated and incorporated into a filter device, such as a filter cartridge, the fabric filter material can withstand thousands of cleaning cycles without failure.
These and other aspects of the present invention will become apparent to those skilled in the art after a reading of the following description of the preferred embodiments when considered with the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a cross-sectional view of the woven fabric filter material of the present invention, illustrating the three layers of the stiffening system applied thereto and a pleated shape;
FIG. 2 is a schematic illustration of the weave pattern for the fabric of the present invention; and
FIG. 3 is a front perspective view of a filter device constructed according to a preferred embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to FIG. 1, a schematic cross-sectional view of the treated fabric material of the present invention for use in high temperature applications is shown generally as 10 .
While many suitable yarns and non-textile materials may be used for forming conventional filtration media for low temperature (ambient) residential and commercial applications, materials suitable for prolonged high-temperature duty (between about 450 and 550 degrees Fahrenheit) are not conventionally known. Fiberglass is well known in the art for its suitability in withstanding elevated temperatures; however, at high temperatures, untreated fiberglass rapidly loses its form and quickly deteriorates. It has been found, however, that a stiffening system applied to a fiberglass fabric solves this problem.
A preferred embodiment of the present invention begins with forming a woven, 100 percent fiberglass fabric; however, the fabric for the present invention need not be limited to a woven construction. The warp yarns are comprised of one end of ECDE 37 1/0 filament and one end of ECDE 75 1/0 texturized. The fill yarns are comprised of three ends of ECDE 75 1/3 texturized. As those skilled in the art will appreciate, these yarns are formed from type DE continuous, electrical grade fiberglass filaments; hence ECDE. ECDE 37 and 75 comprise 3,700 and 7,500 yards of yarn per pound, respectively. The designation 1/0, well known in the art, means that 1 strand is using in making the yarn, and 0 means that no twisted strands are plied together in this construction; 1/3 means that 1 strand is used in making the yarn and 3 twisted strands are plied together. Alternately, the fabric may be comprised of ECDE 75 1/2 warp yarns and ECDE 75 1/4 texturized fill yarns in a double filling weave pattern.
Textured fill yarns have been found to provide a higher wet pickup than untexturized yarns, particularly for those yarns (the fill yarns) that are benefit on the fabric is subsequently pleated. “Wet pickup” refers to the amount of liquid finish (expressed as a percentage) that a finished fabric will absorb. It has also been found that the weave pattern affects the fabric's adaptability to shaping, i.e. a crisper, stiffer pleat. In a preferred embodiment, and as shown in FIG. 2, the weave pattern is a 1/3 right hand twill. This means that each warp yarn, shown oriented vertically, crosses under 3 fill yarns and over 1 fill yarn in staggered relation. A twill weave is one that is characterized as consisting of one or more warp yarns running over and under two or more fill yarns. Warp yarns are shown as 12 and fill yarns as 14 in FIG. 2 . This particular weave has been found to provide optimal pliability, with a wet pickup between about 37 and 42 percent; however, other weave patterns will also provide similar results.
Referring again to FIG. 1, there is shown a cross-sectional schematic view of the treated fabric material 20 of the present invention. After forming the woven fiberglass fabric 22 , a stiffening system is applied thereto. This stiffening system comprises three discrete layers 24 , 26 , and 28 that are sequentially applied. Each of these layers may be applied by any of the conventional finishing methods known in the textile art, including dipping and spraying. The initial, or inner, layer 24 functions as a lubricant for the subsequently applied stiffening layer. This initial layer consists of water, a lubricant, and a polytetrafluorethylene (PTFE) dispersion. The lubricant is preferably a silicon, and more specifically a-phenyl silicon polymer because of its high temperature stability. While the percentages of each ingredient in this mixture can vary widely and still provide acceptable results (phenyl silicon polymer: 5-50%, PTFE dispersion: 1-40%, and water: 10-94%), the preferred mixture and that which provides the optimal results comprises 30% phenyl silicon polymer, 50% water, and 20% PTFE dispersion. It has been found, however, that an initial layer 24 comprised of only water and PTFE, or only of water and a silicon, will still yield acceptable results. After applying this initial lubricating layer 24 , the treated fabric is heated until dry. Heating the fabric at approximately 350 degrees Fahrenheit for about 1 minute is sufficient.
Subsequent to drying the initial layer, the intermediate, or stiffening, layer 26 is applied to the fabric. The stiffening layer comprises a resorcinol-formaldehyde resin solution (5-40%), an acrylic resin emulsion (1-10%), ammonia (0.1-2.0%), hexamethylenetetramine (0.1-5.0%), and water (43-93.8%). Alternatively, the stiffening layer may comprise a phenol-formaldehyde resin solution (30%), an acrylic resin emulsion (5)%, ammonia (1.3%), hexamethylenetetramine (2%), and water (61.7%). In lieu of acrylic resin, any suitable thermoplastic may be used. Similarly, a phenol-formaldehyde resin solution may be substituted for the resorcinol-formaldehyde resin solution. This is because the hexamethylenetetramine also releases formaldehyde into the mixture for cross-linking with the phenol-formaldehyde resin, Ammonia is part of the mixture for pH control purposes only and may eliminated, dependent upon the specific composition of the mixture. Following this application the treated fabric is again heated until dry, however, care must be taken to control the temperature so that premature curing and stiffening of the fabric does not occur. This is well understood in the art, and for this material construction, a maximum temperature of 250 degrees Fahrenheit for a duration of one minute is sufficient; however, longer durations at lower temperatures will also provide equally satisfactory drying.
Lastly, the outer, or protective layer 28 is applied. This layer serves as a durable shield against abrasion and erosion of the stiffening layer. The protective layer 28 is comprised of a PTFE dispersion (5-30%) and water (70-95%), with the performed embodiment comprising 20% PTFE dispersion and 80% water. The protective layer is also heated until dry, but again at a temperature not exceeding 250 degrees Fahrenheit and for a duration not to exceed one minute. The fiberglass fabric, having been treated with the stiffening system described above, may now be packaged and stored for later shaping and final curing, or may be immediately shaped and cured.
The treated fabric 20 is pleated using any one of the several commercially available, and well-known, pleating machines. Any one of these machines can be used to pleat the treated fabric 20 of the present invention in pleats having folds 1/4 inches wide with each crease approximately 3/4 inches in depth, although the pleat width and depth are not critical. Because the treated fabric is still in the B-stage, pleating or other shaping is more easily accomplished. Once the pleats are formed, the pleated material may be heat set to complete the curing and stiffening process. An oven or banks of infrared lights located downstream of the pleating operation may provide this heat. For this fabric construction and the stiffening system described herein, heating at about 375 degrees Fahrenheit for about 45 seconds is sufficient to finish the pleated material. The pleated, stiffened fabric is now suitable for use in high-temperature applications. The surface area of the pleated filter fabric is two to three times the filtration surface area of conventional “flat” filters, depending upon the width and depth of the pleats. The fabric also has a permeability of approximately 25-35 cubic feet per minute when tested in accordance with ASTM D737, “Standard Test Method for Air Permeability of Textile Fabrics”. Additionally, the finished fabric has a filtration efficiency of greater than 99% for particulate matter of 10 microns or larger.
In an alternative embodiment, the treated fabric 20 is incorporated into a filter device, shown generally as 100 in FIG. 3 . While a cartridge-type filter device is shown, those skilled in the art will readily appreciate that there are numerous shapes, sizes, and configurations for filtering devices incorporating fabric 20 , depending upon the specific application. Here, filter device 100 comprises a perforated linen 105 , pleated fabric filter material 110 , flanges 120 , and at least one retainer 115 . The perforated liner 105 is a metallic cylindrically shaped screen or mesh that is open on the ends. The sizes and shapes of the perforations in the liner 105 are not critical to the present invention so long as the perforations provide optimal air passage and adequate structural support for filter material 110 . Filter material 110 is placed or wrapped around the entire cylindrical surfaces of liner 105 . Any conventional technique for overlapping or joining longitudinal ends of the filter material 110 to ensure the ends are adequately jointed together may be used. End caps, or flanges, 120 (only the upper end cap is shown in FIG. 3) are fitted over the ends of the filter material 110 and liner 105 to secure them together in place. The end caps are also preferably metallic. To hold the pleats in relative pleated position within the end caps, a potting compound (not shown) is used. A potting compound is a material that embeds the ends in place and solidifies so that the ends are rigidly held during operation. One suitable potting compound is Duralco 4703, manufactured by Cotronics Corporation of Brooklyn, N.Y. Finally, at least one retainer 115 such as a metallic band or strap is secured around the outer periphery of the filter material 110 so that the band does not compress or crush the pleats 118 , but fits snugly against the pleats 118 . Retainer 115 serves to maintain the integrity and form of the filter material 110 when air is reverse-flowed through the perforated liner 105 during the cleaning cycles.
In operation, a gaseous process or exhaust stream flows through the filter material 110 and though the liner 105 , discharging into a clean plenum through one or both ends of cartridge filter 100 . Cleaning cycles are typically initiated at specified intervals or when the pressure differential across the filter material 110 reaches a predetermined level. When that occurs, clean air is forced from an air source from within the cartridge 100 and out through the filter material 110 .
The cartridge filter 100 constructed accordingly to the present invention will provide acceptable service through well over one hundred thousand cleaning cycles in accordance with testing performed under ASTM D2176, “Standard Test Method for Folding Endurance for Paper”. Using this standard, strips of fabric are loaded into a flex tester where they are flexed to failure.
Certain modifications and improvements will occur to those skilled in the art upon reading the foregoing description It should be understood that all such modifications and improvements have been omitted for the sake of conciseness and readability, but are properly within the scope of the following claims. | A fabric material for high temperature gaseous filtration applications, including a fabric material capable of withstanding temperatures of at least 450 degrees Fahrenheit for prolonged periods without deformation or deterioration, and a chemical stiffener that has been applied to the fabric. | 8 |
BACKGROUND OF THE INVENTION
Wire rope, simply stated, consists of a number of wires twisted together to form a strand, a number of these strands then being twisted together helically and symmetrically to form a rope made of wire. This "stranding" of many small wires together forms a rope of a given aggregate sectional area, which when compared to a single bar of steel having the same sectional area, is of much greater strength and flexibility.
While wire rope is recognized as an immensely applicable haulage device, it is only as strong as its weakest link. This link, in quite a number of cases, is the spliced area on the wire rope. When such wire rope slings fail, they do so at the splice, unless the rope has been kinked or cut elsewhere. The industry has used swage sleeves for protecting this weakened area as well as fortifying it to the extent possible.
Under present practice, considerable time is spent forming and fixing eyes or splices on the end of wire ropes. Among the various alternative methods of formation are the "farmer's eye method", the "flemish eye method" and the "torpedo loop locks method". In all cases, however, the wire rope end is threaded through the small end of a swage sleeve. The end of rope is unlayed such that two groups of wires are formed. One group generally has the same number of strands as the other although this will obviously not be so with wire ropes having an odd number of strands. The two groups of strands are crossed to form a loop of the desired size and the two strands are layed back upon the loop such that they terminate at the point where the two strands originally separated. Once this is accomplished, the swage sleeve is manually pulled onto the "Y-shaped" portion of the eye or sling. The sleeve is then swaged or pressed onto the wire rope under a relatively large load derived from a 500 to 600 ton press. The swaged sleeve then holds the eye or sling from slipping when a load is applied to the sling.
The major problem in this method usually comes in the attempt to manually slide the swage sleeve over the "Y-shaped" portion of the wire rope. Each employee employs a different method to assemble the sleeve over the wire rope splice. In general, after the eye or sling has been formed, the employee must clamp the rope in a vice, hold the rope ends of the splice in position, and at the same time pull the sleeve onto the rope. The employee then unclamps the rope from the vice and goes onto the swaging operation at the large swaging press.
There are several problem areas in the present procedure. For instance, manually forcing the sleeve over the wire rope and its loose ends is time consuming and awkward. Difficulties in this area arise in getting the ends started into the swage sleeve. If the wires are not spread out properly around the rope, it can be difficult to pull the sleeve onto the rope. In this operation, it is possible to pinch a finger or get a puncture wound while holding and pulling the sleeve onto the rope. Furthermore, it is also possible that the sleeve will not always be pulled far enough onto the rope to make a proper connection. How far the rope enters the sleeve is left to the judgment of the employee unless he carefully measures the distance moved. Usually the employee does not take the time to measure the rope movement into the sleeve and accordingly, a weakened splice and swage results.
In the currently-employed method, the wire rope must be placed in a vice to clamp the same. This takes time and can be awkward if a special jaw has not been installed on the vice to protect the rope. It should be noted in this regard that rope damage cannot be tolerated under any circumstance. Excessive pinching or clamping can result in a weakened point on the rope and resulting in a rejection if the product is subject to a quality control. If quality control is not followed, the damaged wire rope may result in a greatly reduced strength limit to a point wherein the specific strength tolerances of the individual wire rope may be exceeded during its usage, and breakage and injury may result.
SUMMARY OF THE INVENTION
The present invention is addressed to an apparatus and method for automatically pulling the swage sleeve onto the wire rope splice prior to the swaging operation. The process and apparatus eliminates the need for employee to hold the wire strands in position while pulling the sleeve onto the rope. Moreover, the apparatus pulls the sleeve onto the rope the same distance each time resulting in more uniform eyes or slings.
Time and economic studies have been made by applicants concerning the above-noted method and apparatus. While substantial time and money may be saved by incorporation of the present apparatus and method, the most important advantages to be realized from the same are the obtaining of a quality connection, the elimination of the physical effort used by the employee, and the elimination of any seizing or special cutting and grinding operations which are performed upon the loose wire ends in an attempt to funnel the wire ends into the swage sleeve.
The apparatus of the present invention has a minimum number of moving parts and generally include a housing upon which is mounted a clamping device. Mounted in movable relationship with the clamping device is a swage sleeve securing or capturing assembly which in turn is selectively opened or closed for inserting or withdrawing a swage sleeve. The clamping assembly and the mechanism for securing or capturing a swage sleeve are located relative to one another on the housing such that movement of the securing and capturing assembly is in a direction parallel to the longitudinal axis of the wire rope when it is clamped in the clamping device. Additionally, a pneumatic system is provided for selectively forcing the securing and capturing assembly in a direction away from the clamping mechanism and toward the end of the wire rope upon which has been spliced an eye or sling loop.
Due to the automatic nature of the invention just described, the swage sleeve is forced upon the splice to the same degree and with the same effort each time it it used by any employee. Consequently, a standardized result is obtained thereby producing a stronger and more easily swaged sleeve-splice combination.
It is therefore a primary object and feature of the present invention to provide a semi-automatic apparatus for securing swage sleeves upon a wire rope having a splice thereon for forming a sling at one end of the wire rope.
It is a further primary object and feature of the present invention to provide an apparatus for securing swage sleeves over a splice formed on a wire rope efficiently and without the necessity for substantial manual manipulation.
It is a general object and feature of the present invention to provide an apparatus for securing swage sleeves upon a wire rope having a splice thereon for forming a sling at one end of the wire rope, the apparatus including a clamping mechanism and a swage sleeve coffin movable in a given direction away from the clamping mechanism for moving a swage sleeve contained therein over the spliced area in the wire rope, both the clamping mechanism and the movement of the swage sleeve coffin being pneumatically powered.
It is another object and feature of the present invention to provide an apparatus for securing swage sleeves upon a wire rope having a splice thereon for forming a sling at one end of the wire rope, the apparatus including a clamping mechanism and a swage sleeve coffin movable in a given direction away from the clamping mechanism for moving a swage sleeve contained therein over the spliced area in the wire rope, both the clamping mechanism and the movement of the swage sleeve coffin being hydraulically powered.
Other objects and features will, in part, be obvious and will, in part, become apparent as the following description proceeds. The features of novelty which characterize the invention will be pointed out with particularity in the claims annexed to and forming part of the specification.
BRIEF DESCRIPTION OF THE DRAWINGS
The novel features that are considered characteristic of the invention are set forth with particularity in the appended claims. The invention itself, however, both as to its structure and its operation together with additional objects and advantages thereof will best be understood from the following description of the preferred embodiment of the invention when read in conjunction with the accompanying drawings wherein:
FIG. 1 is a perspective view of the swage sleeve fitting apparatus according to the present invention;
FIG. 2 is a sectional view of a portion of the apparatus shown in FIG. 1 during one stage of its operation;
FIG. 3 is the apparatus of FIG. 2 during another stage of its operation; and
FIG. 4 is an enlarged perspective view of a portion of the apparatus shown in FIG. 1 to more clearly define detail.
DETAILED DESCRIPTION OF THE INVENTION
Looking to FIG. 1, there is shown a perspective view of a semi-automatic swage sleeve securing apparatus according to the present invention indicated at 10. The apparatus 10 generally includes a support table 12 providing a static basis for the components to be described. These components generally include three main parts. For the first of these parts is an air cylinder 14. The air cylinder 14 is connected to, and provides the necessary pneumatic forces for the operation of a clamping mechanism 16. The clamping mechanism 16 includes a stationary portion 18 and a movable counterpart 20 which is connected to the air cylinder 14 through an air cylinder rod 22. The movable portion 20 is actuated for movement between a first position, in which portion 20 is retracted from operable association with the stationary portion 18, and a second position, shown in FIG. 1, in which it is in wire rope clamping association with portion 18. Actuation as well as retraction of the movable portion 20 with respect to the remaining portion 18 is achieved through the use of an actuation pedal 24 interconnected through the air cylinder 14 through a hose connection 26. The specific manner in which pneumatic actuation may be accomplished is well known, and consequently, will not be shown in detail or described in this specification.
The jaws of the clamping mechanism 16, which are attached to the portions 18 and 20 may have a number of different configurations from flat plate to V-grooves. However, a preferred design incorporates jaws complementarily configured to the wire rope, a configuration which might be described as a half circle in each jaw. In this manner, the wire rope itself is not damaged or distorted when clamped, thereby doing away with the possibility of weakening the wire rope itself.
Positioned co-axially with the longitudinal axis of the jaws of the clamping device 16 is an assembly 30 for capturing and releasably securing a swage sleeve 64 therein. The capturing assembly 30 is configured as a coffin for the swage sleeve and includes a bottom portion 32, an upper portion 34 and a hinge 36 connecting the two as indicated in FIG. 4. Pivotally connected along the outer edge of bottom portion 32 is a handle 38. A slot 40 is formed through the handle proximate its pivotal point of connection with portion 32. Slot 40 is configured to receive a tab 42 located on the outer edge of upper portion 34. Both the handle 38 and the tab 42 are positioned proximate the center of each of their respective edges so that they may interrelate with each other in a manner about to be described.
Looking to FIG. 4, there is shown a perspective view of the capturing assembly or swage sleeve coffin 30. The coffin 30 is movably mounted upon the table 12 within a slide assembly 44 consisting of two parallel-oriented grooved slide members 46 and 48 which include a slide cutout portion therein (not shown) and a stop plate 50 for arresting movement of the coffin 30 toward the clamping device 16 beyond a given point. The bottom portion 32 of the coffin 30 has horizontally-oriented side flanges 76 and 78 which are configured to fit within the above-mentioned slide cutout portions located in the grooved slide members 46 and 48, thereby providing for the sliding movement of the coffin 30 within the latter-mentioned members 46 and 48.
As may be evidenced from FIG. 4, the two halves 32 and 34 of the coffin 30 are substantially identically configured and have hollowed-out portions 56 and 58 located therein, respectively. The two halves, when pivoted into contact with one another have a void or opening therein which, in part, is complementarily configured with respect to the swage sleeve to be located on the wire rope sling splice. Located on either end of both halves 32 and 34 are funneled portions 52 and 54. The funneled portions 52 on portions 32 and 34, when combined in the coffin's closed state, provide for the easy entrance of one end of a wire rope into the coffin and the swage sleeve located therein. As previously explained, one problem area is getting the rope end into the small end 60 of a swage sleeve, a problem which is solved using the funneled portion 52 of the coffin 30. The other funneled portion 54 facilitates the movement of the subsequently formed splice into the larger end 62 of the swage sleeve. This relationship may best be seen by making reference to FIGS. 2 and 3.
Once the swage sleeve is placed in the bottom portion 32 of the coffin 30, the top portion 34 is rotated about the hinge 36 until the coffin is closed. During this closing movement, the tab 42 of upper portion 34 is moved into a position in which it falls through the slot 40 located in handle 38. The handle 38 must be elevated a slight amount beyond the horizontal in order for this to occur. The handle 38 is then moved to its vertical position, thereby "locking" the coffin closed with the swage sleeve 64 located therein. The operation continues when the wire rope clamping jaws 18 and 20 are opened by actuation of the clamping foot pedal 24 which retracts the cylinder rod 22 and the associated clamp jaw 20. One end of the wire rope 66 is pulled through the clamping jaws 18 and 20 and is pushed into the funneled portion 52. The rope is then pulled through the sleeve and coffin to a predetermined length which is dependent upon the size of the sling loop to be formed. The rope is then unraveled and an eye is made by dividing the rope into two parts and wrapping the rope back on itself, the latter procedure being known in the field. The "Y-shaped" portion 68 of the eye or sling is then manually pulled up next to the funneled portion 54 of the coffin 30. The rope which lies between the opened jaws 18 and 20 of the clamping device 16 is clamped by the jaws by actuation of the clamping pedal 24 which operates the air cylinder 14 and extends the air cylinder rod 22 and associated jaw 20. The swage sleeve 64 which is captured within the coffin 30 is now ready for movement onto the splice of the sling eye.
Movement of the swage sleeve 64 onto the sling splice is achieved by actuation of a second foot pedal 70 located adjacent foot pedal 24. The pedal 70 functions as a switch for providing power to the movable coffin 30 from the air cylinder 14 through appropriate pneumatic linkages schematically indicated at lines 72 and 74. Powering of the coffin 30 moves it and its captured swage sleeve 64 along the slide members 46 and 48 such that the swage sleeve is pulled onto the wire rope splice. The funneled portion 54 of the coffin 30 guides the wire rope ends into the sleeve without any other of the above-mentioned time and danger. The handle 38 is then pulled down to unlock the top portion of the capturing assembly 30. The top portion 34 is opened and the swage sleeve 64 is exposed. The foot pedal 24 is again actuated, thereby opening the jaws 18 and 20 and releasing the wire rope contained therein. The swage sleeve is then moved to a swaging area where it is swaged.
The movement of the coffin 30 from its initial position shown in FIG. 2 to its final position shown in FIG. 3 may be regulated in length by adjustment of the size of the stop plate 50. This adjustment should be rarely needed, but might be employed in changing from one size wire rope to another.
The apparatus just described is employed mainly with round or circular carbon steel sleeves because of the prevailing economics. Round or circular carbon steel sleeves are approximately one-third the cost of an oval sleeve. However, since the latter are easier to manually move over the sling splice, they are used instead of the cheaper round sleeves. This problem no longer presents the economically undesirable solution priorly used. Accordingly, the less expensive swage sleeve may be used with greater efficiency and savings.
The present semi-automatic swage sleeve securing apparatus provides many advantages over current sleeve securing procedures. Among these are the reduction of cost by using round sleeves, the reduction in time for assembly by eliminating the manual insertion of the splice into the swage sleeve and the elimination of the need to measure and mark the rope to provide a standardized movement of the sleeve onto the splice. Moreover, the use of an automatically movable assembly drastically reduces the physical efforts previously necessary to pull the sleeve onto the rope. It should become apparent that the greatest advantage to be realized however, is the greatly improved quality of the product being manufactured, a result having a direct relationship to the safety of the employee producing the sling as well as the employee using it.
While certain changes may be made in the above system and assembly without departing from the scope of the invention herein involved, it is intended that all matter contained in the above description or shown in the accompanying drawings shall be interpreted as illustrative and not in a limiting sense. | Method and apparatus for securing swage sleeves upon a wire rope having a sling spliced thereon. The apparatus includes semi-automatic mechanisms for insuring the full and efficient fastening of the swage sleeve upon the splice in preparation for swaging, thereby effecting a stronger wire rope sling. | 8 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional application of prior U.S. application Ser. No. 11/876,820, filed Oct. 23, 2007, which claims the benefit of the filing date of Dec. 21, 2006, for United Kingdom application number 0625656.4, the specifications of which are hereby incorporated by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to an envelope sealing apparatus and to a method of sealing an envelope. The invention finds specific application within a mail piece creation device, and to a method of creating a mail piece.
BACKGROUND OF THE INVENTION
[0003] It has been known to provide devices for automatically creating a finished mail piece. Such devices range from industrial scale units capable of producing a large throughput (high output) of mail pieces for distribution to a wide audience down to so-called SOHO (Small Office Home Office) mail creation devices having much smaller output capacity.
[0004] The functionality of mail piece creation devices typically increases as the size of the device increases. Industrial scale mail piece creation devices represent a production facility in their own right. These facilities are configured to print large numbers of mail items for delivery to individual addressees. Each mail item is printed, collated, accumulated as necessary with other mail items, folded and inserted into an individual envelope. The envelope may bear an address window for displaying an address printed on the mail item, or may be separately addressed, in which case the envelope must be properly addressed to the intended recipient of the enclosed mail items. Once the mail item is inserted into its envelope, the envelope is automatically sealed and processed for delivery. Known devices of this kind are capable of producing individual mail items properly addressed for delivery to large target audiences, perhaps in mail shots of tens or hundreds of thousands of mail pieces, for example as would be required by large service organizations such as banks, utilities companies and governments.
[0005] On a more modest scale, SOHO mail piece creation devices have been proposed for home and office use. Such devices are often also referred to as “desktop” mail piece creation devices, although they may, in fact, be floor-standing. Whereas industrial scale mail piece creation devices typically require a dedicated team of highly trained operators in order to maintain and run the production process, SOHO mail piece creation devices are intended to be facile to use and maintain, for operation by non-dedicated staff with a minimum of training. These devices are typically of the scale to produce a few thousand mail pieces per day, and thus find greatest applicability to medium-sized companies reaching a more modest target audience. Whereas the largest mail piece creation devices can achieve the full functionality described above, and are able to process a range of sizes of envelopes and sheets of paper, as well as being able to insert additional items into the envelopes via special inlet feeds, most SOHO mail piece creation devices are typically of a reduced functionality. Usually, this will entail the mail items being pre-printed, and then loaded into appropriate inlet feed trays. Similarly, the devices may be restricted to one, or maybe two, acceptable standard sizes for the mail items and envelopes from which the mail pieces are to be created. Furthermore, SOHO mail piece creation devices are typically designed to deliver large numbers of an identical mail piece to many receivers, rather than for creating recipient-specific mail pieces.
[0006] Despite having been labeled as SOHO devices, very few existing mail piece creation devices are particularly suited for home use, and it would be very uncommon to find such a device as a piece of household equipment. However, household-related written correspondence continues in vast quantities, despite the recent advances in electronic communication, and a market exists for mail piece creation devices that would be suitable for individual or home use.
[0007] The limiting factor in reducing the size of mail piece creation devices for such suitability has been in the need to retain adequate functionality in the device. Within such mail piece creation devices, each particular function in the above-noted process is carried out by separate mechanical system, requiring a corresponding proportion of space within such a machine for each paper handling or envelope handling process that is to be carried out. One such mechanism is the sealer apparatus that is used to close and seal the flap of an envelope, once the contents of the envelope have been inserted.
[0008] A typical known envelope sealer receives an envelope along a path, with the open flap of the envelope at the trailing end with respect to the envelope feeding direction. The envelope is typically fed around a curved path portion into a straight insertion section, so that the main body of the envelope is held in an aligned configuration at the insertion location. As the envelope is fed so that its main body rests within the insertion chamber, it is halted at a position where the open flap remains partially within the curved path preceding the straight insertion chamber, to thereby hold the envelope in an open configuration, with the mouth of the envelope held open. Mail items can then be inserted into the envelope, into the open mouth. To assist in the insertion operation, insertion fingers may be inserted into the mouth of the envelope, to assist in guiding a mail item there into, while the flap is usually held securely in the open configuration, typically by a roller pair located in the curved path.
[0009] Once the mail item has been inserted into the envelope, the envelope must typically be fed further along the feed path, to bring the hinge between the envelope flap and the main body into line with a sealing roller pair. The envelope is then fed hinge-first through the nip of the sealing roller pair, to close the flap to the main body, thereby sealing the envelope. Where a traditional gum-sealed envelope is to be used, a moistener is provided during this operation, to moisten the gum so that the envelope flap will seal.
[0010] Due to the requirement for further transporting the envelope to bring the hinge into alignment with feed rollers, and in order to feed the envelope hinge-first into the roller nip, such a system is unsuitable for sealing envelopes containing very thick or non-flexible mail items, due to the need for the mail item to pass around a curved path so as to enter the roller nip hinge-first. Moreover, the various transporting, flap holding and flap sealing operations, including, where applicable, a flap moistening operation, require a complex series of mechanical feed devices for transporting and feeding the envelope and contents, resulting in fairly large and complex mechanical arrangements.
SUMMARY OF THE INVENTION
[0011] According to a first aspect of the present invention, there is provided an envelope sealing apparatus for sealing an envelope having a main body and a sealable flap at one end of the main body foldable about a hinge between the flap and main body, the flap being sealable to said main body under applied pressure when folded about said hinge into contact with the main body, the apparatus comprising: a feed path along which an envelope can be fed; driving means associated with said feed path for, at least in part, feeding an envelope along said feed path; flap securing means cooperative with said driving means to secure an open envelope flap in contact with the driving means; and flap sealing means cooperative with said driving means to seal the flap to the main body when the driving means drives the envelope in a flap sealing direction along the feed path, wherein said driving means is movable from a flap securing position to a flap sealing position, the driving means being operable, in use of the sealing apparatus: (i) to secure an open envelope flap in contact therewith cooperatively with said flap securing means; (ii) to move from the flap securing position to the flap sealing position with the flap secured in contact therewith, so as to at least partially fold the flap about the hinge; and (iii) thereafter to drive the envelope in the flap sealing direction along the feed path, so as to seal the flap to the main body by applying pressure cooperatively with said flap sealing means.
[0012] In preferred embodiments said driving means is movable from a flap securing position on one side of the feed path to a flap sealing position on the other side of the feed path.
[0013] In further preferred embodiments, said driving means and said flap securing means may be mounted on a common securing support structure, so that as the driving means moves from the flap securing position to the flap sealing position, the flap securing means is supported to effect a complementary motion to ensure that an envelope flap thereby secured is maintained in contact with the driving means through at least a substantial portion of the motion. Similarly, said driving means and said flap sealing means may be mounted on a common sealing support structure, so that as the driving means moves from the flap securing position to the flap sealing position, the flap sealing means is supported to effect a complementary motion to ensure that, at the flap sealing position, an envelope driven in the flap sealing direction along the feed path by the driving means is subjected to an applied pressure.
[0014] Embodiments of such an envelope sealing apparatus may further comprise a moistener adjacent to the flap sealing position, the moistener being configured and arranged to be capable of applying moisture to a portion of the flap prior to or during the envelope being driven in the flap sealing direction along the feed path.
[0015] Typical embodiments of such an envelope sealing apparatus may comprise an envelope entry path, separate from the envelope feed path, along which envelopes are received into the sealing apparatus, wherein, with the driving means at the flap securing position, the driving means and flap securing means are configured cooperatively to secure the flap at a location along the envelope entry path.
[0016] Further embodiments of the sealing apparatus may usefully comprise a flapper mechanism configured to unfold about the hinge the closed unsealed flap of an envelope received into the sealing apparatus with a closed unsealed flap, thereby to ensure that the envelope flap is open to be secured cooperatively by the flap securing means and the driving means at the flap securing position. In most useful arrangements the flapper mechanism will be located along an envelope entry path, to unfold the closed unsealed envelope flap at a location upstream of the location along the entry path where the driving means and flap securing means are configured cooperatively to secure the flap as the envelope is received into the apparatus.
[0017] Even further preferred embodiments comprise an insertion location, wherein the main body of an envelope extends at least partially into the insertion location when the open flap of the envelope is cooperatively secured by the flap securing means and the driving means at the flap securing position and the envelope is thereby held open for items to be inserted into the main body of the envelope. In such embodiments, the envelope sealing apparatus may preferably further comprise an insertion frame including one or more insertion fingers arranged for insertion into the opening of an envelope held open at the insertion location, thereby to contribute to holding the envelope open for the entry of items into the envelope main body. Moreover, in embodiments including an envelope entry path as described above, then, at the flap securing position, the driving means is preferably arranged to engage an envelope received along the entry path and to drive the envelope along the entry path so that the main body extends at least partially into the insertion location.
[0018] In yet further preferred embodiments said driving means comprises a driven roller movable from the flap securing position to the flap sealing position. In one preferred configuration the flap securing means includes a securing idler roller in cooperative engagement with the driven roller, the securing idler roller being mounted on a common securing support structure as described above; and said securing support structure is configured so that as the driven roller moves from the flap securing position to the flap sealing position the securing support structure rotates about an axis collinear with the driven roller axis to cause the securing idler roller to roll around at least a portion of the outer circumference of the driven roller, thereby to maintain a flap securely in contact with the driven roller as the driven roller moves. Similarly, said flap sealing means may include a sealing idler roller in cooperative engagement with the driven roller and defining a sealing nip between the driven roller and the sealing idler roller, the sealing idler roller being mounted on a common securing support structure as described above, with said sealing support structure configured so that as the driving means moves from the flap securing position to the flap sealing position, with a flap secured in contact with the driving means by said flap securing means, the sealing nip is brought into alignment with the feed path and substantially into engagement with the at least partially folded hinge.
[0019] In still further preferred embodiments, the apparatus comprises a trapdoor forming at least a portion of the feed path, the trapdoor being mounted in proximity to the driving means and being displaceable from an envelope guiding position to a retracted position, thereby to allow the driving means to move from the flap securing position to the flap sealing position. In such embodiments, the trapdoor may be mounted on a trapdoor support frame, the trapdoor support frame being attached at least at one end to a support frame of the driving means, thereby to cause displacement of said trap from the envelope guiding position to the retracted position as the driving means moves from the flap securing position to the flap sealing position.
[0020] The present invention further provides a mail piece creation device: for automatically inserting mail items into an envelope and automatically sealing the envelope, comprising: an envelope sealing apparatus according to any combination of the preferred embodiments set out above.
[0021] According to a second aspect of the present invention, there is provided a method of sealing an envelope having a main body and a sealable flap at one end of the main body foldable about a hinge between the flap and main body, the flap being sealable to said main body under applied pressure when folded about said hinge into contact with the main body, the method comprising the steps of: providing an envelope to a flap securing location with the flap open; securing the flap in contact with driving means at the flap securing location, at least partially folding the flap about the hinge by moving the driving means with the flap secured in contact therewith to a flap sealing position, and driving the envelope with the driving means in a flap sealing direction along a feed path, and applying pressure cooperatively with flap sealing means as the envelope is driven, so as thereby to seal the flap to said main body.
[0022] In the above method, the step of providing an envelope to a flap securing location with the flap open preferably includes opening the flap of a closed unsealed envelope before providing the envelope to the flap securing location. Furthermore, the step of providing an envelope to a flap securing location with the flap open preferably includes providing the envelope along an entry path with the main body trailing the flap.
[0023] In a preferred embodiment of the method, the step of providing an envelope to a flap securing location with the flap open includes providing the flap to the flap securing location so that the main body extends into an insertion location; and the step of securing the flap in contact with driving means at the flap securing location includes holding the envelope open so that items may be inserted into the envelope main body.
[0024] In a further preferred embodiment of the method, the step of at least partially folding the flap about the hinge by moving the driving means with the flap secured in contact therewith to a flap sealing position includes moving the driving means from one side of the feed path to the other side of the feed path.
[0025] In yet further preferred embodiments of the method, the step of at least partially folding the flap about the hinge by moving the driving means with the flap secured in contact therewith to a flap sealing position includes moving the securing means relative to the driving means in order to maintain the flap secured in contact with driving means at least substantially entirely to the flap sealing position.
[0026] In more preferred embodiments of the method, the step of securing the flap in contact with driving means at the flap securing location further includes inserting envelope opening means at least partially into the main body in order to hold the envelope open for the insertion of items into the main body.
[0027] In even more preferred embodiments of the method, the step of at least partially folding the flap about the hinge by moving the driving means with the flap secured in contact therewith to a flap sealing position includes moving the flap sealing means so as to align the flap sealing means with the feed path. Preferably, the step of at least partially folding the flap about the hinge by moving the driving means with the flap secured in contact therewith to a flap sealing position includes substantially engaging the hinge with the flap sealing means.
[0028] Even further preferred embodiments of the method further comprise the step of moistening at least a portion of the flap, before or during the step of driving the envelope with the driving means in a flap sealing direction along a feed path, and applying pressure cooperatively with flap sealing means as the envelope is driven, so as thereby to seal the flap to said main body.
[0029] In yet more preferred embodiments, the step of driving the envelope with the driving means in a flap sealing direction along a feed path, and applying pressure cooperatively with flap sealing means as the envelope is driven, so as thereby to seal the flap to said main body, includes driving the envelope through a sealing nip of a sealing roller pair.
[0030] In particularly preferred embodiments, the method is carried out automatically by an envelope sealing apparatus capable of applying the method to one or a plurality of envelopes sequentially.
[0031] In still further preferred embodiments, the step of at least partially folding the flap about the hinge by moving the driving means with the flap secured in contact therewith to a flap sealing position further includes displacing at least a portion of a guide forming part of the feed path, thereby to allow the driving means to move to the flap sealing position.
[0032] The present invention further provides a method including any combination of the methods set out above, and further comprising the step of inserting at least one mail item into the open envelope before the step of at least partially folding the flap about the hinge by moving the driving means with the flap secured in contact therewith to a flap sealing position.
[0033] Embodiments of the present invention advantageously can provide a sealing apparatus that is useful for sealing envelopes containing thick or non-flexible mail items therein. Embodiments of the invention may also advantageously provide a sealing apparatus having a reduced size and being of relatively simple mechanical complexity, thereby facilitating incorporation of such an apparatus into a mail piece creation device.
[0034] The mail piece creation devices provided according to the invention can be of reduced size and complexity, as well as being capable of creating mail pieces that include thicker or non-flexible mail items.
[0035] Embodiments of the methods of the invention can achieve the aforementioned advantages when applied to a suitable sealing apparatus or mail piece creation device.
BRIEF DESCRIPTION OF THE DRAWINGS
[0036] To enable a better understanding of the present invention, and to show how the same may be carried into effect, reference will now be made, by way of example only, to the accompanying drawings, in which:
[0037] FIG. 1 is an external perspective view of a mail piece creation device loaded with paper and envelopes;
[0038] FIG. 2 is an external perspective view of the mail piece creation device of FIG. 1 in its unloaded state;
[0039] FIG. 3 shows an internal cross-sectional view, schematically depicting the main internal components of the mail piece creation device of FIGS. 1 and 2 ;
[0040] FIG. 4 is an internal cross-sectional view of the mail piece creation device of FIG. 1 , as an envelope is fed into the device;
[0041] FIG. 5 is an internal cross-sectional view of the mail piece creation device of FIG. 1 , showing the flap of an envelope being opened as the envelope is fed into the device;
[0042] FIG. 6 is a close-up view showing the flap opening operation of FIG. 5 in more detail;
[0043] FIG. 7 is an internal cross-sectional view of the mail piece creation device of FIG. 1 , showing the envelope at a flap securing position;
[0044] FIG. 8 is an internal cross-sectional view showing the envelope at the flap securing position, and showing further details of the associated flap sealing apparatus;
[0045] FIG. 9 is an internal cross-sectional view of the flap sealing apparatus of the mail piece creation device of FIG. 1 , showing the envelope at the insertion position;
[0046] FIG. 10 is an internal cross-sectional view of the sealing apparatus of the mail piece creation device of FIG. 1 , showing the envelope at the envelope sealing position, immediately prior to sealing the envelope flap; and
[0047] FIG. 11 is an internal perspective view showing the main components of the flap sealing apparatus and an associated drive mechanism.
DETAILED DESCRIPTION OF THE INVENTION
[0048] FIG. 1 shows a mail piece creation device 1 , loaded with a stack of sheets S held in a sheet feed tray 7 and a plurality of envelopes E held in an envelope feed tray 5 . The mail piece creation device 1 is a desktop mail piece creation device, of an equivalent or similar size to typically known desktop printers for personal or home use. The mail piece creation device 1 is generally contained within a housing 3 , from which project the sheet feed tray 7 and envelope feed tray 5 . At the front of the mail piece creation device 1 , there is provided a mail piece collection tray 9 , onto which completed mail pieces M can be received from mail piece ejection opening 13 . Power is supplied to the mail piece creation device 1 via a typical power supply cable 11 , configured to fit into the socket of a local electrical power supply. As shown in FIG. 1 , the housing 3 is formed from an upper section 3 a and a lower section 3 b , which can be opened about a hinge at the rear of the machine, to gain access to the internal paper handling feed paths of the mail piece creation device 1 , for clearing jammed envelopes and paper sheets. As is also suggested by the illustration in FIG. 1 , the mail piece collection tray 9 is pivotally mounted to the lower housing section 3 b to fit within a complementary recess in the housing 3 , for storing and packaging the device in a compact configuration.
[0049] Referring to FIG. 2 , the mail piece creation device 1 of FIG. 1 is shown, absent the loaded sheets S and envelopes E, and finished mail piece M. As can be seen, sheet feed tray 7 feeds sheets into the mail piece creation device 1 through sheet insertion opening 15 , while envelopes held in the envelope feed tray 5 are fed into the mail piece creation device 1 through envelope insertion opening 17 . As well as mail piece collection tray 9 being retractable, as noted above, sheet feed tray 7 is also telescopically retractable from the position shown in FIG. 2 , to reduce the external configuration of the mail piece creation device 1 . Both sheet feed tray 7 and envelope feed tray 5 may also be pivotally mounted to the upper housing section 3 a , for rotation between a retracted low-profile position and the unretracted operational position of FIG. 2 . Furthermore, the sheet feed tray 7 and envelope feed tray 5 may be removable, if required for storage or transport.
[0050] FIG. 3 shows the main internal components of the mail piece creation device 1 , in schematic form, in cross-sectional view.
[0051] As shown, the mail piece creation device includes a sheet feed tray 7 which delivers sheets held in a stack on the sheet feed tray to a sheet inlet separator 74 . The sheet inlet separator comprises a roller and separator block, as commonly known, for feeding sheets individually one-at-a-time into the sheet insertion opening 15 . Sheets fed into the sheet insertion opening 15 are fed into a sheet inlet feed path 70 , where they are detected by sheet inlet sensors 72 . Sheets are driven along the sheet inlet feed path 70 by a pair of feed rollers 71 . Sheets fed along the sheet inlet feed path 70 pass into a sheet folding location, where they are received by sheet folder feed roller pair 76 . The sheets are then fed into the sheet folder formed by sheet folder rollers 78 a , 78 b , 78 c and 78 d . As a sheet is fed between the first pair of rollers 78 a and 78 b , the sheet leading end is halted (for example in a buckle chute), causing the sheet to buckle. The buckle is fed between the second roller pair 78 b and 78 c , thereby creating a fold as the buckle passes through the nip between rollers 78 b and 78 c . The sheet thus folded is typically formed with the fold one third of the length along the sheet. As the sheet is then fed through the second roller pair 78 b and 78 c , it is again halted at the leading end (now formed by the fold), causing the sheet to buckle at a different location. The second buckle is now fed between the third roller pair 78 b and 78 d , to cause a second, further fold in the sheet, typically two thirds of the length down the sheet. In the depicted arrangement of rollers 78 a , 78 b , 78 c and 78 d , a so-called C-fold is produced, as known in the art, although the rollers may be operated to form a so-called Z-fold, if preferred. For simplicity, since such buckle folders are known in the art (see, for example, EP1 634 840 A1, which discloses a similar sheet folding arrangement), further description of the sheet folding apparatus is omitted. Other sheet folding mechanisms are known in the art, and may be used as appropriate to the particular application.
[0052] Turning now to the envelope handling portion of the mail piece creation device 1 , envelopes are held in a stack on the envelope feed tray 5 . A feeder/separator 18 similar to the sheet inlet separator 74 is provided to feed envelopes one-at-a-time into the envelope insertion opening 17 . The envelopes fed into the envelope insertion opening 17 are received by a roller pair 20 , and detected by envelope inlet sensor 22 . The envelope inlet feed roller pair feeds the envelope, with the sealed end first, along envelope inlet feed path 26 formed by envelope inlet feed path guide plates 26 a and 26 b . Just beyond the envelope inlet feed roller pair 20 is located a flapper 24 for opening the flap of an envelope that is fed into the mail piece creation device with the flap closed. Flapper 24 is actuated by a flapper link mechanism 24 a.
[0053] Further along the envelope inlet feed path 26 there is a flap securing location at which a drive roller 32 and a securing roller 34 form a flap securing nip 35 . Beyond the flap securing location there is a trap door 28 , which forms a shaped guide panel of the feed path, to direct the envelope into an insertion location 30 , where the main body of the envelope can be retained in a straight configuration. Insertion feed roller pair 38 is provided to assist with receiving and feeding an envelope into and out from the insertion location 30 . A common securing support frame 40 links drive roller 32 and securing roller 34 , to thereby maintain these rollers in engagement, to form the securing nip 35 there between. The securing support frame 40 is rotatable about a pivot 40 a . The drive roller 32 is also mounted on a sealing support frame 42 , to which a sealing roller 36 is commonly mounted, preferably biased into engagement with the drive roller 32 .
[0054] Beneath the trap door 28 , there is provided an insertion frame 50 , mounted to be rotatable around a pivot 51 . The insertion frame 50 includes insertion fingers 52 that are spring-mounted to be rotatable on the insertion frame 50 about a further pivot point 55 . The insertion frame is mounted so that as it rotates around pivot 51 , insertion fingers 52 extend to displace trap door 28 (also about a pivot), forcing the insertion fingers into the insertion location 30 , whereby they can extend into the open mouth of an envelope held in the insertion location. An insertion drive roller 53 is provided to assist in feeding items into the mouth of the envelope with the insertion fingers inserted therein. Furthermore, insertion frame 50 includes insertion guide 54 that can direct folded sheets from the sheet folding location along a path between the insertion fingers 52 and trap door 28 , to be driven into an envelope held in the insertion location 30 by a driving force from the drive roller 53 . By mounting drive roller 53 and insertion fingers 52 to be rotatable about a common axis, or closely spaced axes, items to be inserted into the envelope may be assuredly driven fully into the envelope from a position immediately adjacent to the open mouth of the envelope.
[0055] Below the insertion location, there is provided a moistener wick 60 , held within a container 62 of moistening agent 62 a . The moistener wick is located so that, during a sealing operation, it will moisten the gum portion of an envelope flap, to thereby seal the envelope when the flap is closed against the envelope main body.
[0056] Formed mail pieces are fed out of the mail piece creation device 1 by feeding them along feed path 46 , for ejection out of the mail piece ejection opening 13 , under the influence of mail piece ejection roller pair 13 a.
[0057] More detailed description of the operation of mail piece creation device 1 will now be given with reference to FIGS. 4-10 .
[0058] As shown in FIG. 4 , an envelope E has a main body m and a flap f joined to one another along a hinge h. The envelope is loaded on the envelope feed tray 5 either singly or in a stack, with the flap end at the trailing edge. As shown in FIG. 4 , the envelope is fed by separator roller 18 into the mail piece creation device 1 , into the envelope insertion opening 17 , with the flap in the closed position (i.e., folded at hinge h). The single envelope E is fed into the envelope insertion opening 17 , where it is detected by inlet sensor 22 , and received by inlet feed roller pair 20 , at the inlet to envelope inlet feed path 26 .
[0059] As shown in FIG. 5 , an envelope so received is fed along the envelope inlet feed path 26 , between the fixed feed path guide plates 26 a and 26 b , so as to follow a curved path that brings the envelope through the flap securing location by causing the envelope to be fed between nip 35 formed between drive roller 32 and securing roller 34 at a point along the envelope inlet feed path 26 . As shown in FIG. 5 , as the envelope leading end proceeds along the envelope inlet feed path 26 , it engages kicker link 25 of the flapper link mechanism 24 a . With reference also to FIG. 6 , it can be seen that as the envelope forces the toe of kicker link 25 out of the envelope inlet feed path 26 , the rotation of kicker link 25 causes the flapper link mechanism 24 a to be actuated, bringing the flapper 24 into the envelope inlet feed path 26 . The flapper link mechanism 24 a and the flapper 24 are so configured that, for envelopes above a certain size, the flapper 24 will be in the envelope inlet feed path 26 as the envelope flap f approaches the flapper 24 . As shown in detail in FIG. 6 , the flapper 24 becomes forced between the envelope main body m and the envelope flap f. As the envelope E is further fed around the envelope inlet feed path 26 , through nip 35 , driven by drive roller 32 , the leading end of the envelope is directed by trap door 28 into the insertion location 30 . At the same time, the envelope flap f is forced by flapper 24 upwardly out of the envelope inlet feed path 26 , thereby obtaining an open configuration.
[0060] Turning now to FIG. 7 , there is illustrated the situation when envelope E has been fed further around the envelope inlet feed path 26 , so that the main body m of the envelope E is substantially entirely located within the insertion location 30 . The envelope may be driven into such a location by the drive roller 32 , with assistance from insertion feed rollers 38 in the insertion location. Feeding of the envelope E is halted as the envelope hinge h approaches the hinge threshold T (see FIG. 8 ). In this location, the envelope flap f is retained in the nip 35 between drive roller 32 and securing roller 34 . Due to rollers 32 and 34 being cooperatively mounted on a common securing support frame 40 , the envelope flap f becomes securely held in the nip 35 . This may be achieved, for example, by forming the rollers 32 and 34 with an appropriately small clearance, or by biasing the securing roller 34 towards drive roller 32 . Referring to FIG. 8 , the position of the envelope E shown in FIG. 7 is depicted in more detail.
[0061] As shown in FIG. 8 , there is a hinge threshold T to or beyond which the hinge h must travel so as to ensure that the mouth of the envelope is properly received into the insertion location 30 , to enable mail items to be inserted into the envelope.
[0062] FIG. 8 additionally illustrates an example of how the trap door 28 can be mounted onto a trap door frame 29 , to thereby form a guide path for the envelope, in the position shown in FIG. 8 , so as to direct the envelope from the envelope inlet feed path 26 into the insertion location 30 . Trap door 28 is rotatably mounted onto the trap door support frame 29 , biased in a clockwise direction as shown in FIG. 8 . One end of the trap door support frame 29 is pivotally mounted to the securing support frame 40 to which drive roller 32 and securing roller 34 are commonly mounted. The other end of the trap door support frame 29 is mounted on a follower 29 b , constrained to follow trap door frame guide path 29 a.
[0063] In the embodiment shown, the flap f of the envelope E is held securely in the position shown in FIG. 8 by locking the drive roller 32 against rotation. This allows a mail item to be inserted into the envelope at the mouth, during an insertion operation.
[0064] An insertion operation takes place with the apparatus in the configuration depicted in FIG. 9 . Specifically, with the flap f held between drive roller 32 and securing roller 34 , insertion frame 50 is rotated around pivot 51 so that the insertion fingers 52 extend into the mouth of the envelope E near to the envelope hinge h. This is achieved by the insertion fingers 52 forcing the trap door 28 into the feed path, against the trap door biasing force, so as to bring the insertion fingers 52 and insertion drive roller 53 into proximity with, and into, the open mouth of envelope E held in the insertion location 30 . As shown, this rotation by the insertion frame 50 in the direction of arrow A about the pivot 51 brings the insertion guide 54 into alignment both with a sheet insertion path 80 and with an inlet opening formed between the trap door 28 and the insertion fingers 52 . In this manner, folded sheets can be fed between roller pair 78 b and 78 d , along sheet insertion path 80 , to be guided by insertion guide 54 between trap door 28 and insertion fingers 52 , into the mouth of the envelope E. Insertion drive roller 53 is then able to fully drive the folded sheet into the envelope E, due to its proximity to the mouth of the envelope at the location of the hinge h.
[0065] With reference to FIG. 10 , the filled envelope can then be sealed. To achieve this, the insertion frame 50 is first rotated in the direction opposite to arrow A in FIG. 9 , away from the insertion location 30 . The drive roller 32 is then moved from its position at the envelope flap securing location, where it was originally located, to an envelope sealing position. As shown in FIG. 10 , the envelope sealing position is reached by moving the drive roller 32 substantially in the direction of arrow B. This takes the drive roller 32 from one side (the upper side, in FIG. 9 ) to the other side (the lower side, in FIG. 10 ) of the feed path 46 , which is a continuation of the insertion location 30 . As the drive roller 32 moves in the direction of arrow B, securing support frame 40 is caused to rotate about pivot 40 a , giving rise to a relative rotation between drive roller 32 and securing roller 34 in the direction of arrow C around the axis 44 . This causes the securing roller 34 to travel part way around the outer circumference of drive roller 32 , as the drive roller moves in the direction of arrow B. This enables the end of the flap f to be retained securely between the drive roller 32 and securing roller 34 in the nip 35 . To ensure that grip of the flap is not lost, an appropriate amount of rotation of the drive roller 32 may be allowed, in order to maintain the desired position of the flap f in the nip 35 . As shown in FIG. 10 , the rotation and downward motion of the drive and securing roller pair 32 and 34 brings the nip 33 of the drive and sealing roller pair 32 and 36 into the feed path 46 at the insertion location 30 . Furthermore, the motion of the securing roller 34 , constrained by the common securing support frame 40 , assists in maintaining the hinge h at a desired location in the feed path 46 , to thereby force the hinge h into the roller nip 33 between the drive roller 32 and sealing roller 36 . As shown schematically in FIG. 10 , the hinge h of the envelope E is thus positioned ready for sealing in the sealing nip 33 .
[0066] As is further evident from FIG. 10 , the motion of the drive and sealing roller pair 32 and 36 in the direction of arrow B is constrained both by the rotation of the securing support frame 40 about its pivot 40 a , and by a follower portion 43 of the sealing support frame 42 being located within guide path 42 a . Likewise, the follower 29 b of the trap door support frame 29 is constrained to follow the trap door frame guide path 29 a , as the other end supported by the common securing frame 40 is moved in the direction of arrow B while the support frame 40 is rotated in the direction of arrow C. This effectively brings the trap door out of the way of the feed path 46 , during the transition.
[0067] In the configuration shown in FIG. 10 , a moistening wick 60 is positioned adjacent to the drive roller 32 in the sealing position of FIG. 10 . Because the flap is securely held in the nip 35 between drive roller 32 and securing roller 34 , the flap f is also brought into proximity or contact with the moistening wick 60 . The moistening wick 60 is located in a container 62 of moistening agent 62 a , typically water.
[0068] To seal the envelope, drive roller 32 is driven in the direction of arrow C, to force the hinge h through the sealing nip 33 . As shown, driving engagement is maintained by the sealing roller 36 being held in biased engagement with the drive roller 32 by biasing means 36 a . As is evident, as the hinge h is fed through the sealing nip 33 , the envelope E is driven along feed path 46 . As the drive of the envelope E progresses, the flap f released from its held position in nip 35 , due to rotation of drive roller 32 , whereby the natural resiliency of the flap f brings the flap into contact with the moistening wick 60 , to thereby moisten the gum on the envelope flap. As the flap f and main body m are fed through the sealing nip 33 by continued drive of the drive roller 32 , the flap f is brought into pressing engagement with the main body m of the envelope E. This securely seals the envelope flap f against the envelope main body m. To assist in driving the envelope through the sealing nip 33 , drive may be supplied from the insertion feed rollers 38 . The envelope E is then fully fed through the roller nip 33 between drive roller 32 and sealing roller 36 , along the feed path 46 , as a completed mail piece M. Referring once more to FIG. 3 , the completed mail piece M is received by ejection roller pair 13 a and ejected from the mail piece ejection opening 13 onto the mail piece collection tray 9 .
[0069] As an alternative to relying on the natural resiliency of the envelope flap f in order to moisten gum on the underside of the flap, the flap may instead be brought into positive engagement with the moistening wick 60 . One method is to move the hinge threshold T, or to reduce the radius of drive roller 32 , so that as the drive and sealing roller pair 32 and 36 moves to the envelope sealing position, with flap f securely held in the nip 35 , a buckle forms in the flap f that brings it positively into contact with moistening wick 60 . A further alternative is to provide a portion 40 b of the feed path leading into the insertion location 30 , mounted on the securing support frame 40 between the drive roller 32 and the position of the secured flap (see FIGS. 10 and 11 ). This portion 40 b can be configured to press the flap f into engagement with the moistening wick 60 as the securing support frame 40 rotates to the envelope sealing position.
[0070] The envelope sealing apparatus, which includes the drive roller 32 , sealing roller 36 and securing roller 34 , mounted on common support frames 40 and 42 , can then be returned from the envelope sealing position of FIG. 10 to the securing position of, for example, FIG. 3 , ready to receive any further envelope.
[0071] Referring now to FIG. 11 , the main components of the flap sealing apparatus are shown in perspective view, from the bottom-front-left-side of the mail piece creation device. From this view, the arrangement of the various rollers 32 , 34 , 36 on support frames 40 , 42 can be seen.
[0072] In particular, it can be seen how sealing roller 36 is held in biasing engagement with drive roller 32 by biasing means 36 a mounted in sealing support frame 42 . On the right-hand-side of FIG. 11 , the trap door support frame 29 is shown, including follower 29 b in guide path 29 a , for moving the trap door 28 out of the path of the flap sealing mechanism as it descends to the flap sealing position. The feed path portion 40 b for pressing flap f into contact with moistening wick 60 (in selected embodiments) is also visible.
[0073] On the left-hand side of FIG. 11 , detail of the sealing support frame 42 and how it is mounted to follower 43 to follow guide path 42 a is shown. Guide paths 29 a and 42 a may simply be tracks formed in side plates that define the side edges of the paper feed paths, for example. Also shown, schematically, is a motor drive arrangement 90 for supplying drive from a motor 92 to the drive roller 32 . Because gears 94 , 95 are mounted coaxially with the pivot 40 a of securing support frame 40 and axis 44 of drive roller 32 , drive can be supplied from motor 92 to drive roller 32 at both the flap securing and flap sealing positions of the sealing mechanism, without requiring a complex drive-engaging mechanism, such as electronic clutches and the like.
[0074] It will further be apparent that the securing support frame 100 on the left-hand-side of FIG. 11 is shaped as a link mechanism, cooperating with actuating link arm 102 , to move the sealing mechanism between the flap sealing position and flap securing position, differently from securing support frame 40 that is configured to (simultaneously) actuate the trap door 28 by moving trap door support frame 29 . Any suitable means may be utilized to actuate link arm 102 , although a preferred embodiment is cam-driven.
[0075] It will be appreciated that the envelope sealing apparatus described herein will be applicable to envelope sealing operations not restricted to the particular arrangement in the mail piece creation device herein described. For example, while the illustrated embodiment utilizes an insertion frame 50 and trap door 28 for inserting mail items into the envelope, such a configuration is not essential, and mail items may be inserted into envelope E along a different path, such as along feed path 46 .
[0076] It is further to be noted that because the sealing apparatus is mobile from a flap securing position to an envelope flap sealing position, the envelope with mail item inserted therein is fed along a straight feed path from insertion location 30 , through feed path 46 and out of mail piece ejection opening 13 . This enables such an envelope sealing apparatus to be of particular use for sealing envelopes that contain rigid or non-flexible mail items. Such mail items might typically include, for example, CDs or DVDs, thick booklets, cardboard, and many other non-flexible mail items that one might wish to deliver by post.
[0077] Similarly, while the illustrated embodiment is suitable for inserting a single folded sheet into a single envelope, each fed from a respective stack, it will be appreciated that the mail piece creation device is not so limited. In particular, known mail piece creation devices include means for collating a plurality of sheets, folding these simultaneously, and inserting them into an open envelope. The envelope sealing apparatus disclosed herein would be suitable for inclusion within such a mail piece creation device.
[0078] Furthermore, it should be noted that specific components have been described which are useful for handling the envelope E in the described operation. However, flapper 24 and flapper link mechanism 24 a would not be required at all in a device configured to receive envelopes that are provided in the open configuration, while moistening wick 60 and moistening agent container 62 would not be required for envelopes where it is not necessary to moisten the gum on the envelope flap. Envelopes are known, for example, containing gum portions on both the envelope flap f and envelope main body m that react when brought into mutual engagement so as to form a seal.
[0079] Additional modifications are also conceived, for the various components of the sealing apparatus. For example, the flap securing operation could be achieved using an appropriate electromechanical gripping apparatus, other than a securing roller 34 . Likewise, an equivalent sealing operation may be achieved by using alternative cooperating feeding members, such as driving feed belts, to seal the envelope. This might be appropriate, for example, where it is required to fit the sealing apparatus into a mail creation device that has space only for a particular size or shape of sealing apparatus within the housing, within which to accommodate the apparatus.
[0080] It is, of course, also apparent that rather than proceeding to feed the sealed envelope along feed path 46 , the finished mail piece could be ejected out of an opening at the end of insertion location 30 , by reversing the feed motion of the drive roller 32 and feed roller pair 38 , or equivalent driving means, after the sealing operation.
[0081] Although mail piece creation is described above firstly by reference to feeding and folding a sheet and secondly by reference to inserting such a sheet, as one example of a mail item, into an envelope, it will be apparent that the sheet handling and envelope handling steps set out above can be carried out simultaneously or in different sequences of operation, up until the point of inserting the sheet into the envelope prior to sealing. The sequences of such operation are thus open to preference.
[0082] Accordingly, it is to be understood that the present invention is defined by the scope of the appended claims. The accompanying drawings are merely illustrative, by way of example, and not limiting of the scope of protection.
[0083] By utilizing the sealing apparatus and associated method of the present invention, the size of a sealing apparatus and associated mail piece creation device can be reduced, by reducing the amount of motion that the envelope to be sealed must undertake. Furthermore, the sealing apparatus can be utilized for sealing mail pieces including mail items that are thick, non-flexible or rigid, where the mail item could not be fed around a curved path. | An envelope sealing apparatus for sealing an envelope having a main body and a sealable flap foldable about a hinge between the flap and main body, and sealable thereto. The apparatus comprises a feed path along which an envelope can be fed; a driving means associated with the feed path for feeding an envelope along the feed path; a flap securing means cooperative with the driving means to secure an open envelope flap in contact with the driving means; and a flap sealing means cooperative with the driving means to seal the flap to the main body when the driving means drives the envelope in a flap sealing direction along the feed path. A mail piece creation device incorporating such an envelope sealer is further provided, along with corresponding methods. | 1 |
CROSS REFERENCE TO RELATED APPLICATIONS
This is a non-provisional of U.S. Provisional Application Ser. No. 61/502,409, filed Jun. 29, 2011, which is incorporated herein by reference, and to which priority is claimed.
FIELD OF THE INVENTION
The present invention relates generally to implantable medical devices, and more particularly to improved current source architectures for an implantable neurostimulator.
BACKGROUND
Implantable neurostimulator devices are devices that generate and deliver electrical stimuli to body nerves and tissues for the therapy of various biological disorders, such as pacemakers to treat cardiac arrhythmia, defibrillators to treat cardiac fibrillation, cochlear stimulators to treat deafness, retinal stimulators to treat blindness, muscle stimulators to produce coordinated limb movement, spinal cord stimulators to treat chronic pain, cortical and deep brain stimulators to treat motor and psychological disorders, and other neural stimulators to treat urinary incontinence, sleep apnea, shoulder subluxation, etc.
FIGS. 1A and 1B shows a traditional Implantable Pulse Generator (IPG) 100 , which includes a biocompatible device case 30 formed of a conductive material such as titanium for example. The case 30 typically holds the circuitry and a battery necessary for the IPG 100 to function, although IPGs can also be powered via external RF energy and without a battery. The IPG 100 includes in this simple example an electrode array 102 containing a linear arrangement of electrodes 106 . The electrodes 106 are carried on a flexible body 108 , which also houses the individual electrode leads 112 coupled to each electrode. In the illustrated embodiment, there are eight electrodes on array 102 , labeled E 1 -E 8 , although the number of electrodes is application specific and therefore can vary. Array 102 couples to case 30 using a lead connector 38 , which is fixed in a non-conductive header material 36 such as epoxy for example. As is well known, the array 102 is implanted in an appropriate location in a patient to provide suitable simulative therapy, and is coupled through the patient's tissue to the IPG 100 , which may be implanted somewhat distant from the location of the array.
As shown in FIG. 1B , the IPG 100 typically includes an electronic substrate assembly 14 including a printed circuit board (PCB) 16 , along with various electronic components 20 , such as microprocessors, integrated circuits, and capacitors mounted to the PCB 16 . Two coils (more generally, antennas) are generally present in the IPG 100 : a telemetry coil 13 used to transcutaneously transmit/receive data to/from an external controller (not shown); and a charging coil 18 for transcutaneously charging or recharging the IPG's battery 26 using an external charger (also not shown).
A portion of circuitry 20 in the IPG 100 is dedicated to the provision of therapeutic currents to the electrodes 106 . Such currents are typically provided by current sources 150 , as shown in FIGS. 2A and 2B . In many current-source based architectures, some number of current sources 150 are associated with a particular number of electrodes 106 . For example, in FIG. 2A , it is seen that N electrodes E 1 -E N are supported by N dedicated current sources 150 1 - 150 N . In this example, and as is known, the current sources 150 are programmable (programming signals not shown) to provide a current of a certain magnitude and polarity to provide a particular therapeutic current to the patient. For example, if source 150 2 is programmed to source a 5 mA current, and source 150 3 is programmed to sink a 5 mA current, then 5 mA of current would flow from anode E 2 to cathode E 3 through the patient's tissue, R, hopefully with good therapeutic effect. Typically such current is allowed to flow for a duration, thus defining a current pulse, and such current pulses are typically applied to the patient with a given frequency. If the therapeutic effect is not good for the patient, the electrodes chosen for stimulation, the magnitude of the current they provide, their polarities, their durations, or their frequencies could be changed.
( FIG. 2A shows that each of the electrodes is tied to a decoupling capacitor. As is well known, decoupling capacitors promote safety by prevent the direct injection of current form the IPG 100 into the patient. For simplicity, decoupling capacitors are not shown in subsequent drawings, even though they are typically present in practical implementations).
FIG. 2B shows another example current source architecture using a switch matrix 160 . In this architecture, the switch matrix 160 is used to route current from any of the sources 150 P to any of the electrodes E N . For example, if source 105 2 is programmed to source a 5 mA current, and source 105 1 is programmed to sink a 5 mA current, and if source 150 2 is coupled to electrode E 2 by the switch matrix 160 , and if source 150 1 is connected to electrode E 3 by the switch matrix 160 , then 5 mA of current would flow from anode E 2 to cathode E 3 through the patient's tissue, R. In this example, because any of the current sources 150 can be connected to any of the electrodes, it is not strictly required that the number of electrodes (N) and the number of current sources (P) be the same. In fact, because it would perhaps be rare to activate all N electrodes at once, it may be sensible to make P less than N, to reduce the number of sources 150 in the IPG architecture. This however may not be the case, and the number of sources and electrodes could be equal (P=N). Although not shown, it should be understood that switch matrix 160 would contains P×N switches, and as many control signals (C 1,1 -C P,N ), to controllably interconnect all of the sources 150 P to any of the N electrodes. Further details of a suitable switch matrix can be found in U.S. Patent Pub. U.S. Patent Publication 2007/0038250, which is incorporated herein by reference.
The architecture of FIG. 2B , like the architecture of FIG. 2A , also comprises some number of current sources 150 (P) associated with a particular number of electrodes 106 (N). Other more complicated current architectures exist in the implantable stimulator art. See, e.g., the above-incorporated '250 Publication. But again generally such approaches all require some number of current sources 150 to be associated with a particular number of electrodes 106 .
The inventor considers the association of numbers of current sources and electrodes to be limiting because such architectures do not easily lend themselves to scaling. As implantable stimulator systems become more complicated, greater numbers of electrodes will provide patients more flexible therapeutic options. However, as the number of electrodes grows, so too must the number of current sources according to traditional approaches discussed above. This is considered undesirable by the inventor, because current source circuitry—even when embodied on an integrated circuit—is relatively large and complicated. Newer architectural approaches are thus believed necessary by the inventor to enable the growth of more complicated implantable stimulator systems, and such new architectures are presented herein.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1A and 1B show an implantable pulse generator (IPG), and the manner in which an electrode array is coupled to the IPG in accordance with the prior art.
FIGS. 2A and 2B show traditional current source architectures for an IPG in accordance with the prior art.
FIG. 3 shows an IPG in accordance with an embodiment of the invention in which a plurality of electrodes are grouped and provided at different locations in a patient.
FIGS. 4A and 4B show different current source architectures in accordance with embodiments of the invention to support the IPG of FIG. 3 .
FIGS. 5, 6A and 6B show timing diagrams for operating the IPG of FIG. 3 .
FIG. 7 shows logic for enabling the current source architectures described herein.
FIGS. 8A and 8B show alternative arrangements for grouping of electrodes in an IPG in accordance with embodiments of the invention.
DETAILED DESCRIPTION
FIG. 3 shows a more complicated IPG 200 which contains a higher number of electrodes than that illustrated earlier, and which may be indicative of the future progress of IPG technology. In the example shown, there are three electrode arrays 102 1 - 102 3 , each containing eight electrodes, with electrodes E 1 -E 8 on array 102 1 , E 9 -E 16 on array 102 2 , and E 17 -E 24 on array 102 3 . Each of the arrays 102 couples to the IPG 200 at a suitable lead connector 38 1 - 38 3 , which lead connectors can be arranged in the header 36 in any convenient fashion. It should be understood that this is merely an example, and that different numbers of arrays, and different numbers of electrodes on each array, could be used.
In this example, each of the arrays 102 1 - 102 3 comprises a group of electrodes that is implanted (or implantable) in a different location in a patient's body, thus allowing for the provision of complex stimulation patterns and/or stimulation across a wider portion of the patient's body. For example, in a therapy designed to alleviate sciatica, Location 1 for the Group 1 electrodes of array 102 1 (E 1 -E 8 ) might comprise the patient's right leg; Location 2 for the Group 2 electrodes of array 102 2 (E 9 -E 16 ) the left leg; and Location 3 for the Group 3 electrodes of array 102 3 (E 17 -E 24 ) the patient's spinal column. In a therapy designed to alleviate lower back pain, Location 1 of Group 1 might comprise the right side of a patient's spinal column; Location 2 of Group 2 the left side of the spinal column; and Location 3 of Group 3 a central location in the spinal column. Or each of Locations 1 - 3 may comprise different portions of a patient's brain in a deep brain stimulation example. The exact locations of each of the arrays, the number of electrodes in each array, and the particular therapies they provide, are not important to the concepts discussed herein. It is preferred that the Locations are non-overlapping in the patient's body.
As discussed in the Background section, conventional wisdom suggests that tripling the number of electrodes (from eight to 24 in this example) would require tripling the number of current sources in the IPG 200 used to support those electrodes. This is because conventional approaches associate a number of current sources with a particular number of electrodes, and hence the two would scale. As noted earlier, the inventor finds this unfortunate given the complexity and size of typical current course circuitry.
The present current source architecture diverges from this conventional approach by sharing current sources with an increased number of electrodes, such as is shown first in FIG. 4A . Consistent with FIG. 3 , 24 total electrodes are supported by the current source circuitry of FIG. 4A , comprising three arrays 102 1 - 102 3 (e.g., Groups) present in three different Locations in the body. FIG. 4A is somewhat similar to the architecture of FIG. 2A discussed earlier, in that there is a one-to-one correspondence of current sources 150 to electrodes within a given Group. For example, there are eight current sources 150 , and eight electrodes in each Group. New to FIG. 4A is a group select matrix 170 . The group select matrix 170 allows current from the current sources 150 to be sent to particular electrodes in each of the Groups. For example, current source 150 1 can send its current to electrode E 1 in Group 1 , to E 9 in Group 2 , and to E 17 in Group 3 . Current source 150 2 can send its current to E 2 in Group 1 , to E 10 in Group 2 , and E 18 in Group 3 , etc.
Group control is enabled in this example by the use of three group control signals G 1 -G 3 . When G 1 is asserted, switches (e.g., transistors) in the group switch matrix 170 are closed to respectively route the current from each of the current sources 150 1 - 150 8 to Group 1 electrodes E 1 -E 8 . (Of course, not all of the current sources 150 1 - 150 8 may be programmed at a given moment to provide a current, and so current will not necessarily flow at an electrode E 1 -E 8 merely because of the assertion of G 1 ). When G 2 is asserted, each of the current sources 150 1 - 150 8 are coupled to Group 2 electrodes E 9 -E 16 , and likewise when G 3 is asserted, each of the current sources 150 1 - 150 8 are coupled to Group 3 electrodes E 17 -E 24 . Although shown as switches, it should be understood that the group switch matrix 170 may also comprise a plurality of multiplexers.
Assume electrode E 13 is to output 5 mA of current while electrode E 12 is to receive that 5 mA of current. In this example, source 150 5 is programmed to source 5 mA worth of current, source 150 4 is programmed to sink 5 mA of current, and group control signal G 2 is asserted.
With this architecture, there is no need to scale the number of current sources; for example, the number of current sources 150 in this example equals eight, even though 24 electrodes are supported. A fourth group of electrodes (e.g., E 25 -E 32 ) could also be supported by these same eight current sources, etc. This is of great benefit, and conserves current source resources with the IPG 200 .
FIG. 4B shows another current source architecture employing a group select matrix 170 . The architecture of FIG. 4B is somewhat similar to the architecture of FIG. 2B discussed earlier in that it uses a switch matrix 160 to associate P current sources 150 1 - 150 P with a number of switch matrix outputs equal to the number of electrodes (N=8) in each Group. The switch matrix 160 thus allows the current of any of the current sources 150 1 - 150 P to be presented at any of the switch matrix 160 outputs, and the group select matrix 170 then routes those outputs to particular electrodes in the selected group.
Assume again that electrode E 13 is to output 5 mA of current while electrode E 12 is to receive that 5 mA of current. In this example, any of the P sources can be chosen to source and sink the current; assume that source 150 1 will source the current, while source 150 2 will sink the current. Electrode control signals C 1,5 and C 2,4 are asserted to close the necessary switches (not shown) in the switch matrix 160 to respectively connect source 150 1 to the fifth switch matrix output, and source 150 2 to the fourth switch matrix output. Then group control signal G 2 is asserted to respectively route those switch matrix outputs to electrodes E 13 and E 12 .
FIG. 5 shows examples of therapies that can be enabled using the current source architectures of FIG. 4A or 4B . As before, three arrays of electrodes, defining three Groups, are used to provide therapy to three different Locations in the patient. Assume that the therapies appropriate at each of these Locations have already been determined. For example, assume that at Location 1 it has been determined to source current from electrode E 3 and to sink that current from electrodes E 2 and E 4 , and to do so at particular magnitudes and durations t d which are unimportant for purposes of this example. Assume further that such therapy is to be provided at a frequency of f as shown. Assume further that at Location 2 it has been determined to sink current from electrode E 11 and to source that current from electrodes E 10 and E 12 , again at a frequency of f. Assume still further that at Location 3 it has been determined to source current from electrode E 18 and to sink that current from electrode E 19 , again at a frequency of f.
If the architecture of FIG. 4A is used, such therapy can be delivered as shown in FIG. 5 . As shown, the therapies at each of the Locations are interleaved, so that the various therapies are non-overlapping. This allows the current sources 150 to be shared and activated in a time-multiplexed fashion, first being dedicated to provision of therapy at Location 1 , then Location 2 , then Location 3 , and back to Location 1 again, etc. Assume that the architecture of FIG. 4A is used, in which there is a one-to-one correspondence of current sources 150 1 - 150 8 to electrodes within a given Group, i.e., at a particular Location. In this instance, current sources 150 2 - 150 4 are used to provide the therapy to electrodes E 2 -E 4 in Group 1 /Location 1 . Notice that group control signal G 1 is asserted during this time as shown in FIG. 5 . Then later, for example, after a recovery period t as discussed further below, these same current sources 150 2 - 150 4 are used to provide therapy to electrodes E 10 -E 12 in Group 2 /Location 2 , but this time with group control signal G 2 asserted. Again after another recovery period, two of these three same current sources 150 2 - 150 3 are used to provide the therapy to electrodes E 18 and E 19 in Group 3 /Location 3 , but this time with group control signal G 3 asserted. To summarize, by interleaving the therapy pulses at the different Groups/Locations, the current sources 150 can be shared and do not have to be increased in number to support the increased number of electrodes.
As is well known, stimulation pulses such as those shown in FIG. 5 would normally be followed by pulses of opposite polarity at the activated electrodes, and even thereafter additional steps may be taken to reduce the build-up of injected charge or to prepare for the provision of the next stimulation pulse. Such portions of time may be referred to generally as a recovery phase, and are shown in FIG. 5 as taking place during a time period t rp . It is preferable to not issue a next stimulation pulse until the preceding recovery phase is completed. The details of what occurs during the recovery phases are not shown in FIG. 5 for simplicity.
The extent to which therapies at different Locations can be interleaved will depend on several factors, such as the frequency f of simulation, the duration of the stimulation pulses t d , and the duration of the recovery periods t rp . For interleaving and sharing of current sources to occur as shown, these various timing periods should not be in conflict so that access to the current sources can be time multiplexed.
That being said, modifications can be made in the disclosed technique to accommodate at least some potential conflicts. For example, as shown in FIG. 6A , it is seen that the frequency of the therapy provided to the electrodes in Group 2 /Location 2 is different (f 2 ) from the frequency provided at the electrodes in Group 1 /Location 1 and Group 3 /Location 3 (f 1 ). This at times crates periods of conflict, t c , where the Group 2 /Location 2 stimulation may overlap with stimulation in other Groups/Locations. For example, specifically shown in FIG. 6A is a conflict between Group 2 /Location 2 and Group 1 /Location 1 , where both of these Groups/Location would be calling for support from the same current sources 150 2 - 150 4 . In this circumstance, and assuming the conflict would not occur too often, the logic 250 in the IPG 200 (discussed below with reference to FIG. 7 ) may decide to arbitrate the conflict by allowing only the Group 1 /Location 1 electrodes access to the desired current sources 150 2 - 150 4 . In other words, the Group 2 /Location 2 electrodes would simply not be pulsed during the conflict, as represented by dotted lies in FIG. 6A . Again, assuming such conflicts will not occur frequently, occasionally missing a stimulation pulse at a Group/Location should not materially affect patient therapy. Also, the downside to such therapy gaps can be alleviated by alternating the Groups/Locations being allowed access to the current sources during a conflict, e.g., by enabling Group 1 /Location 1 at a first instance of conflict, Group 2 /Location 2 at a second instance of conflict, Group 1 /Location 1 at a third instance of conflict, etc.
Conflicts of this type can also be resolved in different ways depending on the current source architecture used. FIG. 6B shows the same conflict between Group 1 /Location 1 and Group 2 /Location 2 presented in FIG. 6A . However, here the logic 250 in the IPG resolves the conflict not by sharing current sources, but instead providing different current sources to Group 1 /Location 1 and Group 2 /Location 2 . Of course, this assumes a more flexible architecture is used in which current sources can be freely assigned to particular electrodes, such as the architecture of FIG. 4B employing a switch matrix 160 . Recognizing the conflict, the logic 250 assigns current sources 150 1 , 150 5 , and 150 6 to electrodes E 10 , E 11 , and E 12 in Group 2 /Location 2 , rather than the current sources that might otherwise be expected (i.e., sources 150 2 - 150 4 ) which are instead assigned to the electrodes in Group 1 /Location 1 . Note that during the conflict both group control signals G 1 and G 2 can be asserted. Note also that current sources 150 2 - 150 3 are also assigned to the electrodes in Group 3 /Location 3 , which is possible because there is no conflict between Group 1 /Location 1 and Group 3 /Location 3 .
As noted above, control of the various current source architectures disclosed herein can be achieved by suitably programmed logic circuitry 250 , as shown in FIG. 7 . Logic 250 in one example can comprise a microcontroller, as is common in an IPG. While the microcontroller 250 can implement many different IPG functions, as relevant here the microcontroller is responsible for processing one or more stimulation programs 255 dictating therapy for a patient, and for enabling the current sources and groups accordingly. In one embodiment, the stimulation program 255 comprises separate stimulation programs for each Group/Location, which specific programs may have been arrived at through a fitting procedure during which the patient expresses his preference for particular settings. As shown, the microcontroller 250 ultimately issues commands to the current source architecture at appropriate times, including enabling particular current sources 150 , and specifying the magnitude, polarity, and duration of the current pulses. Also ultimately issued by the microcontroller 250 are the group control signals (G 1 , G 2 , etc.), which are received at the group select matrix 170 . If the current source architecture employs a switching matrix 160 as shown and described in FIG. 4B for example, the microcontroller 250 can also issue the control signals for that matrix (C 1,1 -C P,N ). To the extent that the stimulation program 255 presents a conflict, such as those discussed earlier with respect to FIGS. 6A and 6B , special arbitration logic 260 may be used to resolve the conflict, such as by skipping certain stimulation pulses ( FIG. 6A ), rerouting alternative current sources 150 if possible ( FIG. 6B ), or in other ways.
To this point it has been assumed that Groups/Locations of electrodes correspond to particular arrays 102 coupled to the IPG. But this is not necessarily the case, and groups of electrodes and their locations can be established in other ways. For example, FIG. 8A shows a single electrode arrays having 24 electrodes, divided into three Groups of eight. Each of these Groups corresponds to a different Location for therapy, even though present on the same array 102 , and thus this type of electrode grouping arrangement can still benefit from the current source architectures described herein. For example, eight current sources 150 can be employed if the architecture of FIG. 4A is used, or P current sources if the architecture of FIG. 4B is used. FIG. 8B shows another example in which a plurality of arrays ( 102 1 and 102 2 ) are treated as one Group of eight electrodes, even though such arrays would not be at exactly the same location in the patient. Nonetheless, the 24 electrodes present in FIG. 8B can be supported by eight current sources ( FIG. 4A ) or P current sources ( FIG. 4B ).
It should be understood that a “current source” comprises any type of power source capable of delivering a stimulation current to an electrode, such as a constant current source, a constant voltage source, or combinations of such sources.
A “microcontroller” should be understood as any suitable logic circuit, whether integrated or not, or whether implemented in hardware or software.
Although particular embodiments of the present invention have been shown and described, it should be understood that the above discussion is not intended to limit the present invention to these embodiments. It will be obvious to those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the present invention. Thus, the present invention is intended to cover alternatives, modifications, and equivalents that may fall within the spirit and scope of the present invention as defined by the claims. | A group select matrix is added to an implantable stimulator device to allow current sources to be dedicated to particular groups of electrodes at a given time. The group select matrix can time multiplex the current sources to the different groups of electrodes to allow therapy pulses to be delivered at the various groups of electrodes in an interleaved fashion. Each of the groups of electrodes may be confined to a particular electrode array implantable at a particular non-overlapping location in a patient's body. A switch matrix can be used in conjunction with the group select matrix to provide further flexibility to couple the current sources to any of the electrodes. | 0 |
BACKGROUND OF THE INVENTION
The present invention relates to a process for manufacturing semiconductor devices, and particularly to a process for manufacturing semiconductor devices capable of forming an SOI structure in which the laminate structure between a semiconductor and an insulator has good interface properties to such an extent that it can be used as a channel region and a gate insulating film in MOSFET's for LSI's.
Electronic computers and communication equipment have been developed rapidly. In recent years, in particular, a plurality of computers are coupled through communication circuits to form a network in an attempt to realize high degree of functions, opening the door toward the age of information. Therefore, it is urged to develop these equipment to meet the needs of the times, and it is desired to provide large-scale integrated circuits (LSI's) which are fundamental parts and which operate at higher speeds maintaining higher degree of integration. The conventional method to meet this demand was chiefly to scale down the elements. In the future, however, it is considered that the three dimensional integrated circuits and new device concept and/or designs employing the SOI (silicon on insulator) structure will play a leading role. Examples of such devices are shown in FIGS. 8A and 8B.
FIG. 8A is a section view of a three dimensional integrated circuit, and FIG. 8B is a section view showing a one-gate-wide CMOS inverter which is a transistor of a new structure reported in a paper entitled "One-Gate-Wide CMOS Inverter on Laser-Recrystallized Polysilicon" disclosed in IEEE Electron Devices Letters, Vol. EDL-1, No. 6, June, 1980, pp. 117-118 by J.F. Gibbons and K.F. Lee. In either device, a MOS-type field effect transistor (MOSFET) formed in a silicon layer 6 on an insulating film 5 works as a fundamental element. In FIG. 8A, a portion surrounded by a dot-dash line represents a MOSFET. Here, the one-gate-wide CMOS inverter stands for a complementary MOSFET (CMOS) in which the two upper and lower MOSFET's share a single gate electrode 1 as schematically shown in FIG. 9.
The conventional technique for forming the SOI structure can be roughly divided into a method of forming single crystalline silicon on an insulating film or on an insulating substrate, and a method of forming an insulating layer in a single crystalline silicon substrate. An example of the former method includes a technique according to which polycrystalline silicon deposited on an insulating film such as SiO 2 is crystallized by laser annealing, electron beam annealing or strip heater annealing. An example of the latter method includes a technique according to which a damaged layer is formed in the substrate by hydrogen ion implantation, and the damaged layer that can be easily oxidized is selectively oxidized, or a technique which forms an SiO 2 layer in the silicon substrate by oxygen ion implantation. Owing to such technique, at present, it is made possible to form an SOI of good crystallinity which is capable of forming a MOSFET. However, none of the SOI structures formed by these methods exhibit good electric properties on the interface between the silicon layer 6 and the insulating layer 5. If the MOSFET is formed as shown in FIG. 8A, the interface 32 between the insulating film 5 and the silicon layer 6 formed thereon serves as a path for a leakage current across the source 2 and the drain 3, and the element exhibits quite poor performance.
To avoid this problem, therefore, a method was contrived to form a channel stopper by implanting impurity ions into the interface 32, presenting considerably improved results.
However, when an underlying insulating film 5 is to be used as a gate insulating film 4 which is as thin as 5 to 100 nm as in a MOSFET formed in the upper layer of the one-gate-wide CMOS inverter shown in FIG. 8B, a channel is formed in the interface 33 between the underlying insulating film 5 and the silicon layer 6 formed thereon. Therefore, the above-mentioned problem becomes so serious that none of the above-mentioned methods is effective; i.e., the problem remains unsolved.
In FIGS. 8A, 8B and 9, reference numeral 1 denotes a gate electrode, 2 denotes a source region, 3 denotes a drain region, 4 denotes a gate insulating film, 5 denotes an underlying insulating film, 6 denotes a silicon layer, 7 denotes a silicon substrate, and 32 and 33 denote interfaces between the underlying insulating film and the silicon layer.
SUMMARY OF THE INVENTION
The object of the present invention is to provide a process for manufacturing semiconductor devices having an SOI structure which exhibits good interface properties between the insulating film and the semiconductor layer to such an extent that the underlying insulating film can be utilized as a gate insulating film, eliminating the defects involved in the above-mentioned conventional art.
To achieve the above object according to the present invention, the process for manufacturing semiconductor devices comprises a step for forming a bridge-type connecting bar or one-side supported bar (hereinafter referred to as microbridge) using a semiconductor as a material, and a step for forming an insulating film in at least a portion of the upper layer or the lower layer of the microbridge by oxidation or nitridation, to thereby form a multilayered structure consisting of a semiconductor and an insulator.
Further, the process for manufacturing semiconductor devices according to the present invention comprises:
(i) a step for forming at least one first insulating film of a predetermined shape on a substrate;
(ii) a step for forming a continuous semiconductor film on said substrate and said first insulating film;
(iii) a step for forming at least one island region of a predetermined shape by a lithography, said island region being comprised of the continuous semiconductor film on said substrate and on said first insulating film and said first insulating film under said semiconductor film;
(iv) a step for forming a microbridge which consists of said semiconductor film by removing said first insulating film of said island region from at least the side of said semiconductor film; and
(v) a step for forming a second insulating film on the exposed surface of said microbridge.
When the MOSFET's are to be produced by the process for manufacturing semiconductor devices of the present invention, a step (vi) for forming, in said microbridge, a MOSFET with said second insulating film as a gate insulating film, may be added after the aforementioned step (v).
The substrate may be the one that is usually used for the semiconductor devices. Though there is no particular limitation, a semiconductor substrate should be used when an active element such as MOSFET is to be formed in the substrate.
The second insulating film formed in the above step (v) may be an oxide film that is formed by an oxide-forming step such as thermal oxidation or plasma oxidation, or may be a nitride film formed by a nitride-forming step such as nitriding.
After the step (v), another step for providing the first insulating film on said microbridge, and the above-mentioned steps (ii) to (vi) may further be repeated at least one time, in order to form a multilayered microbridge.
When a semiconductor substrate is used, furthermore, the MOSFET's can be formed on both the substrate and the microbridge by the process for manufacturing semiconductor devices, which comprises:
(i) a step for forming at least one first insulating film of a predetermined shape on a semiconductor substrate;
(ii) a step for forming a continuous semiconductor film on said semiconductor substrate and said first insulating film;
(iii) a step for forming at least one island region of a predetermined shape by a lithography, said island region being comprised of the continuous semiconductor film on said semiconductor substrate and on said first insulating film and said first insulating film under said semiconductor film;
(iv) a step for forming a source region and a drain region in said semiconductor substrate and in said semiconductor film, respectively, by ion implantation;
(v) a step for forming a microbridge by removing the first insulating film from the island region, and for forming a second insulating film on the exposed surface of said microbridge; and
(vi) a step for forming a gate electrode in a gap under said microbridge.
In this case, the MOSFET's are self-aligned with respect to each other. In this case, furthermore, a one-gate-wide CMOS inverter structure can be formed by adding, after the step (vi), a step (vii) for removing a portion of said microbridge that is contacted to the source region of said semiconductor substrate.
In either case, the semiconductor constituting the microbridge should be a single crystalline semiconductor from the standpoint of forming elements. Single crystalline silicon is generally used.
The size of the microbridge should be determined depending upon the element that is to be formed in the microbridge. When a MOS is to be formed, the size is determined with reference to MOS's in general. Though there is no particular limitation, the height of the microbridge should desirably be smaller than 10 μm when the gate electrode is to be formed in the gap under the microbridge. If this height is exceeded, it becomes difficult to deposit the gate electrode.
Silicon and oxygen exhibit good chemical interaction relative to each other, and an SiO 2 layer/silicon layer structure which exhibits very good interface properties is formed owing to the chemical reaction between them, i.e., owing to the oxidation of a mechanism in which oxygen diffuses and enters into the substrate to meet silicon, to thereby form a silicon-oxygen bond. In other words, (1) a solid silicon without damage is oxidized to form an SiO 2 film, and (2) at this moment, oxygen is supplied by diffusion. The above two points serve as requirements for forming an Si/SiO 2 system that exhibits good interface properties. If the conventional SOI technology is considered from such a point of view, the method having the process for forming the silicon layer on the insulating film is not satisfying the above requirement (1), and in the method having the process for forming a SiO 2 layer inside the Si substrate, the requirement (2) is not satisfied, either, since the SiO 2 layer is formed in the silicon substrate by introducing oxygen by the ion implantation. It is therefore difficult to form a good interface.
Based upon the consideration on silicon, the present invention was contrived in an attempt to satisfy the above-mentioned requirements (1) and (2).
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1A to 1E are section views and perspective views illustrating the steps according to a first embodiment of the present invention;
FIGS. 2A to 2E are section views and perspective views illustrating the steps according to a second embodiment of the present invention;
FIGS. 3A and 3B are section views illustrating the steps according to a third embodiment of the present invention;
FIGS. 4A to 4O are section views and perspective views illustrating the steps according to a fourth embodiment of the present invention;
FIGS. 4P and 4Q are a section view and a perspective view illustrating the steps according to a fifth embodiment of the present invention;
FIGS. 5A to 5F are perspective views and section views illustrating the steps according to a seventh embodiment of the present invention;
FIG. 6 is a section view illustrating a semiconductor device according to an eighth embodiment of the present invention;
FIG. 7 is a section view illustrating a semiconductor device according to a ninth embodiment of the present invention;
FIG. 8A is a section view illustrating a conventional multilayered integrated circuit;
FIG. 8B is a sectional view showing a conventional one-gate-wide CMOS inverter; and
FIG. 9 is a diagram to schematically illustrate the one-gate-wide CMOS inverter.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Embodiments of the invention will be described hereinbelow.
Embodiment 1
This embodiment deals with the case where MOSFET's are formed in a silicon layer on an insulator.
As shown in FIG. 1A, an SiO 2 film 8 is formed maintaining a thickness of 7000 Angstroms by the CVD (chemical vapor deposition) method on a single crystalline silicon substrate 7, and is isolated in the form of an oblong island by the ordinary photolithography technique. Here, an insulating film composed of Si 3 N 4 or the like may be formed instead of forming the SiO 2 film. Or, the insulating film may be composed of a material other than SiO 2 or Si 3 N 4 , provided it exhibits a markedly large etching rate compared with that of a semiconductor film deposited thereon. Further, the island may be formed in any other shape such as circular shape, square shape, oblong shape, or the like. A polycrystalline silicon film is deposited thereon maintaining a thickness of 3500 Angstroms by the CVD method, and is transformed into a single crystalline form by the irradiation with a laser beam to form a single crystalline silicon film 9. That is, the SOI structure is formed by the conventional SOI-forming technique relying upon the laser annealing. Any other conventional SOI-forming technique may be employed such as SOI-forming technique based upon the strip heater annealing, SOI-forming technique which utilizes the solid phase epitaxial growth of silicon, or the like technique. In this embodiment, the whole semiconductor film is transformed into a single crystalline form. However, the semiconductor film may remain in a polycrystalline form if at least the element region is transformed into the single crystalline form. A photomask is applied thereon followed by anisotropic dry etching, in order to divide the SOI region into several island regions as shown in FIG. 1B (two islands are shown here). The SiO 2 film 8 is then selectively etched to form a microbridge 30 consisting of silicon as shown in FIG. lC. The thermal oxidation is then effected in dry oxygen at 1000° C., so that the surface of the microbridge is covered with an SiO 2 film 48 which has good quality and which is 450 Angstrom's thick. Thereafter, a MOSFET is formed by a widely known method on the microbridge 30 to use the SiO 2 film 48 as a gate oxide 4. FIG. 1D is a section view thereof. Here, the plasma oxidation may be effected instead of the thermal oxidation, and the SiO 2 film may be replaced by any other insulating film such as Si 3 N 4 . Further, if a gap 31 under the microbridge 30 is filled with polycrystalline silicon by the combination of CVD and etching, there can be formed not only a gate electrode 1 of the upper layer but also a gate electrode 1' of the lower layer as shown in FIG. 1E.
In FIGS. 1D and 1E, reference numerals 2 and 3 denote a source region and a drain region, respectively.
Embodiment 2
In this embodiment, a multilayered integrated circuit is prepared by forming a MOSFET on the silicon substrate, forming thereon a microbridge which consists of silicon, and forming a MOSFET on the bridge.
First, as shown in FIG. 2A, a MOSFET consisting of a gate electrode 1, a source region 2, a drain region 3 and a gate insulating film 4, is formed on a silicon substrate 7 by an ordinary process. An SiO 2 film 8 is deposited thereon by the CVD method maintaining a thickness of about 1.3 μm, and is patterned into an oblong shape by the known photolithography like in the embodiment 1. Then, the polycrystalline silicon film is deposited thereon maintaining a thickness of 3500 Angstroms by the CVD method, and is scanned by a laser beam, so that silicon deposited thereon is transformed into a single crystalline form, to thereby obtain a single crystalline silicon film 9. It needs not be pointed out that the SOI-forming technique using the electron beam, the SOI-forming technique utilizing the solid phase epitaxial growth, or the like technique may be employed in place of the SOI-forming technique which uses the laser beam. The oblong SOI region is cut off at predetermined portions by the etching using a mask to form island regions in a shape as shown in FIG. 2B. In this case, however, attention should be given such that a requirement d>W/2 is satisfied (see FIG. 2B where d denotes a thickness of the SiO 2 film 8 that remains on the region which is cut off, and W denotes a width of the SOI region which is not cut off). Concretely speaking, the width W is selected to be 0.8 μm and the thickness d is selected to be 0.8 μm. Then, the SiO 2 film 8 is etched by 0.5 μm by the widely known highly selective isotropic etching to remove part of the SiO 2 film 8 under the silicon film 9 in the SOI structure, to thereby form microbridge 30 consisting of silicon as shown in FIG. 2C. In this case, the depth by which the SiO 2 film 8 is etched has not been reaching the gate oxide of the MOSFET on the silicon substrate 7. Therefore, there is no probability that the FET is damaged. The requirement d>W/2 makes it possible to carry out the etching as mentioned above. Then, as shown in FIG. 2D, an SiO 2 film 48 is formed to have a thickness of 450 Angstroms by the thermal oxidation like in the embodiment 1. With the SiO 2 film 48 as a gate oxide 4, a MOSFET is formed on the microbridge through an ordinary process. The oxidation may be carried out by the plasma oxidation or by any other oxidation method like in the embodiment 1.
Thereafter the gap under the microbridge is filled with SiO 2 8 by the low-pressure CVD method, and the whole surface of the substrate is covered with the SiO 2 film 28. Thereafter, though not diagrammed, through holes are formed and a wiring composed of aluminum is formed to complete a multilayered integrated circuit. In this embodiment, upper and lower semiconductor layers having different types of conduction are formed, the gates are electrically connected together, and the heavily impurity doped semiconductor region of MOSFET of the upper layer is electrically connected to the heavily impurity doped semiconductor region of MOSFET of the lower layer, to thereby form a CMOS inverter. It need not be pointed out that the heavily impurity doped semiconductor regions of the upper and lower layers may be connected without using the wiring, by so forming the impurity doped regions that they are directly superposed upon one another over the drain regions 3 as shown in FIG. 2E, in which the SiO 2 film 48 is not diagrammed.
Embodiment 3
The structure shown in FIG. 2E is formed by the process of the embodiment 2. Then, using a photomask, the SiO 2 film 28 is removed by etching but leaving it on the microbridge only (FIG. 3A). Then, as shown in FIG. 3B, a single crystalline silicon film 25 is deposited only on the regions where silicon is exposed to a height of the microbridge by the well-known selective epitaxial growth method, and the surface is flattened. Nearly a flat structure can be obtained if the single crystalline silicon film is deposited to the height of the SiO 2 film 28. Thereafter, a microbridge is formed again by the process of the embodiment 2, and MOSFETs are formed in the layers to obtain the structure shown in FIG. 3B. Though not diagrammed, through holes are formed in an SiO 2 film 38 formed on the surface, and wirings are formed to complete a three-layered integrated circuit. In this embodiment, however, polycrystalline silicon having a high impurity concentration is used instead of forming aluminum wirings.
In FIGS. 3A and 3B, reference numerals other than 25 such as 3B denotes the same portions as those of FIGS. 2A to 2E, and the SiO 2 film 48 is not diagrammed.
Embodiment 4
This embodiment deals with the case where a one-gate-wide CMOS inverter is prepared according to the present invention. In both the upper and lower layers, the source and drain regions are formed being self-aligned to the gate electrode.
As shown in FIG. 4A, an n-type single crystalline silicon substrate 7 is prepared, and boron is implanted thereinto as designated at 11 using a mask 10 composed of a photoresist in order to form a p + -type region 2. This region finally serves as a source region of MOSFET of the lower layer. Then, as shown in FIG. 4B, the SOI structure is formed so as to be partly overlapped on the p + -type region by the conventional SOI-forming technique based upon the laser annealing as in the embodiment 1. Other SOI-forming technique may be employed like in the embodiment 1, as a matter of course. Boron ions are implanted into the single crystalline silicon film 9 that is deposited to impart the p-type of electric conduction. Reference numeral 8 denotes an SiO 2 film. Then, a mask is applied thereon, and the SOI region is divided by etching into several islands as shown in FIG. 1B of the first embodiment. Then, as Si 3 N 4 film 14 is deposited by the CVD method on the surface of the substrate, and is etched through a mask to form a shape as shown in FIG. 4C (which shows only one island region). The Si 3 N 4 film 14 is used as a mask for ion implantation to form the source and drain, and is further used to determine the position for forming the gate electrode. That is, boron ions are implanted with an acceleration energy of 500 keV and 200 keV to form p + -type regions 2 and 3 as shown in FIG. 4D. The p + -type region 2 superposed on the p + -type region that had been formed in the substrate in advance prior to forming the SOI structure, is used as the source region 2 of MOSFET of the lower layer in the one-gate-wide CMOS inverter, and another p + -type region is used as the drain region 3 of MOSFET of the lower layer. Then, phosphorus ions are implanted with an acceleration energy of 200 keV to form n + -type regions 12 and 13 in the deposited silicon film 9 as shown in FIG. 4E. The n + -type region 12 contacted to the source region 2 of the lower layer is used as a source region 12 of MOSFET formed in the upper layer, and the n + -type region 13 contacted to the drain region 3 of the lower layer is used as a drain 13 of the upper layer. With reference to FIG. 4F, a photoresist 10 is applied onto the surface of the substrate, and is patterned by the photolithography to form a mask as shown. The Si 3 N 4 film is subjected to the selective etching and is removed from around the SOI islands. The resist 10 is then removed to obtain a shape as shown in FIG. 4G. Here, if a specimen is exposed in a plasma, the surface of the specimen is covered with a field region called sheath. In the sheath, the positive ions are accelerated toward the specimen. Therefore, if the plasma etching is effected in a region where the gas pressure is low enough that a mean free path of ions becomes greater than the thickness of the sheath, the etching proceeds only in a direction perpendicular to the surface of the object. The SiO 2 film 8 on the specimen is selectively etched by utilizing this property. Namely, as shown in FIG. 4H, the SiO 2 film 8 is removed except a portion concealed by the Si 3 N 4 film 14, and whereby a microbridge composed of silicon is formed. The remaining SiO 2 film 8 forms a dummy gate 17. The Si 3 N 4 film 14 is then selectively removed by etching. The surface of the specimen is covered with an SiO 2 film 48 of a thickness of 1000 Angstroms by thermal oxidation in the same manner as in the embodiment 1, as shown in FIG. 4I. With reference to FIG. 4J, the Si 3 N 4 films 44, 16 are deposited by the CVD method followed by anisotropic etching as designated at 15. The Si 3 N 4 film 44 is removed except the Si 3 N 4 films 16 that are formed under the microbridge. The SiO 2 film is then selectively removed by etching so that the SiO 2 film 17 is removed from under the microbridge. The thermal oxidation is then effected in the same manner as described above in order to form an SiO 2 film maintaining a thickness of 250 Angstroms under the lower surface of the microbridge and on the surface of the substrate under the microbridge as shown in FIG. 4K. This SiO 2 film is a gate oxide 4 of the one-gate-wide CMOS inverter. Thereafter, a polycrystalline silicon film 1 having a high impurity concentration is deposited by the CVD method followed by anisotropic etching so as to be charged under the microbridge as shown in FIG. 4K, just like when the Si 3 N 4 film 16 was charged under the microbridge and was anisotropically etched in the previous step shown in FIG. 4J. This polycrystalline silicon film 1 forms a gate electrode 1 of the one-gate-wide CMOS inverter. Major portions of the devices are thus completed through the above-mentioned procedure.
Then, the processing is effected to achieve electric connection to the gate 1, and to the sources 12, 2 of the upper and lower layers. First, as shown in FIG. 4L, a photoresist 18 is applied onto the surface of the specimen. The photoresist film is then removed from the region surrounded by a dot-dash line in FIG. 4L, and the surface of the specimen is subjected to the etching until the gate electrode buried under the microbridge is exposed. The resist 18 is then removed so that the specimen assumes the form as shown in FIGS. 4M and 4N. As will be understand from the top view of FIG. 4N, the gate electrode 1 is exposed in a trapezoidal shape. This is because, the mask 14 used for forming the dummy gate assumed such a shape as shown in FIG. 4H.
The contact resistance can be reduced since the wiring is formed on the region of the trapezoidal shape. However, when even a slightly large contact resistance of the gate is permissible, the gate electrode 1 need not necessarily assume the trapezoidal shape. Here, the mask for forming the dummy gate further serves as a mask for forming the source and drain by ion implantation. Therefore, the shape at the ends of source and drain matches the shape of the gate electrode, as a matter of course. Through this step, the gate electrode 1 is partly exposed, and the source 12 in MOSFET of the upper layer is isolated from the source 2 of MOSFET of the lower layer. Finally, as shown in FIG. 4O, an SiO 2 film 28 is deposited by bias sputtering, contact holes are formed by etching using a mask, and aluminum wiring is formed to complete the one-gate-wide CMOS inverter. Here, it needs not be pointed out that a similar one-gate-wide CMOS inverter can also be produced through the same process even when the types of electric conduction employed in the above embodiments are reversed.
In FIG. 4O, reference numeral 19 denotes a gate electrode terminal, 20 denotes a source terminal of MOSFET of the upper layer, and 21 denotes a source electrode terminal of MOSFET of the lower layer.
Embodiment 5
This embodiment is a simplified form of the embodiment 4. That is, when the stray capacitance between the source or drain and the gate must be reduced to a small value, the device of the embodiment 4 is required. When the stray capacitance does not present much of a problem, on the other hand, the device of this embodiment is desirable.
The structure shown in FIG. 4E is formed by the same procedure as the one explained in the embodiment 4. The Si 3 N 4 film 14 is removed by the same selective etching method as that of the embodiment 4, and the SiO 2 film 8 is removed by another selective etching method. An SiO 2 film 48 is formed on the surface of the specimen maintaining a thickness of 250 Angstroms by the thermal oxidation. Then, polycrystalline silicon films 22 of a high impurity concentration are formed on the surface of the substrate, on the microbridge and under the microbridge by the low-pressure CVD method, in order to realize the structure shown in FIG. 4P (section view). Then, the polycrystalline silicon film 22 on the substrate is removed by the anisotropic etching except the portion on the microbridge and the portion that will be used as an electrode for drawing the gate electrode. Thereafter, the resist is applied, selectively removed, and the etching is effected using the resist as a mask, in the same manner as in the embodiment 4 shown in FIGS. 4L and 4M, in order to isolate the source 12 of MOSFET of the upper layer from the source 2 of MOSFET of the lower layer (FIG. 4Q). The specimen is then covered with a passivation film and contact holes are formed therein like the case of the SiO 2 film 28 shown in FIG. 4O of the embodiment 4. Then, wiring is formed to complete a one-gate-wide CMOS inverter. Even in this embodiment, it need not be pointed out that the one-gate-wide CMOS inverter can be produced through the same process with the types of conduction being reversed.
Embodiment 6
A MOSFET is produced in which the channel of the upper layer and the channel of the lower layer can be driven simultaneously by a single gate 1, in accordance with the process of the embodiment 4 but eliminating the ion implantation 11 shown in FIG. 4A, selecting the type of conduction of the deposited silicon film 9 to be the same as that of the substrate 7, selecting those ions that form the same type of conduction to form the source and drain, and eliminating the step for isolating the source regions 12 and 2 of the upper and lower layers. Compared with the conventional MOSFET, this means that the channel width is doubled without increasing the stray capacitance between the source and the drain, exhibiting twice as great transconductance g m .
Embodiment 7
This embodiment is to produce a MOSFET of the new structure described earlier in accordance with the present invention.
The structure shown in FIG. 1C is formed by the same procedure as the one illustrated in the embodiment 1, the conduction type of the deposited silicon film 9 is rendered to be the same as the conduction type of the substrate 7 by implanting ions, and the surface is covered with an oxide film 48 of a thickness of 250 Angstroms by thermal oxidation. Then, a polycrystalline silicon film 22 of a high impurity concentration is deposited by the CVD method, and a photomask 10 is formed thereon as shown in FIG. 5A. Through the anisotropic etching, the polycrystalline silicon film 22 is allowed to remain only under the mask 10 and under the microbridge. The polycrystalline silicon film 22 is then removed except a portion concealed by the mask 10 as shown in FIG. 5B by the anisotropic etching utilizing the sheath potential that was used for forming the dummy gate in the embodiment 4. The mask 10 is then removed, an oxide film 48 is formed maintaining a thickness of 500 Angstroms on the silicon surface by the thermal oxidation as shown in FIGS. 5C and 5D, and ions are implanted with the polycrystalline silicon film 22 as a mask, in order to form a source 2 and a drain 3 in the microbridge. When the stray capacitance between the source 2 or the drain 3 and the gate electrode 1 does not become much of a problem, the ordinary isotropic etching may be employed instead of the etching that utilizes the sheath potential. In this case, the polycrystalline silicon film 22 remains entirely under the microbridge, and the device is 10 formed as shown in FIGS. 5E and 5F. Though thermal oxidation was employed in this embodiment, it is also allowable to use the plasma oxidation, magnet-active microwave-discharged plasma CVD or the like in its place.
In FIGS. 5A to 5F, reference numeral 4 denotes a gate insulating film, 9 denotes a single crystalline silicon film, 19 denotes a gate electrode terminal, 23 denotes a source electrode terminal, and 24 denotes a drain electrode terminal.
Embodiment 8
In the step of the embodiment 7, a step is introduced to implant ions of the same conduction type as that of the source 2 and drain 3 of the microbridge with such a high acceleration energy that they reach the substrate 7, prior to implanting the ions that form the source 2 and drain 3 in the microbridge, in order to form a MOSFET of the structure shown in FIG. 6. The thus constructed device of this embodiment exhibits a transconductance g m which is increased by more than three times.
In FIG. 6, reference numerals denote the same portions as those of FIGS. 5A to 5F.
Embodiment 9
In the step of the embodiment 7, a step is introduced to implant ions that make the conduction type of the deposited silicon film 9 opposite to the conduction type of the substrate 7, instead of the step in which ions are implanted to make the conduction type of the deposited silicon film 9 the same as that of the substrate 7, a step is introduced to implant ions of the conduction type opposite to the conduction type of the source 12 and drain 13 in the microbridge with such a high acceleration energy that they reach the substrate 7 prior to implanting the ions that form the source 12 and drain 13 in the microbridge. A step is introduced to remove part of the source region 12 of the deposited silicon film 9 by etching using a mask in order to isolate the source region 12 from the source 2 formed in the substrate 7, after the sources 2, 12 and drains 3, 13 have been formed, to thereby obtain MOSFETs in the form shown in FIG. 7. This is a one-gate-wide CMOS inverter in which the MOSFET of the upper layer is the one that was explained in the embodiment 7.
In FIG. 7, reference numeral 1 denotes a gate electrode, 19 denotes a gate electrode terminal, 20 denotes a source electrode terminal of the MOSFET of the upper layer, 21 denotes a source electrode terminal of the MOSFET of the lower layer, and 22 denotes a polycrystalline silicon film.
In the foregoing were explained several embodiments. Among them, the air layer was used as an intermediate insulation between the MOSFET of the upper layer and the MOSFET of the lower layer or the substrate 7 in the embodiment 1 (FIG. 1D), embodiment 2 (FIG. 2D), embodiment 7 (FIG. 5D), embodiment 8 (FIG. 6) and embodiment 9 (FIG. 7). However, it needs not be pointed out that other insulator such as SiO 2 , Si 3 N 4 or the like may be charged into the air gap. Here, the dielectric constant of the intermediate insulator should be as small as possible. Therefore, vacuum having the smallest dielectric constant is most desired, and nitrogen or air having a small dielectric constant is desired in the next place. In the aforementioned embodiments, the elements that are obtained are mounted being filled with dry nitrogen.
In the aforementioned embodiments, furthermore, devices of the two-layered structure consisting of the deposited silicon layer and the silicon substrate, or of the three-layered structure, were obtained. However, it is also allowable to produce devices having four or more layers by further superimposing microbridges in several stages thereon in accordance with the procedure explained in the aforementioned embodiments. In the embodiment 2 and in the device of the multistage structure, furthermore, elements other than MOSFETs, such as capacitors may be formed in the microbridge or in the substrate.
In the aforementioned embodiments, furthermore, the density of surface states between the insulator and the silicon film on the insulator can be decreased to as small as about 2×10 -10 cm -2 . Accordingly, the leakage current between the source and the drain of the MOSFET formed in the silicon film can be decreased to be equal to, or smaller than, that of the MOSFET formed on the silicon substrate, without the need of forming the channel stopper in the interface. Widely known etching techniques may be employed to effect a variety of etchings in the above-mentioned embodiments.
According to the present invention as described above, the interface properties can be markedly improved between the underlying insulating film and the semiconductor layer formed on the insulating layer. This makes it possible to prevent the flow of leakage current between the source and the drain of the MOSFET without the need of forming a channel stopper in the interface, and to establish a fundamental process for producing a MOSFET in which the underlying insulating film serves as a gate insulating film. According to the present invention, furthermore, there is no need of forming a channel stopper as described above, eliminating the step for forming the channel stopper, and making it possible to easily obtain a one-gate-wide CMOS inverter and MOSFETs with a large transconductance. | A process for manufacturing semiconductor devices, comprising steps for obtaining a multilayered structure consisting of semiconductors and insulating films, by forming a microbridge which consists of a semiconductor in the form of a connecting bar or a one-side supported bar, and by forming an insulating film by oxidizing the exposed surface of the microbridge. The semiconductor device manufactured by the process of the invention exhibits good interface properties between the insulating film and the semiconductor layer. The invention makes it possible to easily manufacture a variety of MOSFETs with the SOI structure, which exhibit excellent characteristics. | 8 |
[0001] This application claims the benefit of Korea Patent Application No. 10-2009-00119398 filed on Dec. 3, 2009, the entire contents of which is incorporated herein by reference for all purposes as if fully set forth herein.
BACKGROUND
[0002] 1. Field
[0003] This document relates to a liquid crystal display which drives a liquid crystal display panel in a dot inversion by using a source drive integrated circuit outputting data voltages of which polarities are reversed by a column inversion scheme.
[0004] 2. Related Art
[0005] An active matrix type liquid crystal display (“LCD”) displays moving pictures by the use of thin film transistors (“TFTs”) as switching elements. The LCD can be made small-sized compared with a cathode ray tube (CRT) and is thus applied to portable information devices, office devices, computers, or the like, and further to television sets, as a substitute for the CRT.
[0006] The LCD includes an LC display panel, a backlight unit which provides light to the LC display panel, source drive integrated circuits (ICs) which supply data voltage for data lines in the LC display panel, gate drive ICs which supply gate pulses (or scan pulses) for gate lines (or scan lines) in the LC display panel, a control circuit which controls the above-described ICs, and a light source driving circuit which drives light sources of the backlight unit.
[0007] With the rapid development of the process techniques and the driving techniques for the LCD, a manufacturing cost of the LCD has been lowered and its image quality has been much improved. The power consumption, the image quality, and the manufacturing cost of the LCD are required to be further improved suitable for the demand for low power consumption and a low cost in an information terminal device.
SUMMARY
[0008] Embodiments of the present invention provide a liquid crystal display (LCD) comprising an LC display panel provided with a plurality of data lines, a plurality of gate lines intersecting the data lines, LC cells arranged in a matrix, and TFTs disposed at the intersections of the data lines and the gate lines; source drive ICs configured to supply data voltages to the data lines, wherein polarities of data voltages are reversed by a column inversion scheme; and a gate driving circuit configured to sequentially supply gate pulses for the gate lines.
[0009] Here, polarities of the data voltages charged in the LC cells in the LC display panel are reversed in dot unit.
[0010] In addition, at least a part of the LC display panel includes two LC cells disposed between data lines adjacent to each other in a (m+1)-th (where m is an odd number) horizontal display line so as to be spaced apart from two LC cells disposed between data lines adjacent to each other in an m-th horizontal display line.
[0011] The two LC cells in the m-th horizontal display line and the two LC cells in the (m+1)-th horizontal display line sequentially charge therein data voltages with the same polarity supplied from the same data line.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention. In the drawings:
[0013] FIG. 1 is a block diagram illustrating an LCD according to an embodiment of this document;
[0014] FIG. 2 is a detailed circuit diagram illustrating a first embodiment of the pixel array shown in FIG. 1 ;
[0015] FIG. 3 is a diagram illustrating an example where the first data line is connected to the (m+1)-th data line;
[0016] FIG. 4 is a waveform diagram illustrating data voltages supplied for the data lines in the LCD as shown in FIG. 3 ;
[0017] FIG. 5 is a diagram illustrating an example where the (m+1)-th data line is connected to an output channel of the source drive IC;
[0018] FIG. 6 is a waveform diagram illustrating data voltages supplied for the data lines in the LCD shown in FIG. 5 ;
[0019] FIG. 7 is a detailed circuit diagram illustrating a second embodiment of the pixel array shown in FIG. 1 ;
[0020] FIG. 8 is a detailed circuit diagram illustrating a third embodiment of the pixel array shown in FIG. 1 ;
[0021] FIG. 9 is a detailed circuit diagram illustrating a fourth embodiment of the pixel array shown in FIG. 1 ;
[0022] FIG. 10 is a detailed circuit diagram illustrating a fifth embodiment of the pixel array shown in FIG. 1 ;
[0023] FIG. 11 is a detailed circuit diagram illustrating a sixth embodiment of the pixel array shown in FIG. 1 ;
[0024] FIG. 12 is a detailed circuit diagram illustrating a seventh embodiment of the pixel array shown in FIG. 1 ;
[0025] FIG. 13 is a detailed circuit diagram illustrating an eighth embodiment of the pixel array shown in FIG. 1 ;
[0026] FIG. 14 is a detailed circuit diagram illustrating a ninth embodiment of the pixel array shown in FIG. 1 ;
[0027] FIG. 15 is a detailed circuit diagram illustrating a tenth embodiment of the pixel array shown in FIG. 1 ; and
[0028] FIG. 16 is a detailed circuit diagram illustrating an eleventh embodiment of the pixel array shown in FIG. 1 .
DETAILED DESCRIPTION
[0029] With reference to the accompanying drawings, exemplary embodiments of this document will be described by exemplifying an LCD. Like reference numerals designate like elements throughout the specification. In the following explanations, when a detailed description of well-known functions or configurations related to this document is determined to unnecessarily cloud a gist of this document, the detailed description thereof will be omitted.
[0030] Names of the respective elements used in the following explanations are selected for convenience of writing the specification and may be thus different from those in actual products.
[0031] Referring to FIG. 1 , an LCD according to an embodiment of this document an LC display panel provided with a pixel array 10 , source drive ICs 12 , and a timing controller 11 . A backlight unit, which uniformly provides light to the LC display panel, may be placed at a lower part of the LC display panel.
[0032] The LC display panel comprises an upper glass substrate and a lower glass substrate opposite to each other with an LC layer therebetween. The LC display panel is provided with the pixel array 10 . The pixel array 10 includes LC cells arranged in a matrix by the intersection structure of data lines and gate lines. The lower glass substrate of the pixel array 10 is provided with the data lines, the gate lines, TFTs, pixel electrodes of the LC cells connected to the TFTs, storage capacitors Cst connected to the pixel electrodes of the LC cells and so on. Each of the LC cells in the pixel array 10 is driven by a voltage difference between a voltage charged in the pixel electrode via the TFT and a common voltage applied to a common electrode, and this voltage difference controls transmittance of light passing the LC cell to display images corresponding to video data. A structure of the pixel array 10 will be described in detail with reference to following figures.
[0033] The upper glass substrate of the LC display panel is provided with black matrices, color filters and the common electrodes. The common electrodes are disposed on the upper glass substrate in a vertical field driving type such as a TN (twisted nematic) mode and a VA (vertically aligned) mode, and are disposed on the lower glass substrate along with the pixel electrodes in a horizontal field driving type such as an IPS (in-plane switching) mode and an FFS (fringe field switching) mode.
[0034] Polarizers are respectively attached to the outer surfaces of the lower and upper glass substrates of the LC display panel, and alignment layers are formed on the inner surfaces having contact to the LC layer to set pretilt angles of the LC layer.
[0035] The LCD may be implemented by not only the TN mode, the VA mode, the IPS mode, and the FFS mode, but also any other LC mode. The LCD may be implemented by any other type LCD such as a transmissive LCD, a transflective LCD, a reflective LCD, or the like. The transmissive LCD and the reflective LCD require the backlight unit. The backlight unit may be implemented by a direct type backlight unit or an edge type backlight unit.
[0036] The source drive ICs 12 are mounted on tape carrier packages (TCPs) 15 , joined to the lower glass substrate of the LC display panel and connected to a source printed circuit board (PCB) 14 by a TAB (tap automated bonding) process. The source drive ICs 12 may be attached to the lower glass substrate of the LC display panel. Each of data output channels of the source drive ICs 12 is connected to each data line in the pixel array 10 . The total number of the output channels of the source drive ICs 12 is about a half the total number of the data lines.
[0037] Each of the source drive ICs 12 receives digital video data from the timing controller 11 . The source drive ICs 12 convert the digital video data into positive/negative data voltage in response to source timing control signals from the timing controller 11 , and supply the converted data voltages for the data lines in the pixel array 10 via the output channels. The source drive ICs 12 supply the data voltages with polarities opposite to each other for adjacent data lines under the control of the timing controller 11 , and the polarities of the data voltages supplied for the respective data lines are maintained unchanged during one frame period. Thus, the source drive ICs 12 output the data voltages of which the polarities are reversed by a column inversion scheme as shown in FIGS. 4 and 6 .
[0038] The gate drivers 13 sequentially supply the gate pulses (or scan pulses) for the gate lines in the pixel array in response to gate timing control signals from the timing controller 11 . The gate drivers 13 may be mounted on TCPs and joined to the lower glass substrate of the LC display panel by the TAB process, or may be directly formed on the lower glass substrate along with the pixel array 10 by a GIP (gate in panel) process. The gate drivers 13 may be disposed at both sides of the pixel array 10 as shown in FIG. 2 , or may be disposed at one side of the pixel array 10 .
[0039] The timing controller 11 transmits the digital video data from an external system board to the source drive ICs 12 . The timing controller 11 generates the source timing control signals for controlling operation timings of the source drive ICs 12 and the gate timing control signals for controlling operation timings of the gate drivers 13 . The timing controller 11 is mounted on a control PCB 16 . The control PCB 16 and the source PCB 14 are connected to each other via a flexible printed circuit board 17 such as an FFC (flexible flat cable) or an FPC (flexible printed circuit).
[0040] FIG. 2 is a circuit diagram illustrating a first embodiment of the pixel array 10 .
[0041] In FIG. 2 , the pixel array 10 is provided with (m+1) data lines D 1 to Dm+1, the gate lines G 1 to G 2 n intersecting the data lines D 1 to Dm+1, and the TFTs T 11 to T 14 and T 21 to T 24 which switch current paths formed between the pixel electrodes PIX 11 to PIX 14 and PIX 21 to PIX 24 in the LC cells and the data lines D 1 to Dm+1 in response to the gate pulses. The number of the LC cells arranged in a single horizontal display line in this pixel array is 2m.
[0042] For the data voltages charged in the LC cells due to the pixel array structure in FIG. 2 , their polarities are reversed in a unit of horizontal 2-dot and vertical 1-dot inversion. In FIG. 2 , the arrow indicates an order of the data voltages being charged in the LC cells.
[0043] The source drive ICs 12 output to the data lines D 1 to Dm+1 the data voltages of which the polarities are reversed by the column inversion scheme. The gate drivers 13 sequentially supply the gate pulses for the first to 2n-th gate lines G 1 to G 2 n . A first gate pulse is provided to the first gate line G 1 , and then second to 2n-th gate pulses are provided to the second to 2n-th gate lines G 2 to Gln.
[0044] During an N-th (where N is an odd number) frame period, the source drive ICs 12 supply only negative data voltages for the odd-numbered data lines D 1 , D 3 , . . . , Dm−1 and Dm+1, and supply only positive data voltages for the even-numbered data lines D 2 , D 4 , . . . , and Dm. During a (N+1)-th frame period, the source drive ICs 12 supply only the positive data voltages for the odd-numbered data lines D 1 , D 3 , . . . , Dm−1 and Dm+1, and supply only the negative data voltages for the even-numbered data lines D 2 , D 4 , . . . , and Dm.
In embodiments described below, a character i for the data lines has a value equal to or less than m, and may have different values in each embodiment. The a character i is natural number. For example, in the embodiments shown in FIGS. 2 , 7 , 8 , 10 , 11 , 12 , 15 and 16 , the character i=3k−2 (where k is a natural number), and, in the embodiments shown in FIGS. 9 , 13 and 14 , the character i=4k−3. In the respective odd-numbered horizontal display lines LINE# 1 , LINE# 3 , . . . , and LINE#n−1, first and second LC cells in the odd-numbered horizontal display lines disposed between an i-th data line and a (i+1)-th data line charge therein the positive data voltages supplied from the (i+1)-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the (i+1)-th data line during the (N+1)-th frame period. In FIG. 2 , the reference numeral “PIX 11 ” denotes the first pixel electrodes formed in the first LC cells in the odd-numbered horizontal display lines, and the reference numeral “PIX 12 ” denotes the second pixel electrodes formed in the second LC cells in the odd-numbered horizontal display lines. In addition, in the respective even-numbered horizontal display lines LINE# 2 , LINE# 4 , . . . , and LINE#n, third and fourth LC cells in the even-numbered horizontal display lines disposed between the (i+1)-th data line and a (i+2) data line charge therein the positive data voltages supplied from the (i+1)-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the (i+1)-th data line during the (N+1)-th frame period. In FIG. 2 , the reference numeral “PIX 23 ” denotes the third pixel electrodes formed in the third LC cells in the even-numbered horizontal display lines, and the reference numeral “PIX 24 ” denotes the fourth pixel electrodes formed in the fourth LC cells in the even-numbered horizontal display lines. Therefore, the first and second LC cells in the odd-numbered horizontal display lines and the third and fourth LC cells in the even-numbered horizontal display lines charge therein the voltages with the same polarity supplied from the (i+1)-th data line.
[0046] In the respective odd-numbered horizontal display lines LINE# 1 , LINE# 3 , . . . , and LINE#n−1, third and fourth LC cells in the odd-numbered horizontal display lines disposed between the (i+1)-th data line and the (i+2)-th data line charge therein the negative data voltages supplied from the (i+2)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+2)-th data line during the (N+1)-th frame period. In FIG. 2 , the reference numeral “PIX 13 ” denotes the third pixel electrodes formed in the third LC cells in the odd-numbered horizontal display lines, and the reference numeral “PIX 14 ” denotes the fourth pixel electrodes formed in the fourth LC cells in the odd-numbered horizontal display lines. In addition, in the respective even-numbered horizontal display lines LINE# 2 , LINE# 4 , . . . , and LINE#n, fifth and sixth LC cells in the even-numbered horizontal display lines disposed between the (i+2)-th data line and a (i+3)-th data line charge therein the negative data voltages supplied from the (i+2)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+2)-th data line during the (N+1)-th frame period. In FIG. 2 , the fifth and sixth LC cells in the even-numbered horizontal display lines are not shown, and their connection structures are substantially the same as those of the first and second LC cells. Therefore, the third and fourth LC cells in the odd-numbered horizontal display lines and the fifth and sixth LC cells in the even-numbered horizontal display lines charge therein the voltages with the same polarity supplied from the (i+2)-th data line. Meanwhile, the first and second LC cells in the even-numbered horizontal display lines charge therein the data voltages with the same polarity supplied from the i-th data line.
[0047] In the pixel array 10 shown in FIG. 2 , connection relations among the TFTs, the pixel electrodes, and the data lines will be described by exemplifying the first to fourth LC cells in the first horizontal display line LINE# 1 , and the first to fourth LC cells in the second horizontal display line LINE# 2 .
[0048] In the first horizontal display line LINE# 1 , the first and second LC cells disposed between the first data line D 1 and the second data line D 2 charge therein data voltages sequentially supplied from the second data line D 2 . The first TFT T 11 in the first horizontal display line transmits the data voltage from the second data line D 2 to the first pixel electrode PIX 11 in response to the second gate pulse from the second gate line G 2 . The first pixel electrode PIX 11 charges the data voltage therein during about ½ horizontal period. A gate terminal of the first TFT T 11 is connected to the second gate line G 2 . A drain terminal of the first TFT T 11 is connected to the second data line D 2 , and a source terminal thereof is connected to the first pixel electrode PIX 11 . The second TFT T 12 in the first horizontal display line transmits the data voltage from the second data line D 2 to the second pixel electrode PIX 12 in response to the first gate pulse from the first gate line G 1 . The second pixel electrode PIX 12 charges the data voltage therein during about ½ horizontal period. A gate terminal of the second TFT T 12 is connected to the first gate line G 1 . A drain terminal of the second TFT T 12 is connected to the second data line D 2 , and a source terminal thereof is connected to the second pixel electrode PIX 12 .
[0049] In the first horizontal display line LINE# 1 , the third and fourth LC cells disposed between the second data line D 2 and the third data line D 3 charge therein data voltages sequentially supplied from the third data line D 3 . The third TFT T 13 in the first horizontal display line transmits the data voltage from the third data line D 3 to the third pixel electrode PIX 13 in response to the second gate pulse from the second gate line G 2 . The third pixel electrode PIX 13 charges the data voltage therein during about ½ horizontal period. A gate terminal of the third TFT T 13 is connected to the second gate line G 2 . A drain terminal of the third TFT T 13 is connected to the third data line D 3 , and a source terminal thereof is connected to the third pixel electrode PIX 13 . The fourth TFT T 14 in the first horizontal display line transmits the data voltage from the third data line D 3 to the fourth pixel electrode PIX 14 in response to the first gate pulse from the first gate line G 1 . The fourth pixel electrode PIX 14 charges the data voltage therein during about ½ horizontal period. A gate terminal of the fourth TFT T 14 is connected to the first gate line G 1 . A drain terminal of the fourth TFT T 14 is connected to the third data line D 3 , and a source terminal thereof is connected to the fourth pixel electrode PIX 14 .
[0050] In the second horizontal display line LINE# 2 , the first and second LC cells disposed between the first data line D 1 and the second data line D 2 charge therein data voltages sequentially supplied from the first data line D 1 . The first TFT T 21 in the second horizontal display line transmits the data voltage from the first data line D 1 to the first pixel electrode PIX 21 in response to the third gate pulse from the third gate line G 3 . The first pixel electrode PIX 21 charges the data voltage therein during about ½ horizontal period. A gate terminal of the first TFT T 21 is connected to the third gate line G 3 . A drain terminal of the first TFT T 21 is connected to the first data line D 1 , and a source terminal thereof is connected to the first pixel electrode PIX 21 . The second TFT T 22 in the second horizontal display line transmits the data voltage from the first data line D 1 to the second pixel electrode PIX 22 in response to the fourth gate pulse from the fourth gate line G 4 . The second pixel electrode PIX 22 charges the data voltage therein during about ½ horizontal period. A gate terminal of the second TFT T 22 is connected to the fourth gate line G 4 . A drain terminal of the second TFT T 22 is connected to the first data line D 1 , and a source terminal thereof is connected to the second pixel electrode PIX 22 .
[0051] In the second horizontal display line LINE# 2 , the third and fourth LC cells disposed between the second data line D 2 and the third data line D 3 charge therein the data voltages sequentially supplied from the second data line D 2 . The third and fourth LC cells in the second horizontal display line LINE# 2 are spaced apart from the first and the second LC cells in the first horizontal display line LINE# 1 in the diagonal direction, and share the second data line D 2 with the first and the second LC cells in the first horizontal display line LINE# 1 . Therefore, the first and second in the first horizontal display line LINE# 1 and the third and fourth LC cells sequentially charge therein the data voltages with the same polarity which are consecutively supplied via the second data line D 2 .
[0052] The third TFT T 23 in the second horizontal display line transmits the data voltage from the second data line D 2 to the third pixel electrode PIX 23 in response to the third gate pulse from the third gate line G 3 . The third pixel electrode PIX 23 charges the data voltage therein during about ½ horizontal period. A gate terminal of the third TFT T 23 is connected to the third gate line G 3 . A drain terminal of the third TFT T 23 is connected to the second data line D 2 , and a source terminal thereof is connected to the third pixel electrode PIX 23 . The fourth TFT T 24 in the second horizontal display line transmits the data voltage from the second data line D 2 to the fourth pixel electrode PIX 24 in response to the fourth gate pulse from the fourth gate line G 4 . The fourth pixel electrode PIX 24 charges the data voltage therein during about ½ horizontal period. A gate terminal of the fourth TFT T 24 is connected to the fourth gate line G 4 . A drain terminal of the fourth TFT T 24 is connected to the second data line D 2 , and a source terminal thereof is connected to the fourth pixel electrode PIX 24 .
[0053] In the LCD according to the embodiment of this document, the polarity of the data voltages charged in the LC cells connected to the same data line is the same, thereby it is possible to reduce power consumption in the source drive ICs and also make an amount of data charged in each LC cell uniform. Thus, according to this document, it is possible to prevent degradation in image quality such as brightness unevenness, color distortion, or the like resulting from the unevenness of the amount of data charged due to the inversion method in the related art. In addition, according to this document, it is possible to reduce the number of the data lines and the channels of the source drive ICs by the use of the TFT connection relation where the LC cells adjacent to each other in the horizontal direction share one data line with each other, and furthermore, to reduce the manufacturing cost of the LCD.
[0054] The pixel array 10 is not limited to that shown in FIG. 2 . For example, the pixel array 10 may be modified as shown in FIGS. 7 to 16 . In the embodiments in FIGS. 7 to 16 as well, the number of data lines is reduced by half, and the data voltages from the source drive ICs 12 are output by the column inversion scheme, and the LC cells in the pixel array 10 are driven by the dot inversion scheme.
[0055] The (m+1)-th data line Dm+1 disposed at the rightmost of the pixel array 10 may be connected to the first data line D 1 disposed at the leftmost of the pixel array 10 like in FIG. 3 . FIG. 4 is a waveform diagram illustrating the data voltages provided to the data lines D 1 to Dm+1 in the LCD shown in FIG. 3 .
[0056] Referring to FIGS. 3 and 4 , the LCD further comprises a connection line 111 extending via the TCPs 15 and the source PCB 14 .
[0057] The one end of the connection line 111 is connected to the first data line D 1 , and the other end of the connection line 111 is connected to the (m+1)-th data line Dm+1. Among the source drive ICs 12 , the output channel of the first source drive IC 12 disposed at the uppermost left of the pixel array 10 provide the data voltages to the first data line D 1 and the (m+1)-th data line Dm+1.
[0058] The (m+1)-th data Dm+1 disposed at the rightmost of the pixel array 10 may be connected to the output channel of the source drive IC 12 in the state of not being connected to the first data line D 1 as shown in FIG. 5 . FIG. 6 is a waveform diagram illustrating waveforms of the data voltages provided to the data lines in the LCD shown in FIG. 5 .
[0059] Referring to FIGS. 5 and 6 , the source drive IC 12 , which is disposed at the uppermost right of the LC display panel, further comprises an output channel connected to the (m+1)-th data line Dm+1. Therefore, the (m+1)-th data line Dm+1 is directly supplied with data voltages from the last source drive IC 12 disposed at the uppermost right of the pixel array 10 , among the source drive ICs 12 .
[0060] FIG. 7 is a circuit diagram illustrating a second embodiment of the pixel array 10 .
[0061] In FIG. 7 , the pixel array 10 is provided with data lines D 1 to Dm+1, gate lines G 1 to G 2 n intersecting the data lines D 1 to Dm+1, and TFTs T 11 to T 14 and T 21 to T 24 which switch current paths formed between the pixel electrodes PIX 11 to PIX 14 and PIX 21 to PIX 24 in LC cells and the data lines D 1 to Dm+1 in response to gate pulses. For the data voltages charged in the LC cells due to the pixel array structure in FIG. 7 , their polarities are reversed in a unit of horizontal 2-dot and vertical 1-dot (1×2 dots).
[0062] The source drive ICs 12 output to the data lines D 1 to Dm+1 the data voltages of which the polarities are reversed by the column inversion scheme. The gate drivers 13 sequentially supply the gate pulses for the first to 2n-th gate lines G 1 to G 2 n . A first gate pulse is provided to the first gate line G 1 , and then second to 2n-th gate pulses are provided to the second to 2n-th gate lines G 2 to G 2 n.
[0063] During an N-th frame period, the source drive ICs 12 supply only positive data voltages for the odd-numbered data lines D 1 , D 3 , . . . , Dm−1 and Dm+1, and supply only negative data voltages for the even-numbered data lines D 2 , D 4 , . . . , and Dm. During a (N+1)-th frame period, the source drive ICs 12 supply only the negative data voltages for the odd-numbered data lines D 1 , D 3 , . . . , Dm−1 and Dm+1, and supply only the positive data voltages for the even-numbered data lines D 2 , D 4 , . . . , and Dm.
[0064] In the respective odd-numbered horizontal display lines LINE# 1 , LINE# 3 , . . . , and LINE#n−1, first and second LC cells in the odd-numbered horizontal display lines disposed between an i-th data line and a (i+1)-th data line charge therein the positive data voltages supplied from the (i+1)-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the i-th data line during the (N+1)-th frame period. In FIG. 7 , the reference numeral “PIX 11 ” denotes the first pixel electrodes formed in the first LC cells in the odd-numbered horizontal display lines, and the reference numeral “PIX 12 ” denotes the second pixel electrodes formed in the second LC cells in the odd-numbered horizontal display lines.
[0065] In the respective odd-numbered horizontal display lines LINE# 1 , LINE# 3 , . . . , and LINE#n−1, third and fourth LC cells in the odd-numbered horizontal display lines disposed between the (i+1)-th data line and a (i+2)-th data line charge therein the negative data voltages supplied from the (i+1)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+1)-th data line during the (N+1)-th frame period. In FIG. 7 , the reference numeral “PIX 13 ” denotes the third pixel electrodes formed in the third LC cells in the odd-numbered horizontal display lines, and the reference numeral “PIX 14 ” denotes the fourth pixel electrodes formed in the fourth LC cells in the odd-numbered horizontal display lines. In addition, in the respective even-numbered horizontal display lines LINE# 2 , LINE# 4 , . . . , and LINE#n, first and second LC cells in the even-numbered horizontal display lines disposed between the i-th data line and the (i+1) data line charge therein the negative data voltages supplied from the (i+1)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+1)-th data line during the (N+1)-th frame period. In FIG. 7 , the reference numeral “PIX 21 ” denotes the first pixel electrodes formed in the first LC cells in the even-numbered horizontal display lines, and the reference numeral “PIX 22 ” denotes the second pixel electrodes formed in the second LC cells in the even-numbered horizontal display lines. Therefore, the third and fourth LC cells in the odd-numbered horizontal display lines and the first and second LC cells in the even-numbered horizontal display lines charge therein the voltages with the same polarity supplied from the (i+1)-th data line.
[0066] In the respective even-numbered horizontal display lines LINE# 2 , LINE# 4 , . . . , and LINE#n, third and fourth LC cells in the even-numbered horizontal display lines disposed between the (i+1)-th data line and a (i+2) data line charge therein the positive data voltages supplied from the (i+2)-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the (i+2)-th data line during the (N+1)-th frame period. In FIG. 7 , the reference numeral “PIX 23 ” denotes the third pixel electrodes formed in the third LC cells in the even-numbered horizontal display lines, and the reference numeral “PIX 24 ” denotes the fourth pixel electrodes formed in the fourth LC cells in the even-numbered horizontal display lines.
[0067] In the pixel array 10 shown in FIG. 7 , connection relations among the TFTs, the pixel electrodes, and the data lines will be described by exemplifying the first to fourth LC cells in the first horizontal display line LINE# 1 , and the first to fourth LC cells in the second horizontal display line LINE# 2 .
[0068] In the first horizontal display line LINE# 1 , the first and second LC cells disposed between the first data line D 1 and the second data line D 2 charge therein data voltages sequentially supplied from the first data line D 1 . The first TFT T 11 in the first horizontal display line transmits the data voltage from the first data line D 1 to the first pixel electrode PIX 11 in response to the second gate pulse from the second gate line G 2 . The first pixel electrode PIX 11 charges the data voltage therein during about ½ horizontal period. A gate terminal of the first TFT T 11 is connected to the second gate line G 2 . A drain terminal of the first TFT T 11 is connected to the first data line D 1 , and a source terminal thereof is connected to the first pixel electrode PIX 11 . The second TFT T 12 in the first horizontal display line transmits the data voltage from the first data line D 1 to the second pixel electrode PIX 12 in response to the first gate pulse from the first gate line G 1 . The second pixel electrode PIX 12 charges the data voltage therein during about ½ horizontal period. A gate terminal of the second TFT T 12 is connected to the first gate line G 1 . A drain terminal of the second TFT T 12 is connected to the first data line D 1 , and a source terminal thereof is connected to the second pixel electrode PIX 12 .
[0069] In the first horizontal display line LINE# 1 , the third and fourth LC cells disposed between the second data line D 2 and the third data line D 3 charge therein data voltages sequentially supplied from the second data line D 2 . The third TFT T 13 in the first horizontal display line transmits the data voltage from the second data line D 2 to the third pixel electrode PIX 13 in response to the second gate pulse from the second gate line G 2 . The third pixel electrode PIX 13 charges the data voltage therein during about ½ horizontal period. A gate terminal of the third TFT T 13 is connected to the second gate line G 2 . A drain terminal of the third TFT T 13 is connected to the second data line D 2 , and a source terminal thereof is connected to the third pixel electrode PIX 13 . The fourth TFT T 14 in the first horizontal display line transmits the data voltage from the second data line D 2 to the fourth pixel electrode PIX 14 in response to the first gate pulse from the first gate line G 1 . The fourth pixel electrode PIX 14 charges the data voltage therein during about ½ horizontal period. A gate terminal of the fourth TFT T 14 is connected to the first gate line G 1 . A drain terminal of the fourth TFT T 14 is connected to the second data line D 2 , and a source terminal thereof is connected to the fourth pixel electrode PIX 14 .
[0070] In the second horizontal display line LINE# 2 , the first and second LC cells disposed between the first data line D 1 and the second data line D 2 charge therein data voltages sequentially supplied from the second data line D 2 . The first TFT T 21 in the second horizontal display line transmits the data voltage from the second data line D 2 to the first pixel electrode PIX 21 in response to the third gate pulse from the third gate line G 3 . The first pixel electrode PIX 21 charges the data voltage therein during about ½ horizontal period. A gate terminal of the first TFT T 21 is connected to the third gate line G 3 . A drain terminal of the first TFT T 21 is connected to the second data line D 2 , and a source terminal thereof is connected to the first pixel electrode PIX 21 . The second TFT T 22 in the second horizontal display line transmits the data voltage from the second data line D 2 to the second pixel electrode PIX 22 in response to the fourth gate pulse from the fourth gate line G 4 . The second pixel electrode PIX 22 charges the data voltage therein during about ½ horizontal period. A gate terminal of the second TFT T 22 is connected to the fourth gate line G 4 . A drain terminal of the second TFT T 22 is connected to the second data line D 2 , and a source terminal thereof is connected to the second pixel electrode PIX 22 .
[0071] In the second horizontal display line LINE# 2 , the third and fourth LC cells disposed between the second data line D 2 and the third data line D 3 charge therein the data voltages sequentially supplied from the third data line D 3 . The third TFT T 23 in the second horizontal display line transmits the data voltage from the third data line D 3 to the third pixel electrode PIX 23 in response to the third gate pulse from the third gate line G 3 . The third pixel electrode PIX 23 charges the data voltage therein during about ½ horizontal period. A gate terminal of the third TFT T 23 is connected to the third gate line G 3 . A drain terminal of the third TFT T 23 is connected to the third data line D 3 , and a source terminal thereof is connected to the third pixel electrode PIX 23 . The fourth TFT T 24 in the second horizontal display line transmits the data voltage from the third data line D 3 to the fourth pixel electrode PIX 24 in response to the fourth gate pulse from the fourth gate line G 4 . The fourth pixel electrode PIX 24 charges the data voltage therein during about ½ horizontal period. A gate terminal of the fourth TFT T 24 is connected to the fourth gate line G 4 . A drain terminal of the fourth TFT T 24 is connected to the third data line D 3 , and a source terminal thereof is connected to the fourth pixel electrode PIX 24 .
[0072] FIG. 8 is a circuit diagram illustrating a third embodiment of the pixel array 10 .
[0073] Referring to FIG. 8 , the pixel array 10 is provided with data lines D 1 to Dm+1, gate lines G 1 to G 2 n intersecting the data lines D 1 to Dm+1, and TFTs T 11 to T 14 and T 21 to T 24 which switch current paths formed between the pixel electrodes PIX 11 to PIX 14 and PIX 21 to PIX 24 in LC cells and the data lines D 1 to Dm+1 in response to gate pulses. For the data voltages charged in the LC cells due to the pixel array structure in FIG. 8 , their polarities are reversed in a unit of horizontal 2-dot and vertical 1-dot.
[0074] The source drive ICs 12 output to the data lines D 1 to Dm+1 the data voltages of which the polarities are reversed by the column inversion scheme. The gate drivers 13 sequentially supply the gate pulses for the first to 2n-th gate lines G 1 to G 2 n . A first gate pulse is provided to the first gate line G 1 , and then second to 2n-th gate pulses are provided to the second to 2n-th gate lines G 2 to G 2 n.
[0075] During an N-th frame period, the source drive ICs 12 supply only positive data voltages for the odd-numbered data lines D 1 , D 3 , . . . , Dm−1 and Dm+1, and supply only negative data voltages for the even-numbered data lines D 2 , D 4 , . . . , and Dm.
[0076] During a (N+1)-th frame period, the source drive ICs 12 supply only the negative data voltages for the odd-numbered data lines D 1 , D 3 , . . . , Dm−1 and Dm+1, and supply only the positive data voltages for the even-numbered data lines D 2 , D 4 , . . . , and Dm.
[0077] In the respective odd-numbered horizontal display lines LINE# 1 , LINE# 3 , . . . , and LINE#n−1, first and second LC cells in the odd-numbered horizontal display lines disposed between an i-th data line and a (i+1)-th data line charge therein the positive data voltages supplied from the (i+1)-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the i-th data line during the (N+1)-th frame period. In FIG. 8 , the reference numeral “PIX 11 ” denotes the first pixel electrodes formed in the first LC cells in the odd-numbered horizontal display lines, and the reference numeral “PIX 12 ” denotes the second pixel electrodes formed in the second LC cells in the odd-numbered horizontal display lines.
[0078] In the respective odd-numbered horizontal display lines LINE# 1 , LINE# 3 , . . . , and LINE#n−1, third and fourth LC cells in the odd-numbered horizontal display lines disposed between the (i+1)-th data line and a (i+2)-th data line charge therein the negative data voltages supplied from the (i+1)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+1)-th data line during the (N+1)-th frame period. In FIG. 8 , the reference numeral “PIX 13 ” denotes the third pixel electrodes formed in the third LC cells in the odd-numbered horizontal display lines, and the reference numeral “PIX 14 ” denotes the fourth pixel electrodes formed in the fourth LC cells in the odd-numbered horizontal display lines. In addition, in the respective even-numbered horizontal display lines LINE# 2 , LINE# 4 , . . . , and LINE#n, first and second LC cells in the even-numbered horizontal display lines disposed between the i-th data line and the (i+1) data line charge therein the negative data voltages supplied from the (i+1)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+1)-th data line during the (N+1)-th frame period. In FIG. 8 , the reference numeral “PIX 21 ” denotes the first pixel electrodes formed in the first LC cells in the even-numbered horizontal display lines, and the reference numeral “PIX 22 ” denotes the second pixel electrodes formed in the second LC cells in the even-numbered horizontal display lines. Therefore, the third and fourth LC cells in the odd-numbered horizontal display lines and the first and second LC cells in the even-numbered horizontal display lines charge therein the voltages with the same polarity supplied from the (i+1)-th data line.
[0079] In the respective even-numbered horizontal display lines LINE# 2 , LINE# 4 , . . . , and LINE#n, third and fourth LC cells in the even-numbered horizontal display lines disposed between the (i+1)-th data line and a (i+2) data line charge therein the positive data voltages supplied from the (i+2)-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the (i+2)-th data line during the (N+1)-th frame period. In FIG. 8 , the reference numeral “PIX 23 ” denotes the third pixel electrodes formed in the third LC cells in the even-numbered horizontal display lines, and the reference numeral “PIX 24 ” denotes the fourth pixel electrodes formed in the fourth LC cells in the even-numbered horizontal display lines.
[0080] In the pixel array 10 shown in FIG. 8 , connection relations among the TFTs, the pixel electrodes, and the data lines will be described by exemplifying the first to fourth LC cells in the first horizontal display line LINE# 1 , and the first to fourth LC cells in the second horizontal display line LINE# 2 .
[0081] In the first horizontal display line LINE# 1 , the first and second LC cells disposed between the first data line D 1 and the second data line D 2 charge therein data voltages sequentially supplied from the first data line D 1 . The first TFT T 11 in the first horizontal display line transmits the data voltage from the first data line D 1 to the first pixel electrode PIX 11 in response to the first gate pulse from the first gate line G 1 . The first pixel electrode PIX 11 charges the data voltage therein during about ½ horizontal period. A gate terminal of the first TFT T 11 is connected to the first gate line G 1 . A drain terminal of the first TFT T 11 is connected to the first data line D 1 , and a source terminal thereof is connected to the first pixel electrode PIX 11 . The second TFT T 12 in the first horizontal display line transmits the data voltage from the first data line D 1 to the second pixel electrode PIX 12 in response to the second gate pulse from the second gate line G 2 . The second pixel electrode PIX 12 charges the data voltage therein during about ½ horizontal period. A gate terminal of the second TFT T 12 is connected to the second gate line G 2 . A drain terminal of the second TFT T 12 is connected to the first data line D 1 , and a source terminal thereof is connected to the second pixel electrode PIX 12 .
[0082] In the first horizontal display line LINE# 1 , the third and fourth LC cells disposed between the second data line D 2 and the third data line D 3 charge therein data voltages sequentially supplied from the second data line D 2 . The third TFT T 13 in the first horizontal display line transmits the data voltage from the second data line D 2 to the third pixel electrode PIX 13 in response to the second gate pulse from the second gate line G 2 . The third pixel electrode PIX 13 charges the data voltage therein during about ½ horizontal period. A gate terminal of the third TFT T 13 is connected to the second gate line G 2 . A drain terminal of the third TFT T 13 is connected to the second data line D 2 , and a source terminal thereof is connected to the third pixel electrode PIX 13 . The fourth TFT T 14 in the first horizontal display line transmits the data voltage from the second data line D 2 to the fourth pixel electrode PIX 14 in response to the first gate pulse from the first gate line G 1 . The fourth pixel electrode PIX 14 charges the data voltage therein during about ½ horizontal period. A gate terminal of the fourth TFT T 14 is connected to the first gate line G 1 . A drain terminal of the fourth TFT T 14 is connected to the second data line D 2 , and a source terminal thereof is connected to the fourth pixel electrode PIX 14 .
[0083] In the second horizontal display line LINE# 2 , the first and second LC cells disposed between the first data line D 1 and the second data line D 2 charge therein data voltages sequentially supplied from the second data line D 2 . The first TFT T 21 in the second horizontal display line transmits the data voltage from the second data line D 2 to the first pixel electrode PIX 21 in response to the fourth gate pulse from the fourth gate line G 4 . The first pixel electrode PIX 21 charges the data voltage therein during about ½ horizontal period. A gate terminal of the first TFT T 21 is connected to the fourth gate line G 4 . A drain terminal of the first TFT T 21 is connected to the second data line D 2 , and a source terminal thereof is connected to the first pixel electrode PIX 21 . The second TFT T 22 in the second horizontal display line transmits the data voltage from the second data line D 2 to the second pixel electrode PIX 22 in response to the third gate pulse from the third gate line G 3 . The second pixel electrode PIX 22 charges the data voltage therein during about ½ horizontal period. A gate terminal of the second TFT T 22 is connected to the third gate line G 3 . A drain terminal of the second TFT T 22 is connected to the second data line D 2 , and a source terminal thereof is connected to the second pixel electrode PIX 22 .
[0084] In the second horizontal display line LINE# 2 , the third and fourth LC cells disposed between the second data line D 2 and the third data line D 3 charge therein the data voltages sequentially supplied from the third data line D 3 . The third TFT T 23 in the second horizontal display line transmits the data voltage from the third data line D 3 to the third pixel electrode PIX 23 in response to the third gate pulse from the third gate line G 3 . The third pixel electrode PIX 23 charges the data voltage therein during about ½ horizontal period. A gate terminal of the third TFT T 23 is connected to the third gate line G 3 . A drain terminal of the third TFT T 23 is connected to the third data line D 3 , and a source terminal thereof is connected to the third pixel electrode PIX 23 . The fourth TFT T 24 in the second horizontal display line transmits the data voltage from the third data line D 3 to the fourth pixel electrode PIX 24 in response to the fourth gate pulse from the fourth gate line G 4 . The fourth pixel electrode PIX 24 charges the data voltage therein during about ½ horizontal period. A gate terminal of the fourth TFT T 24 is connected to the fourth gate line G 4 . A drain terminal of the fourth TFT T 24 is connected to the third data line D 3 , and a source terminal thereof is connected to the fourth pixel electrode PIX 24 .
[0085] FIG. 9 is a circuit diagram illustrating a fourth embodiment of the pixel array 10 .
[0086] In FIG. 9 , the pixel array 10 is provided with data lines D 1 to Dm+1, gate lines G 1 to G 2 n intersecting the data lines D 1 to Dm+1, and TFTs T 11 to T 16 and T 21 to T 26 which switch current paths formed between the pixel electrodes PIX 11 to PIX 16 and PIX 21 to PIX 26 in LC cells and the data lines D 1 to Dm+1 in response to gate pulses. For the data voltages charged in the LC cells due to the pixel array structure in FIG. 9 , their polarities are reversed in a unit of horizontal 2-dot and vertical 1-dot.
[0087] The source drive ICs 12 output to the data lines D 1 to Dm+1 the data voltages of which the polarities are reversed by the column inversion scheme. The gate drivers 13 sequentially supply the gate pulses for the first to 2n-th gate lines G 1 to G 2 n . A first gate pulse is provided to the first gate line G 1 , and then second to 2n-th gate pulses are provided to the second to 2n-th gate lines G 2 to G 2 n.
[0088] During an N-th frame period, the source drive ICs 12 supply only positive data voltages for the odd-numbered data lines D 1 , D 3 , . . . , Dm−1 and Dm+1, and supply only negative data voltages for the even-numbered data lines D 2 , D 4 , . . . , and Dm. During a (N+1)-th frame period, the source drive ICs 12 supply only the negative data voltages for the odd-numbered data lines D 1 , D 3 , . . . , Dm−1 and Dm+1, and supply only the positive data voltages for the even-numbered data lines D 2 , D 4 , . . . , and Dm.
[0089] In the respective odd-numbered horizontal display lines LINE# 1 , LINE# 3 , . . . , and LINE#n−1, first and second LC cells in the odd-numbered horizontal display lines disposed between an i-th data line and a (i+1)-th data line charge therein the positive data voltages supplied from the i-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the i-th data line during the (N+1)-th frame period. In FIG. 9 , the reference numeral “PIX 11 ” denotes the first pixel electrodes formed in the first LC cells in the odd-numbered horizontal display lines, and the reference numeral “PIX 12 ” denotes the second pixel electrodes formed in the second LC cells in the odd-numbered horizontal display lines.
[0090] In the respective odd-numbered horizontal display lines LINE# 1 , LINE# 3 , . . . , and LINE#n−1, third and fourth LC cells in the odd-numbered horizontal display lines disposed between the (i+1)-th data line and a (i+2)-th data line charge therein the negative data voltages supplied from the (i+1)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+1)-th data line during the (N+1)-th frame period. In FIG. 9 , the reference numeral “PIX 13 ” denotes the third pixel electrodes formed in the third LC cells in the odd-numbered horizontal display lines, and the reference numeral “PIX 14 ” denotes the fourth pixel electrodes formed in the fourth LC cells in the odd-numbered horizontal display lines. In addition, in the respective even-numbered horizontal display lines LINE# 2 , LINE# 4 , . . . , and LINE#n, first and second LC cells in the even-numbered horizontal display lines disposed between the i-th data line and the (i+1) data line charge therein the negative data voltages supplied from the (i+1)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+1)-th data line during the (N+1)-th frame period. In FIG. 9 , the reference numeral “PIX 21 ” denotes the first pixel electrodes formed in the first LC cells in the even-numbered horizontal display lines, and the reference numeral “PIX 22 ” denotes the second pixel electrodes formed in the second LC cells in the even-numbered horizontal display lines. Therefore, the third and fourth LC cells in the odd-numbered horizontal display lines and the first and second LC cells in the even-numbered horizontal display lines charge therein the data voltages with the same polarity supplied from the (i+1)-th data line.
[0091] In the respective odd-numbered horizontal display lines LINE# 1 , LINE# 3 , . . . , and LINE#n−1, fifth and sixth LC cells in the odd-numbered horizontal display lines disposed between the (i+2)-th data line and a (i+3)-th data line charge therein the positive data voltages supplied from the (i+2)-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the (i+2)-th data line during the (N+1)-th frame period. In FIG. 9 , the reference numeral “PIX 15 ” denotes the fifth pixel electrodes formed in the fifth LC cells in the odd-numbered horizontal display lines, and the reference numeral “PIX 16 ” denotes the sixth pixel electrodes formed in the sixth LC cells in the odd-numbered horizontal display lines. In addition, in the respective even-numbered horizontal display lines LINE# 2 , LINE# 4 , . . . , and LINE#n, third and fourth LC cells in the even-numbered horizontal display lines disposed between the (i+1)-th data line and the (i+2) data line charge therein the positive data voltages supplied from the (i+2)-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the (i+2)-th data line during the (N+1)-th frame period. In FIG. 9 , the reference numeral “PIX 23 ” denotes the third pixel electrodes formed in the third LC cells in the even-numbered horizontal display lines, and the reference numeral “PIX 24 ” denotes the fourth pixel electrodes formed in the fourth LC cells in the even-numbered horizontal display lines. Therefore, the fifth and sixth LC cells in the odd-numbered horizontal display lines and the third and fourth LC cells in the even-numbered horizontal display lines charge therein the data voltages with the same polarity supplied from the (i+2)-th data line.
[0092] In the respective even-numbered horizontal display lines LINE# 2 , LINE# 4 , . . . , and LINE#n, fifth and sixth LC cells in the even-numbered horizontal display lines disposed between the (i+2)-th data line and the (i+3)-th data line charge therein the negative data voltages supplied from the (i+3)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+3)-th data line during the (N+1)-th frame period. In FIG. 9 , the reference numeral “PIX 25 ” denotes the fifth pixel electrodes formed in the fifth LC cells in the even-numbered horizontal display lines, and the reference numeral “PIX 26 ” denotes the sixth pixel electrodes formed in the sixth LC cells in the even-numbered horizontal display lines.
[0093] In the pixel array 10 shown in FIG. 9 , connection relations among the TFTs, the pixel electrodes, and the data lines will be described by exemplifying the first to sixth LC cells in the first horizontal display line LINE# 1 , and the first to sixth LC cells in the second horizontal display line LINE# 2 .
[0094] In the first horizontal display line LINE# 1 , the first and second LC cells disposed between the first data line D 1 and the second data line D 2 charge therein data voltages sequentially supplied from the first data line D 1 . The first TFT T 11 in the first horizontal display line transmits the data voltage from the first data line D 1 to the first pixel electrode PIX 11 in response to the second gate pulse from the second gate line G 2 . The first pixel electrode PIX 11 charges the data voltage therein during about ½ horizontal period. A gate terminal of the first TFT T 11 is connected to the second gate line G 2 . A drain terminal of the first TFT T 11 is connected to the first data line D 1 , and a source terminal thereof is connected to the first pixel electrode PIX 11 . The second TFT T 12 in the first horizontal display line transmits the data voltage from the first data line D 1 to the second pixel electrode PIX 12 in response to the first gate pulse from the first gate line G 1 . The second pixel electrode PIX 12 charges the data voltage therein during about ½ horizontal period. A gate terminal of the second TFT T 12 is connected to the first gate line G 1 . A drain terminal of the second TFT T 12 is connected to the first data line D 1 , and a source terminal thereof is connected to the second pixel electrode PIX 12 .
[0095] In the first horizontal display line LINE# 1 , the third and fourth LC cells disposed between the second data line D 2 and the third data line D 3 charge therein data voltages sequentially supplied from the second data line D 2 . The third TFT T 13 in the first horizontal display line transmits the data voltage from the second data line D 2 to the third pixel electrode PIX 13 in response to the second gate pulse from the second gate line G 2 . The third pixel electrode PIX 13 charges the data voltage therein during about ½ horizontal period. A gate terminal of the third TFT T 13 is connected to the second gate line G 2 . A drain terminal of the third TFT T 13 is connected to the second data line D 2 , and a source terminal thereof is connected to the third pixel electrode PIX 13 . The fourth TFT T 14 in the first horizontal display line transmits the data voltage from the second data line D 2 to the fourth pixel electrode PIX 14 in response to the first gate pulse from the first gate line G 1 . The fourth pixel electrode PIX 14 charges the data voltage therein during about ½ horizontal period. A gate terminal of the fourth TFT T 14 is connected to the first gate line G 1 . A drain terminal of the fourth TFT T 14 is connected to the second data line D 2 , and a source terminal thereof is connected to the fourth pixel electrode PIX 14 .
[0096] In the first horizontal display line LINE# 1 , the fifth and sixth LC cells disposed between the third data line D 3 and the fourth data line D 4 charge therein data voltages sequentially supplied from the third data line D 3 . The fifth TFT T 15 in the first horizontal display line transmits the data voltage from the third data line D 3 to the fifth pixel electrode PIX 15 in response to the first gate pulse from the first gate line G 1 . The fifth pixel electrode PIX 15 charges the data voltage therein during about ½ horizontal period. A gate terminal of the fifth TFT T 15 is connected to the first gate line G 1 . A drain terminal of the fifth TFT T 15 is connected to the third data line D 3 , and a source terminal thereof is connected to the fifth pixel electrode PIX 15 . The sixth TFT T 16 in the first horizontal display line transmits the data voltage from the third data line D 3 to the sixth pixel electrode PIX 16 in response to the second gate pulse from the second gate line G 2 . The sixth pixel electrode PIX 16 charges the data voltage therein during about ½ horizontal period. A gate terminal of the fourth TFT T 16 is connected to the second gate line G 2 . A drain terminal of the sixth TFT T 16 is connected to the third data line D 3 , and a source terminal thereof is connected to the sixth pixel electrode PIX 16 .
[0097] In the second horizontal display line LINE# 2 , the first and second LC cells disposed between the first data line D 1 and the second data line D 2 charge therein data voltages sequentially supplied from the second data line D 2 . The first TFT T 21 in the second horizontal display line transmits the data voltage from the second data line D 2 to the first pixel electrode PIX 21 in response to the third gate pulse from the third gate line G 3 . The first pixel electrode PIX 21 charges the data voltage therein during about ½ horizontal period. A gate terminal of the first TFT T 21 is connected to the third gate line G 3 . A drain terminal of the first TFT T 21 is connected to the second data line D 2 , and a source terminal thereof is connected to the first pixel electrode PIX 21 . The second TFT T 22 in the second horizontal display line transmits the data voltage from the second data line D 2 to the second pixel electrode PIX 22 in response to the fourth gate pulse from the fourth gate line G 4 . The second pixel electrode PIX 22 charges the data voltage therein during about ½ horizontal period. A gate terminal of the second TFT T 22 is connected to the fourth gate line G 4 . A drain terminal of the second TFT T 22 is connected to the second data line D 2 , and a source terminal thereof is connected to the second pixel electrode PIX 22 .
[0098] In the second horizontal display line LINE# 2 , the third and fourth LC cells disposed between the second data line D 2 and the third data line D 3 charge therein the data voltages sequentially supplied from the third data line D 3 . The third TFT T 23 in the second horizontal display line transmits the data voltage from the third data line D 3 to the third pixel electrode PIX 23 in response to the third gate pulse from the third gate line G 3 . The third pixel electrode PIX 23 charges the data voltage therein during about ½ horizontal period. A gate terminal of the third TFT T 23 is connected to the third gate line G 3 . A drain terminal of the third TFT T 23 is connected to the third data line D 3 , and a source terminal thereof is connected to the third pixel electrode PIX 23 . The fourth TFT T 24 in the second horizontal display line transmits the data voltage from the third data line D 3 to the fourth pixel electrode PIX 24 in response to the fourth gate pulse from the fourth gate line G 4 . The fourth pixel electrode PIX 24 charges the data voltage therein during about ½ horizontal period. A gate terminal of the fourth TFT T 24 is connected to the fourth gate line G 4 . A drain terminal of the fourth TFT T 24 is connected to the third data line D 3 , and a source terminal thereof is connected to the fourth pixel electrode PIX 24 .
[0099] In the second horizontal display line LINE# 2 , the fifth and sixth LC cells disposed between the third data line D 3 and the fourth data line D 4 charge therein the data voltages sequentially supplied from the fourth data line D 4 . The fifth TFT T 25 in the second horizontal display line transmits the data voltage from the fourth data line D 4 to the fifth pixel electrode PIX 25 in response to the fourth gate pulse from the fourth gate line G 4 . The fifth pixel electrode PIX 25 charges the data voltage therein during about ½ horizontal period. A gate terminal of the fifth TFT T 25 is connected to the fourth gate line G 4 . A drain terminal of the fifth TFT T 25 is connected to the fourth data line D 4 , and a source terminal thereof is connected to the fifth pixel electrode PIX 25 . The sixth TFT T 26 in the second horizontal display line transmits the data voltage from the fourth data line D 4 to the sixth pixel electrode PIX 26 in response to the third gate pulse from the third gate line G 3 . The sixth pixel electrode PIX 26 charges the data voltage therein during about ½ horizontal period. A gate terminal of the sixth TFT T 26 is connected to the third gate line G 3 . A drain terminal of the sixth TFT T 26 is connected to the fourth data line D 4 , and a source terminal thereof is connected to the sixth pixel electrode PIX 26 .
[0100] FIG. 10 is a circuit diagram illustrating a fifth embodiment of the pixel array 10 .
[0101] Referring to FIG. 10 , the pixel array 10 is provided with data lines D 1 to Dm+1, gate lines G 1 to G 2 n intersecting the data lines D 1 to Dm+1, and TFTs T 11 to T 14 and T 21 to T 24 which switch current paths formed between the pixel electrodes PIX 11 to PIX 14 and PIX 21 to PIX 24 in LC cells and the data lines D 1 to Dm+1 in response to gate pulses. For the data voltages charged in the LC cells due to the pixel array structure in FIG. 10 , their polarities are reversed in a unit of horizontal 2-dot and vertical 1-dot.
[0102] The source drive ICs 12 output to the data lines D 1 to Dm+1 the data voltages of which the polarities are reversed by the column inversion scheme. The gate drivers 13 sequentially supply the gate pulses for the first to 2n-th gate lines G 1 to G 2 n . A first gate pulse is provided to the first gate line G 1 , and then second to 2n-th gate pulses are provided to the second to 2n-th gate lines G 2 to G 2 n.
[0103] During an N-th frame period, the source drive ICs supply only positive data voltages for the odd-numbered data lines D 1 , D 3 , . . . , Dm−1 and Dm+1, and supply only negative data voltages for the even-numbered data lines D 2 , D 4 , . . . , and Dm. During a (N+1)-th frame period, the source drive ICs 12 supply only the negative data voltages for the odd-numbered data lines D 1 , D 3 , . . . , Dm−1 and Dm+1, and supply only the positive data voltages for the even-numbered data lines D 2 , D 4 , . . . , and Dm.
[0104] In the respective odd-numbered horizontal display lines LINE# 1 , LINE# 3 , . . . , and LINE#n−1, first and second LC cells in the odd-numbered horizontal display lines are disposed between an i-th data line and a (i+1)-th data line. The first LC cells in the odd-numbered horizontal display lines charge therein the positive data voltages supplied from the i-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the i-th data line during the (N+1)-th frame period. The second LC cells in the odd-numbered horizontal display lines charge therein the negative data voltages supplied from the (i+1)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+1)-th data line during the (N+1)-th frame period. In FIG. 10 , the reference numeral “PIX 11 ” denotes the first pixel electrodes formed in the first LC cells in the odd-numbered horizontal display lines, and the reference numeral “PIX 12 ” denotes the second pixel electrodes formed in the second LC cells in the odd-numbered horizontal display lines.
[0105] In the respective odd-numbered horizontal display lines LINE# 1 , LINE# 3 , . . . , and LINE#n−1, third and fourth LC cells in the odd-numbered horizontal display lines are disposed between the (i+1)-th data line and a (i+2)-th data line. The third LC cells in the odd-numbered horizontal display lines charge therein the negative data voltages supplied from the (i+1)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+1)-th data line during the (N+1)-th frame period. The fourth LC cells in the odd-numbered horizontal display lines charge therein the positive data voltages supplied from the (i+2)-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the (i+2)-th data line during the (N+1)-th frame period. In FIG. 10 , the reference numeral “PIX 13 ” denotes the third pixel electrodes formed in the third LC cells in the odd-numbered horizontal display lines, and the reference numeral “PIX 14 ” denotes the fourth pixel electrodes formed in the fourth LC cells in the odd-numbered horizontal display lines.
[0106] In The respective even-numbered horizontal display lines LINE# 2 , LINE# 4 , . . . , and LINE#n, first and second LC cells in the even-numbered horizontal display lines are disposed between the i-th data line and the (i+1) data line. The first LC cells in the even-numbered horizontal display lines charge therein the negative data voltages supplied from the (i+1)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+1)-th data line during the (N+1)-th frame period. The second LC cells in the even-numbered horizontal display lines charge therein the positive data voltages supplied from the i-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the i-th data line during the (N+1)-th frame period. In FIG. 10 , the reference numeral “PIX 21 ” denotes the first pixel electrodes formed in the first LC cells in the even-numbered horizontal display lines, and the reference numeral “PIX 22 ” denotes the second pixel electrodes formed in the second LC cells in the even-numbered horizontal display lines.
[0107] In the respective even-numbered horizontal display lines LINE# 2 , LINE# 4 , . . . , and LINE#n, third and fourth LC cells in the even-numbered horizontal display lines are disposed between the (i+1)-th data line and a (i+2) data line. The third LC cells in the even-numbered horizontal display lines charge therein the positive data voltages supplied from the (i+2)-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the (i+2)-th data line during the (N+1)-th frame period. The fourth LC cells in the even-numbered horizontal display lines charge therein the negative data voltages supplied from the (i+1)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+1)-th data line during the (N+1)-th frame period. In FIG. 10 , the reference numeral “PIX 23 ” denotes the third pixel electrodes formed in the third LC cells in the even-numbered horizontal display lines, and the reference numeral “PIX 24 ” denotes the fourth pixel electrodes formed in the fourth LC cells in the even-numbered horizontal display lines.
[0108] As can be seen from FIG. 10 , the second and third LC cells in the odd-numbered horizontal display lines and the first and fourth LC cells in the even-numbered horizontal display lines charge therein the data voltages with the same polarity which are supplied from the (i+1)-th data line. The polarity of the data voltages charged in the second and third cells in the odd-numbered horizontal display lines and the first and fourth LC cells in the even-numbered horizontal display lines is opposite to that of the data voltages charged in the first and fourth LC cells in the odd-numbered horizontal display lines and the second and third LC cells in the even-numbered horizontal display lines.
[0109] In the pixel array 10 shown in FIG. 10 , connection relations among the TFTs, the pixel electrodes, and the data lines will be described by exemplifying the first to fourth LC cells in the first horizontal display line LINE# 1 , and the first to fourth LC cells in the second horizontal display line LINE# 2 .
[0110] The second LC cell in the first horizontal display line LINE# 1 charges therein the data voltage supplied from the second data line D 2 . Successively, the first LC cell in the first horizontal display line LINE# 1 charges therein the data voltage supplied from the first data line D 1 . The first TFT T 11 in the first horizontal display line transmits the data voltage from the first data line D 1 to the first pixel electrode PIX 11 in response to the second gate pulse from the second gate line G 2 . The first pixel electrode PIX 11 charges the data voltage therein during about ½ horizontal period. A gate terminal of the first TFT T 11 is connected to the second gate line G 2 . A drain terminal of the first TFT T 11 is connected to the first data line D 1 , and a source terminal thereof is connected to the first pixel electrode PIX 11 . The second TFT T 12 in the first horizontal display line transmits the data voltage from the second data line D 2 to the second pixel electrode PIX 12 in response to the first gate pulse from the first gate line G 1 . The second pixel electrode PIX 12 charges the data voltage therein during about ½ horizontal period. A gate terminal of the second TFT T 12 is connected to the first gate line G 1 . A drain terminal of the second TFT T 12 is connected to the second data line D 2 , and a source terminal thereof is connected to the second pixel electrode PIX 12 .
[0111] The fourth LC cell in the first horizontal display line LINE# 1 charges therein the data voltage supplied from the third data line D 3 . Successively, the third LC cell in the first horizontal display line LINE# 1 charges therein the data voltage supplied from the second data line D 2 . The third TFT T 13 in the first horizontal display line transmits the data voltage from the second data line D 2 to the third pixel electrode PIX 13 in response to the second gate pulse from the second gate line G 2 . The third pixel electrode PIX 13 charges the data voltage therein during about ½ horizontal period. A gate terminal of the third TFT T 13 is connected to the second gate line G 2 . A drain terminal of the third TFT T 13 is connected to the second data line D 2 , and a source terminal thereof is connected to the third pixel electrode PIX 13 . The fourth TFT T 14 in the first horizontal display line transmits the data voltage from the third data line D 3 to the fourth pixel electrode PIX 14 in response to the first gate pulse from the first gate line G 1 . The fourth pixel electrode PIX 14 charges the data voltage therein during about ½ horizontal period. A gate terminal of the fourth TFT T 14 is connected to the first gate line G 1 . A drain terminal of the second TFT T 12 is connected to the third data line D 3 , and a source terminal thereof is connected to the fourth pixel electrode PIX 14 .
[0112] The first LC cell in the second horizontal display line LINE# 2 charges therein the data voltage supplied from the second data line D 2 . Successively, the second LC cell in the second horizontal display line LINE# 2 charges therein the data voltage supplied from the first data line D 1 . The first TFT T 21 in the second horizontal display line transmits the data voltage from the second data line D 2 to the first pixel electrode PIX 21 in response to the third gate pulse from the third gate line G 3 . The first pixel electrode PIX 21 charges the data voltage therein during about ½ horizontal period. A gate terminal of the first TFT T 21 is connected to the third gate line G 3 . A drain terminal of the first TFT T 21 is connected to the second data line D 2 , and a source terminal thereof is connected to the first pixel electrode PIX 21 . The second TFT T 22 in the second horizontal display line transmits the data voltage from the first data line D 1 to the second pixel electrode PIX 22 in response to the fourth gate pulse from the fourth gate line G 4 . The second pixel electrode PIX 22 charges the data voltage therein during about ½ horizontal period. A gate terminal of the second TFT T 22 is connected to the fourth gate line G 4 . A drain terminal of the second TFT T 22 is connected to the first data line D 1 , and a source terminal thereof is connected to the second pixel electrode PIX 22 .
[0113] The third LC cell in the second horizontal display line LINE# 2 charges therein the data voltage supplied from the third data line D 3 . Successively, the fourth LC cell in the second horizontal display line LINE# 2 charges therein the data voltage supplied from the second data line D 2 . The third TFT T 23 in the second horizontal display line transmits the data voltage from the third data line D 3 to the third pixel electrode PIX 23 in response to the third gate pulse from the third gate line G 3 . The third pixel electrode PIX 23 charges the data voltage therein during about ½ horizontal period. A gate terminal of the third TFT T 23 is connected to the third gate line G 3 . A drain terminal of the third TFT T 23 is connected to the third data line D 3 , and a source terminal thereof is connected to the third pixel electrode PIX 23 . The fourth TFT T 24 in the second horizontal display line transmits the data voltage from the second data line D 2 to the fourth pixel electrode PIX 24 in response to the fourth gate pulse from the fourth gate line G 4 . The fourth pixel electrode PIX 24 charges the data voltage therein during about ½ horizontal period. A gate terminal of the fourth TFT T 24 is connected to the fourth gate line G 4 . A drain terminal of the second TFT T 22 is connected to the second data line D 2 , and a source terminal thereof is connected to the fourth pixel electrode PIX 24 .
[0114] FIG. 11 is a circuit diagram illustrating a sixth embodiment of the pixel array 10 .
[0115] Referring to FIG. 11 , the pixel array 10 is provided with data lines D 1 to Dm+1, gate lines G 1 to G 2 n intersecting the data lines D 1 to Dm+1, and TFTs T 11 to T 14 and T 21 to T 24 which switch current paths formed between the pixel electrodes PIX 11 to PIX 14 and PIX 21 to PIX 24 in LC cells and the data lines D 1 to Dm+1 in response to gate pulses. For the data voltages charged in the LC cells due to the pixel array structure in FIG. 11 , their polarities are reversed in a unit of horizontal 2-dot and vertical 1-dot.
[0116] The source drive ICs 12 output to the data lines D 1 to Dm+1 the data voltages of which the polarities are reversed by the column inversion scheme. The gate drivers 13 sequentially supply the gate pulses for the first to 2n-th gate lines G 1 to G 2 n . A first gate pulse is provided to the first gate line G 1 , and then second to 2n-th gate pulses are provided to the second to 2n-th gate lines G 2 to G 2 n.
[0117] During an N-th frame period, the source drive ICs 12 supply only positive data voltages for the odd-numbered data lines D 1 , D 3 , . . . , Dm−1 and Dm+1, and supply only negative data voltages for the even-numbered data lines D 2 , D 4 , . . . , and Dm. During a (N+1)-th frame period, the source drive ICs 12 supply only the negative data voltages for the odd-numbered data lines D 1 , D 3 , . . . , Dm−1 and Dm+1, and supply only the positive data voltages for the even-numbered data lines D 2 , D 4 , . . . , and Dm.
[0118] In the respective odd-numbered horizontal display lines LINE# 1 , LINE# 3 , . . . , and LINE#n−1, first and second LC cells in the odd-numbered horizontal display lines are disposed between an i-th data line and a (i+1)-th data line. The first LC cells in the odd-numbered horizontal display lines charge therein the positive data voltages supplied from the i-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the i-th data line during the (N+1)-th frame period. The second LC cells in the odd-numbered horizontal display lines charge therein the negative data voltages supplied from the (i+1)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+1)-th data line during the (N+1)-th frame period. In FIG. 11 , the reference numeral “PIX 11 ” denotes the first pixel electrodes formed in the first LC cells in the odd-numbered horizontal display lines, and the reference numeral “PIX 12 ” denotes the second pixel electrodes formed in the second LC cells in the odd-numbered horizontal display lines.
[0119] In the respective odd-numbered horizontal display lines LINE# 1 , LINE# 3 , . . . , and LINE#n−1, third and fourth LC cells in the odd-numbered horizontal display lines are disposed between the (i+1)-th data line and a (i+2)-th data line. The third LC cells in the odd-numbered horizontal display lines charge therein the negative data voltages supplied from the (i+1)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+1)-th data line during the (N+1)-th frame period. The fourth LC cells in the odd-numbered horizontal display lines charge therein the positive data voltages supplied from the (i+2)-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the (i+2)-th data line during the (N+1)-th frame period. In FIG. 11 , the reference numeral “PIX 13 ” denotes the third pixel electrodes formed in the third LC cells in the odd-numbered horizontal display lines, and the reference numeral “PIX 14 ” denotes the fourth pixel electrodes formed in the fourth LC cells in the odd-numbered horizontal display lines.
[0120] In The respective even-numbered horizontal display lines LINE# 2 , LINE# 4 , . . . , and LINE#n, first and second LC cells in the even-numbered horizontal display lines are disposed between the i-th data line and the (i+1) data line. The first LC cells in the even-numbered horizontal display lines charge therein the negative data voltages supplied from the (i+1)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+1)-th data line during the (N+1)-th frame period. The second LC cells in the even-numbered horizontal display lines charge therein the positive data voltages supplied from the i-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the i-th data line during the (N+1)-th frame period. In FIG. 11 , the reference numeral “PIX 21 ” denotes the first pixel electrodes formed in the first LC cells in the even-numbered horizontal display lines, and the reference numeral “PIX 22 ” denotes the second pixel electrodes formed in the second LC cells in the even-numbered horizontal display lines.
[0121] In the respective even-numbered horizontal display lines LINE# 2 , LINE# 4 , . . . , and LINE#n, third and fourth LC cells in the even-numbered horizontal display lines are disposed between the (i+1)-th data line and a (i+2) data line. The third LC cells in the even-numbered horizontal display lines charge therein the positive data voltages supplied from the (i+2)-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the (i+2)-th data line during the (N+1)-th frame period. The fourth LC cells in the even-numbered horizontal display lines charge therein the negative data voltages supplied from the (i+1)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+1)-th data line during the (N+1)-th frame period. In FIG. 11 , the reference numeral “PIX 23 ” denotes the third pixel electrodes formed in the third LC cells in the even-numbered horizontal display lines, and the reference numeral “PIX 24 ” denotes the fourth pixel electrodes formed in the fourth LC cells in the even-numbered horizontal display lines.
[0122] As can be seen from FIG. 11 , the second and third LC cells in the odd-numbered horizontal display lines and the first and fourth LC cells in the even-numbered horizontal display lines charge therein the data voltages with the same polarity which are supplied from the (i+1)-th data line. The polarity of the data voltages charged in the second and third cells in the odd-numbered horizontal display lines and the first and fourth LC cells in the even-numbered horizontal display lines is opposite to that of the data voltages charged in the first and fourth LC cells in the odd-numbered horizontal display lines and the second and third LC cells in the even-numbered horizontal display lines.
[0123] In the pixel array 10 shown in FIG. 11 , connection relations among the TFTs, the pixel electrodes, and the data lines will be described by exemplifying the first to fourth LC cells in the first horizontal display line LINE# 1 , and the first to fourth LC cells in the second horizontal display line LINE# 2 .
[0124] The first LC cell in the first horizontal display line LINE# 1 charges therein the data voltage supplied from the first data line D 1 . Successively, the second LC cell in the first horizontal display line LINE# 1 charges therein the data voltage supplied from the second data line D 2 . The first TFT T 11 in the first horizontal display line transmits the data voltage from the first data line D 1 to the first pixel electrode PIX 11 in response to the first gate pulse from the first gate line G 1 . The first pixel electrode PIX 11 charges the data voltage therein during about ½ horizontal period. A gate terminal of the first TFT T 11 is connected to the first gate line G 1 . A drain terminal of the first TFT T 11 is connected to the first data line D 1 , and a source terminal thereof is connected to the first pixel electrode PIX 11 . The second TFT T 12 in the first horizontal display line transmits the data voltage from the second data line D 2 to the second pixel electrode PIX 12 in response to the second gate pulse from the second gate line G 2 . The second pixel electrode PIX 12 charges the data voltage therein during about ½ horizontal period. A gate terminal of the second TFT T 12 is connected to the second gate line G 2 . A drain terminal of the second TFT T 12 is connected to the second data line D 2 , and a source terminal thereof is connected to the second pixel electrode PIX 12 .
[0125] The third LC cell in the first horizontal display line LINE# 1 charges therein the data voltage supplied from the second data line D 2 . Successively, the fourth LC cell in the first horizontal display line LINE# 1 charges therein the data voltage supplied from the third data line D 3 . The third TFT T 13 in the first horizontal display line transmits the data voltage from the second data line D 2 to the third pixel electrode PIX 13 in response to the first gate pulse from the first gate line G 1 . The third pixel electrode PIX 13 charges the data voltage therein during about ½ horizontal period. A gate terminal of the third TFT T 13 is connected to the first gate line G 1 . A drain terminal of the third TFT T 13 is connected to the second data line D 2 , and a source terminal thereof is connected to the third pixel electrode PIX 13 . The fourth TFT T 14 in the first horizontal display line transmits the data voltage from the third data line D 3 to the fourth pixel electrode PIX 14 in response to the second gate pulse from the second gate line G 2 . The fourth pixel electrode PIX 14 charges the data voltage therein during about ½ horizontal period. A gate terminal of the fourth TFT T 14 is connected to the second gate line G 2 . A drain terminal of the second TFT T 12 is connected to the third data line D 3 , and a source terminal thereof is connected to the fourth pixel electrode PIX 14 .
[0126] The second LC cell in the second horizontal display line LINE# 2 charges therein the data voltage supplied from the first data line D 1 . Successively, the first LC cell in the second horizontal display line LINE# 2 charges therein the data voltage supplied from the second data line D 2 . The first TFT T 21 in the second horizontal display line transmits the data voltage from the second data line D 2 to the first pixel electrode PIX 21 in response to the fourth gate pulse from the fourth gate line G 4 . The first pixel electrode PIX 21 charges the data voltage therein during about ½ horizontal period. A gate terminal of the first TFT T 21 is connected to the fourth gate line G 4 . A drain terminal of the first TFT T 21 is connected to the second data line D 2 , and a source terminal thereof is connected to the first pixel electrode PIX 21 . The second TFT T 22 in the second horizontal display line transmits the data voltage from the first data line D 1 to the second pixel electrode PIX 22 in response to the third gate pulse from the third gate line G 3 . The second pixel electrode PIX 22 charges the data voltage therein during about ½ horizontal period. A gate terminal of the second TFT T 22 is connected to the third gate line G 3 . A drain terminal of the second TFT T 22 is connected to the first data line D 1 , and a source terminal thereof is connected to the second pixel electrode PIX 22 .
[0127] The fourth LC cell in the second horizontal display line LINE# 2 charges therein the data voltage supplied from the second data line D 2 . Successively, the third LC cell in the second horizontal display line LINE# 2 charges therein the data voltage supplied from the third data line D 3 . The third TFT T 23 in the second horizontal display line transmits the data voltage from the third data line D 3 to the third pixel electrode PIX 23 in response to the fourth gate pulse from the fourth gate line G 4 . The third pixel electrode PIX 23 charges the data voltage therein during about ½ horizontal period. A gate terminal of the third TFT T 23 is connected to the fourth gate line G 4 . A drain terminal of the third TFT T 23 is connected to the third data line D 3 , and a source terminal thereof is connected to the third pixel electrode PIX 23 . The fourth TFT T 24 in the second horizontal display line transmits the data voltage from the second data line D 2 to the fourth pixel electrode PIX 24 in response to the third gate pulse from the third gate line G 3 . The fourth pixel electrode PIX 24 charges the data voltage therein during about ½ horizontal period. A gate terminal of the fourth TFT T 24 is connected to the third gate line G 3 . A drain terminal of the second TFT T 22 is connected to the second data line D 2 , and a source terminal thereof is connected to the fourth pixel electrode PIX 24 .
[0128] FIG. 12 is a circuit diagram illustrating a fourth embodiment of the pixel array 10 .
[0129] In FIG. 12 , the pixel array 10 is provided with data lines D 1 to Dm+1, gate lines G 1 to G 2 n intersecting the data lines D 1 to Dm+1, and TFTs T 11 to T 16 and T 21 to T 26 which switch current paths formed between the pixel electrodes PIX 11 to PIX 16 and PIX 21 to PIX 26 in LC cells and the data lines D 1 to Dm+1 in response to gate pulses. For the data voltages charged in the LC cells due to the pixel array structure in FIG. 12 , their polarities are reversed in a unit of horizontal 2-dot and vertical 1-dot.
[0130] The source drive ICs 12 output to the data lines D 1 to Dm+1 the data voltages of which the polarities are reversed by the column inversion scheme. The gate drivers 13 sequentially supply the gate pulses for the first to 2n-th gate lines G 1 to G 2 n . A first gate pulse is provided to the first gate line G 1 , and then second to 2n-th gate pulses are provided to the second to 2n-th gate lines G 2 to G 2 n.
[0131] During an N-th frame period, the source drive ICs 12 supply only positive data voltages for the odd-numbered data lines D 1 , D 3 , . . . , Dm−1 and Dm+1, and supply only negative data voltages for the even-numbered data lines D 2 , D 4 , . . . , and Dm. During a (N+1)-th frame period, the source drive ICs 12 supply only the negative data voltages for the odd-numbered data lines D 1 , D 3 , . . . , Dm−1 and Dm+1, and supply only the positive data voltages for the even-numbered data lines D 2 , D 4 , . . . , and Dm.
[0132] In the respective odd-numbered horizontal display lines LINE# 1 , LINE# 3 , . . . , and LINE#n−1, first and second LC cells in the odd-numbered horizontal display lines are disposed between an i-th data line and a (i+1)-th data line. The first LC cells in the odd-numbered horizontal display lines charge therein the positive data voltages supplied from the i-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the i-th data line during the (N+1)-th frame period. The second LC cells in the odd-numbered horizontal display lines charge therein the negative data voltages supplied from the (i+1)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+1)-th data line during the (N+1)-th frame period. In FIG. 12 , the reference numeral “PIX 11 ” denotes the first pixel electrodes formed in the first LC cells in the odd-numbered horizontal display lines, and the reference numeral “PIX 12 ” denotes the second pixel electrodes formed in the second LC cells in the odd-numbered horizontal display lines.
[0133] In the respective odd-numbered horizontal display lines LINE# 1 , LINE# 3 , . . . , and LINE#n−1, third and fourth LC cells in the odd-numbered horizontal display lines are disposed between the (i+1)-th data line and a (i+2)-th data line. The third LC cells in the odd-numbered horizontal display lines charge therein the negative data voltages supplied from the (i+1)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+1)-th data line during the (N+1)-th frame period. The fourth LC cells in the odd-numbered horizontal display lines charge therein the positive data voltages supplied from the (i+2)-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the (i+2)-th data line during the (N+1)-th frame period. In FIG. 12 , the reference numeral “PIX 13 ” denotes the third pixel electrodes formed in the third LC cells in the odd-numbered horizontal display lines, and the reference numeral “PIX 14 ” denotes the fourth pixel electrodes formed in the fourth LC cells in the odd-numbered horizontal display lines.
[0134] In The respective even-numbered horizontal display lines LINE# 2 , LINE# 4 , . . . , and LINE#n, first and second LC cells in the even-numbered horizontal display lines are disposed between the i-th data line and the (i+1) data line. The first LC cells in the even-numbered horizontal display lines charge therein the negative data voltages supplied from the (i+1)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+1)-th data line during the (N+1)-th frame period. The second LC cells in the even-numbered horizontal display lines charge therein the positive data voltages supplied from the i-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the i-th data line during the (N+1)-th frame period. In FIG. 12 , the reference numeral “PIX 21 ” denotes the first pixel electrodes formed in the first LC cells in the even-numbered horizontal display lines, and the reference numeral “PIX 22 ” denotes the second pixel electrodes formed in the second LC cells in the even-numbered horizontal display lines.
[0135] In the respective even-numbered horizontal display lines LINE# 2 , LINE# 4 , . . . , and LINE#n, third and fourth LC cells in the even-numbered horizontal display lines are disposed between the (i+1)-th data line and a (i+2) data line. The third LC cells in the even-numbered horizontal display lines charge therein the positive data voltages supplied from the (i+2)-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the (i+2)-th data line during the (N+1)-th frame period. The fourth LC cells in the even-numbered horizontal display lines charge therein the negative data voltages supplied from the (i+1)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+1)-th data line during the (N+1)-th frame period. In FIG. 12 , the reference numeral “PIX 23 ” denotes the third pixel electrodes formed in the third LC cells in the even-numbered horizontal display lines, and the reference numeral “PIX 24 ” denotes the fourth pixel electrodes formed in the fourth LC cells in the even-numbered horizontal display lines.
[0136] As can be seen from FIG. 12 , the second and third LC cells in the odd-numbered horizontal display lines and the first and fourth LC cells in the even-numbered horizontal display lines charge therein the data voltages with the same polarity which are supplied from the (i+1)-th data line. The polarity of the data voltages charged in the second and third LC cells in the odd-numbered horizontal display lines and the first and fourth LC cells in the even-numbered horizontal display lines is opposite to that of the data voltages charged in the first and fourth LC cells in the odd-numbered horizontal display lines and the second and third LC cells in the even-numbered horizontal display lines.
[0137] In the pixel array 10 shown in FIG. 12 , connection relations among the TFTs, the pixel electrodes, and the data lines will be described by exemplifying the first to fourth LC cells in the first horizontal display line LINE# 1 , and the first to fourth LC cells in the second horizontal display line LINE# 2 .
[0138] The first LC cell in the first horizontal display line LINE# 1 charges therein the data voltage supplied from the first data line D 1 . At the same time, the second LC cell in the first horizontal display line LINE# 1 charges therein the data voltage supplied from the second data line D 2 . The first TFT T 11 in the first horizontal display line transmits the data voltage from the first data line D 1 to the first pixel electrode PIX 11 in response to the first gate pulse from the first gate line G 1 . The first pixel electrode PIX 11 charges the data voltage therein during about ½ horizontal period. A gate terminal of the first TFT T 11 is connected to the first gate line G 1 . A drain terminal of the first TFT T 11 is connected to the first data line D 1 , and a source terminal thereof is connected to the first pixel electrode PIX 11 . The second TFT T 12 in the first horizontal display line transmits the data voltage from the second data line D 2 to the second pixel electrode PIX 12 in response to the first gate pulse from the first gate line G 1 . The second pixel electrode PIX 12 charges the data voltage therein during about ½ horizontal period. A gate terminal of the second TFT T 12 is connected to the first gate line G 1 . A drain terminal of the second TFT T 12 is connected to the second data line D 2 , and a source terminal thereof is connected to the second pixel electrode PIX 12 .
[0139] The third LC cell in the first horizontal display line LINE# 1 charges therein the data voltage supplied from the second data line D 2 . At the same time, the fourth LC cell in the first horizontal display line LINE# 1 charges therein the data voltage supplied from the third data line D 3 . The third TFT T 13 in the first horizontal display line transmits the data voltage from the second data line D 2 to the third pixel electrode PIX 13 in response to the second gate pulse from the second gate line G 2 . The third pixel electrode PIX 13 charges the data voltage therein during about ½ horizontal period. A gate terminal of the third TFT T 13 is connected to the second gate line G 2 . A drain terminal of the third TFT T 13 is connected to the second data line D 2 , and a source terminal thereof is connected to the third pixel electrode PIX 13 . The fourth TFT T 14 in the first horizontal display line transmits the data voltage from the third data line D 3 to the fourth pixel electrode PIX 14 in response to the second gate pulse from the second gate line G 2 . The fourth pixel electrode PIX 14 charges the data voltage therein during about ½ horizontal period. A gate terminal of the fourth TFT T 14 is connected to the second gate line G 2 . A drain terminal of the second TFT T 12 is connected to the third data line D 3 , and a source terminal thereof is connected to the fourth pixel electrode PIX 14 .
[0140] The second LC cell in the second horizontal display line LINE# 2 charges therein the data voltage supplied from the first data line D 1 . Successively, the first LC cell in the second horizontal display line LINE# 2 charges therein the data voltage supplied from the second data line D 2 . The first TFT T 21 in the second horizontal display line transmits the data voltage from the second data line D 2 to the first pixel electrode PIX 21 in response to the fourth gate pulse from the fourth gate line G 4 . The first pixel electrode PIX 21 charges the data voltage therein during about ½ horizontal period. A gate terminal of the first TFT T 21 is connected to the fourth gate line G 4 . A drain terminal of the first TFT T 21 is connected to the second data line D 2 , and a source terminal thereof is connected to the first pixel electrode PIX 21 . The second TFT T 22 in the second horizontal display line transmits the data voltage from the first data line D 1 to the second pixel electrode PIX 22 in response to the third gate pulse from the third gate line G 3 . The second pixel electrode PIX 22 charges the data voltage therein during about ½ horizontal period. A gate terminal of the second TFT T 22 is connected to the third gate line G 3 . A drain terminal of the second TFT T 22 is connected to the first data line D 1 , and a source terminal thereof is connected to the second pixel electrode PIX 22 .
[0141] The fourth LC cell in the second horizontal display line LINE# 2 charges therein the data voltage supplied from the second data line D 2 . Successively, the third LC cell in the second horizontal display line LINE# 2 charges therein the data voltage supplied from the third data line D 3 . The third TFT T 23 in the second horizontal display line transmits the data voltage from the third data line D 3 to the third pixel electrode PIX 23 in response to the fourth gate pulse from the fourth gate line G 4 . The third pixel electrode PIX 23 charges the data voltage therein during about ½ horizontal period. A gate terminal of the third TFT T 23 is connected to the fourth gate line G 4 . A drain terminal of the third TFT T 23 is connected to the third data line D 3 , and a source terminal thereof is connected to the third pixel electrode PIX 23 . The fourth TFT T 24 in the second horizontal display line transmits the data voltage from the second data line D 2 to the fourth pixel electrode PIX 24 in response to the third gate pulse from the third gate line G 3 . The fourth pixel electrode PIX 24 charges the data voltage therein during about ½ horizontal period. A gate terminal of the fourth TFT T 24 is connected to the third gate line G 3 . A drain terminal of the second TFT T 22 is connected to the second data line D 2 , and a source terminal thereof is connected to the fourth pixel electrode PIX 24 .
[0142] FIG. 13 is a circuit diagram illustrating an eighth embodiment of the pixel array 10 .
[0143] In FIG. 13 , the pixel array 10 is provided with data lines D 1 to Dm+1, gate lines G 1 to G 2 n intersecting the data lines D 1 to Dm+1, and TFTs T 11 to T 16 and T 21 to T 26 which switch current paths formed between the pixel electrodes PIX 11 to PIX 16 and PIX 21 to PIX 26 in LC cells and the data lines D 1 to Dm+1 in response to gate pulses. For the data voltages charged in the LC cells due to the pixel array structure in FIG. 13 , their polarities are reversed in a unit of horizontal 2-dot and vertical 1-dot. In addition, the polarities of the data voltages charged in a part of the LC cells of the pixel array 10 in FIG. 13 are reversed in a unit of horizontal 1-dot and vertical 1-dot (1×1 dot). Therefore, in the pixel array in FIG. 13 , there are mixed the LC cells where the polarities of the data voltages charged therein are reversed in a unit of horizontal 2-dot and vertical 1-dot and in a unit of horizontal 1-dot and vertical 1-dot.
[0144] The source drive ICs 12 output to the data lines D 1 to Dm+1 the data voltages of which the polarities are reversed by the column inversion scheme. The gate drivers 13 sequentially supply the gate pulses for the first to 2n-th gate lines G 1 to G 2 n . A first gate pulse is provided to the first gate line G 1 , and then second to 2n-th gate pulses are provided to the second to 2n-th gate lines G 2 to G 2 n.
[0145] During an N-th frame period, the source drive ICs 12 supply only positive data voltages for the odd-numbered data lines D 1 , D 3 , . . . , Dm−1 and Dm+1, and supply only negative data voltages for the even-numbered data lines D 2 , D 4 , . . . , and Dm. During a (N+1)-th frame period, the source drive ICs 12 supply only the negative data voltages for the odd-numbered data lines D 1 , D 3 , . . . , Dm−1 and Dm+1, and supply only the positive data voltages for the even-numbered data lines D 2 , D 4 , . . . , and Dm.
[0146] In the respective odd-numbered horizontal display lines LINE# 1 , LINE# 3 , . . . , and LINE#n−1, first and second LC cells in the odd-numbered horizontal display lines are disposed between an i-th data line and a (i+1)-th data line. The first LC cells in the odd-numbered horizontal display lines charge therein the positive data voltages supplied from the i-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the i-th data line during the (N+1)-th frame period. The second LC cells in the odd-numbered horizontal display lines charge therein the negative data voltages supplied from the (i+1)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+1)-th data line during the (N+1)-th frame period. In FIG. 13 , the reference numeral “PIX 11 ” denotes the first pixel electrodes formed in the first LC cells in the odd-numbered horizontal display lines, and the reference numeral “PIX 12 ” denotes the second pixel electrodes formed in the second LC cells in the odd-numbered horizontal display lines.
[0147] In the respective odd-numbered horizontal display lines LINE# 1 , LINE# 3 , . . . , and LINE#n−1, third and fourth LC cells in the odd-numbered horizontal display lines are disposed between the (i+1)-th data line and a (i+2)-th data line. The third LC cells in the odd-numbered horizontal display lines charge therein the negative data voltages supplied from the (i+1)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+1)-th data line during the (N+1)-th frame period. The fourth LC cells in the odd-numbered horizontal display lines charge therein the positive data voltages supplied from the (i+2)-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the (i+2)-th data line during the (N+1)-th frame period. In FIG. 13 , the reference numeral “PIX 13 ” denotes the third pixel electrodes formed in the third LC cells in the odd-numbered horizontal display lines, and the reference numeral “PIX 14 ” denotes the fourth pixel electrodes formed in the fourth LC cells in the odd-numbered horizontal display lines.
[0148] In the respective odd-numbered horizontal display lines LINE# 1 , LINE# 3 , . . . , and LINE#n−1, fifth and sixth LC cells in the odd-numbered horizontal display lines are disposed between the (i+2)-th data line and a (i+3)-th data line. The fifth LC cells in the odd-numbered horizontal display lines charge therein the negative data voltages supplied from the (i+3)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+3)-th data line during the (N+1)-th frame period. The sixth LC cells in the odd-numbered horizontal display lines charge therein the positive data voltages supplied from the (i+2)-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the (i+2)-th data line during the (N+1)-th frame period. In FIG. 13 , the reference numeral “PIX 15 ” denotes the fifth pixel electrodes formed in the fifth LC cells in the odd-numbered horizontal display lines, and the reference numeral “PIX 16 ” denotes the sixth pixel electrodes formed in the sixth LC cells in the odd-numbered horizontal display lines.
[0149] In The respective even-numbered horizontal display lines LINE# 2 , LINE# 4 , . . . , and LINE#n, first and second LC cells in the even-numbered horizontal display lines are disposed between the i-th data line and the (i+1) data line. The first LC cells in the even-numbered horizontal display lines charge therein the negative data voltages supplied from the (i+1)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+1)-th data line during the (N+1)-th frame period. The second LC cells in the even-numbered horizontal display lines charge therein the positive data voltages supplied from the i-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the i-th data line during the (N+1)-th frame period. In FIG. 13 , the reference numeral “PIX 21 ” denotes the first pixel electrodes formed in the first LC cells in the even-numbered horizontal display lines, and the reference numeral “PIX 22 ” denotes the second pixel electrodes formed in the second LC cells in the even-numbered horizontal display lines.
[0150] In the respective even-numbered horizontal display lines LINE# 2 , LINE# 4 , . . . , and LINE#n, third and fourth LC cells in the even-numbered horizontal display lines are disposed between the (i+1)-th data line and a (i+2) data line. The third LC cells in the even-numbered horizontal display lines charge therein the positive data voltages supplied from the (i+2)-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the (i+2)-th data line during the (N+1)-th frame period. The fourth LC cells in the even-numbered horizontal display lines charge therein the negative data voltages supplied from the (i+1)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+1)-th data line during the (N+1)-th frame period. In FIG. 13 , the reference numeral “PIX 23 ” denotes the third pixel electrodes formed in the third LC cells in the even-numbered horizontal display lines, and the reference numeral “PIX 24 ” denotes the fourth pixel electrodes formed in the fourth LC cells in the even-numbered horizontal display lines.
[0151] In the respective even-numbered horizontal display lines LINE# 2 , LINE# 4 , . . . , and LINE#n, fifth and sixth LC cells in the even-numbered horizontal display lines are disposed between the (i+2)-th data line and a (i+3) data line. The fifth LC cells in the even-numbered horizontal display lines charge therein the positive data voltages supplied from the (i+2)-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the (i+2)-th data line during the (N+1)-th frame period. The sixth LC cells in the even-numbered horizontal display lines charge therein the negative data voltages supplied from the (i+3)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+3)-th data line during the (N+1)-th frame period. In FIG. 13 , the reference numeral “PIX 25 ” denotes the fifth pixel electrodes formed in the fifth LC cells in the even-numbered horizontal display lines, and the reference numeral “PIX 26 ” denotes the sixth pixel electrodes formed in the sixth LC cells in the even-numbered horizontal display lines.
[0152] As can be seen from FIG. 13 , the second and third LC cells in the odd-numbered horizontal display lines and the first and fourth LC cells in the even-numbered horizontal display lines charge therein the data voltages with the same polarity which are supplied from the (i+1)-th data line. The polarity of the data voltages charged in the second and third LC cells in the odd-numbered horizontal display lines and the first and fourth LC cells in the even-numbered horizontal display lines is opposite to that of the data voltages charged in the first and fourth LC cells in the odd-numbered horizontal display lines and the second and third LC cells in the even-numbered horizontal display lines. The polarities of the data voltages charged in the first to fourth LC cells in the odd-numbered horizontal display lines and the first to fourth LC cells in the even-numbered horizontal display lines are reversed in a unit of horizontal 2-dot and vertical 1-dot. On the other hand, the polarities of the data voltages charged in the third to sixth LC cells in the odd-numbered horizontal display lines and the third to sixth LC cells in the even-numbered horizontal display lines are reversed in a unit of horizontal 1-dot and vertical 1-dot.
[0153] In the pixel array 10 shown in FIG. 13 , connection relations among the TFTs, the pixel electrodes, and the data lines will be described by exemplifying the first to sixth LC cells in the first horizontal display line LINE# 1 , and the first to sixth LC cells in the second horizontal display line LINE# 2 .
[0154] The second LC cell in the first horizontal display line LINE# 1 charges therein the data voltage supplied from the second data line D 2 . Successively, the first LC cell in the first horizontal display line LINE# 1 charges therein the data voltage supplied from the first data line D 1 . The first TFT T 11 in the first horizontal display line transmits the data voltage from the first data line D 1 to the first pixel electrode PIX 11 in response to the second gate pulse from the second gate line G 2 . The first pixel electrode PIX 11 charges the data voltage therein during about ½ horizontal period. A gate terminal of the first TFT T 11 is connected to the second gate line G 2 . A drain terminal of the first TFT T 11 is connected to the first data line D 1 , and a source terminal thereof is connected to the first pixel electrode PIX 11 . The second TFT T 12 in the first horizontal display line transmits the data voltage from the second data line D 2 to the second pixel electrode PIX 12 in response to the first gate pulse from the first gate line G 1 . The second pixel electrode PIX 12 charges the data voltage therein during about ½ horizontal period. A gate terminal of the second TFT T 12 is connected to the first gate line G 1 . A drain terminal of the second TFT T 12 is connected to the second data line D 2 , and a source terminal thereof is connected to the second pixel electrode PIX 12 .
[0155] The fourth LC cell in the first horizontal display line LINE# 1 charges therein the data voltage supplied from the third data line D 3 . Successively, the third LC cell in the first horizontal display line LINE# 1 charges therein the data voltage supplied from the second data line D 2 . The third TFT T 13 in the first horizontal display line transmits the data voltage from the second data line D 2 to the third pixel electrode PIX 13 in response to the second gate pulse from the second gate line G 2 . The third pixel electrode PIX 13 charges the data voltage therein during about ½ horizontal period. A gate terminal of the third TFT T 13 is connected to the second gate line G 2 . A drain terminal of the third TFT T 13 is connected to the second data line D 2 , and a source terminal thereof is connected to the third pixel electrode PIX 13 . The fourth TFT T 14 in the first horizontal display line transmits the data voltage from the third data line D 3 to the fourth pixel electrode PIX 14 in response to the first gate pulse from the first gate line G 1 . The fourth pixel electrode PIX 14 charges the data voltage therein during about ½ horizontal period. A gate terminal of the fourth TFT T 14 is connected to the first gate line G 1 . A drain terminal of the second TFT T 12 is connected to the third data line D 3 , and a source terminal thereof is connected to the fourth pixel electrode PIX 14 .
[0156] The fifth LC cell in the first horizontal display line LINE# 1 charges therein the data voltage supplied from the fourth data line D 4 . Successively, the sixth LC cell in the first horizontal display line LINE# 1 charges therein the data voltage supplied from the third data line D 3 . The fifth TFT T 15 in the first horizontal display line transmits the data voltage from the fourth data line D 4 to the fifth pixel electrode PIX 15 in response to the first gate pulse from the first gate line G 1 . The fifth pixel electrode PIX 15 charges the data voltage therein during about ½ horizontal period. A gate terminal of the fifth TFT T 15 is connected to the first gate line G 1 . A drain terminal of the fifth TFT T 15 is connected to the fourth data line D 4 , and a source terminal thereof is connected to the fifth pixel electrode PIX 15 . The sixth TFT T 16 in the first horizontal display line transmits the data voltage from the third data line D 3 to the sixth pixel electrode PIX 16 in response to the second gate pulse from the second gate line G 2 . The sixth pixel electrode PIX 16 charges the data voltage therein during about ½ horizontal period. A gate terminal of the sixth TFT T 16 is connected to the second gate line G 2 . A drain terminal of the second TFT T 12 is connected to the third data line D 3 , and a source terminal thereof is connected to the sixth pixel electrode PIX 16 .
[0157] The first LC cell in the second horizontal display line LINE# 2 charges therein the data voltage supplied from the second data line D 2 . Successively, the second LC cell in the second horizontal display line LINE# 2 charges therein the data voltage supplied from the first data line D 1 . The first TFT T 21 in the second horizontal display line transmits the data voltage from the second data line D 2 to the first pixel electrode PIX 21 in response to the third gate pulse from the third gate line G 3 . The first pixel electrode PIX 21 charges the data voltage therein during about ½ horizontal period. A gate terminal of the first TFT T 21 is connected to the third gate line G 3 . A drain terminal of the first TFT T 21 is connected to the second data line D 2 , and a source terminal thereof is connected to the first pixel electrode PIX 21 . The second TFT T 22 in the second horizontal display line transmits the data voltage from the first data line D 1 to the second pixel electrode PIX 22 in response to the fourth gate pulse from the fourth gate line G 4 . The second pixel electrode PIX 22 charges the data voltage therein during about ½ horizontal period. A gate terminal of the second TFT T 22 is connected to the fourth gate line G 4 . A drain terminal of the second TFT T 22 is connected to the first data line D 1 , and a source terminal thereof is connected to the second pixel electrode PIX 22 .
[0158] The third LC cell in the second horizontal display line LINE# 2 charges therein the data voltage supplied from the third data line D 3 . Successively, the fourth LC cell in the second horizontal display line LINE# 2 charges therein the data voltage supplied from the second data line D 2 . The third TFT T 23 in the second horizontal display line transmits the data voltage from the third data line D 3 to the third pixel electrode PIX 23 in response to the third gate pulse from the third gate line G 3 . The third pixel electrode PIX 23 charges the data voltage therein during about ½ horizontal period. A gate terminal of the third TFT T 23 is connected to the third gate line G 3 . A drain terminal of the third TFT T 23 is connected to the third data line D 3 , and a source terminal thereof is connected to the third pixel electrode PIX 23 . The fourth TFT T 24 in the second horizontal display line transmits the data voltage from the second data line D 2 to the fourth pixel electrode PIX 24 in response to the fourth gate pulse from the fourth gate line G 4 . The fourth pixel electrode PIX 24 charges the data voltage therein during about ½ horizontal period. A gate terminal of the fourth TFT T 24 is connected to the fourth gate line G 4 . A drain terminal of the fourth TFT T 24 is connected to the second data line D 2 , and a source terminal thereof is connected to the fourth pixel electrode PIX 24 .
[0159] The sixth LC cell in the second horizontal display line LINE# 2 charges therein the data voltage supplied from the fourth data line D 4 . Successively, the fifth LC cell in the second horizontal display line LINE# 2 charges therein the data voltage supplied from the third data line D 3 . The fifth TFT T 25 in the second horizontal display line transmits the data voltage from the third data line D 3 to the fifth pixel electrode PIX 25 in response to the fourth gate pulse from the fourth gate line G 4 . The fifth pixel electrode PIX 25 charges the data voltage therein during about ½ horizontal period. A gate terminal of the fifth TFT T 25 is connected to the fourth gate line G 4 . A drain terminal of the fifth TFT T 25 is connected to the third data line D 3 , and a source terminal thereof is connected to the fifth pixel electrode PIX 25 . The sixth TFT T 26 in the second horizontal display line transmits the data voltage from the fourth data line D 4 to the sixth pixel electrode PIX 26 in response to the third gate pulse from the third gate line G 3 . The sixth pixel electrode PIX 26 charges the data voltage therein during about ½ horizontal period. A gate terminal of the sixth TFT T 26 is connected to the third gate line G 3 . A drain terminal of the sixth TFT T 26 is connected to the fourth data line D 4 , and a source terminal thereof is connected to the sixth pixel electrode PIX 26 .
[0160] FIG. 14 is a circuit diagram illustrating a ninth embodiment of the pixel array 10 .
[0161] In FIG. 14 , the pixel array 10 is provided with data lines D 1 to Dm+1, gate lines G 1 to Gln intersecting the data lines D 1 to Dm+1, and TFTs T 11 to T 16 and T 21 to T 26 which switch current paths formed between the pixel electrodes PIX 11 to PIX 16 and PIX 21 to PIX 26 in LC cells and the data lines D 1 to Dm+1 in response to gate pulses. For the data voltages charged in the LC cells due to the pixel array structure in FIG. 14 , their polarities are reversed in a unit of horizontal 2-dot and vertical 1-dot. In addition, the polarities of the data voltages charged in a part of the LC cells of the pixel array 10 in FIG. 14 are reversed in a unit of horizontal 1-dot and vertical 1-dot. Therefore, in the pixel array in FIG. 14 , there are mixed the LC cells where the polarities of the data voltages charged therein are reversed in a unit of horizontal 2-dot and vertical 1-dot and in a unit of horizontal 1-dot and vertical 1-dot.
[0162] The source drive ICs 12 output to the data lines D 1 to Dm+1 the data voltages of which the polarities are reversed by the column inversion scheme. The gate drivers 13 sequentially supply the gate pulses for the first to 2n-th gate lines G 1 to G 2 n . A first gate pulse is provided to the first gate line G 1 , and then second to 2n-th gate pulses are provided to the second to 2n-th gate lines G 2 to G 2 n.
[0163] During an N-th frame period, the source drive ICs 12 supply only positive data voltages for the odd-numbered data lines D 1 , D 3 , . . . , Dm−1 and Dm+1, and supply only negative data voltages for the even-numbered data lines D 2 , D 4 , . . . , and Dm. During a (N+1)-th frame period, the source drive ICs 12 supply only the negative data voltages for the odd-numbered data lines D 1 , D 3 , . . . , Dm−1 and Dm+1, and supply only the positive data voltages for the even-numbered data lines D 2 , D 4 , . . . , and Dm.
[0164] In the respective odd-numbered horizontal display lines LINE# 1 , LINE# 3 , . . . , and LINE#n−1, first and second LC cells in the odd-numbered horizontal display lines are disposed between an i-th data line and a (i+1)-th data line. The first LC cells in the odd-numbered horizontal display lines charge therein the positive data voltages supplied from the i-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the i-th data line during the (N+1)-th frame period. The second LC cells in the odd-numbered horizontal display lines charge therein the negative data voltages supplied from the (i+1)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+1)-th data line during the (N+1)-th frame period.
[0165] In FIG. 14 , the reference numeral “PIX 11 ” denotes the first pixel electrodes formed in the first LC cells in the odd-numbered horizontal display lines, and the reference numeral “PIX 12 ” denotes the second pixel electrodes formed in the second LC cells in the odd-numbered horizontal display lines.
[0166] In the respective odd-numbered horizontal display lines LINE# 1 , LINE# 3 , . . . , and LINE#n−1, third and fourth LC cells in the odd-numbered horizontal display lines are disposed between the (i+1)-th data line and a (i+2)-th data line. The third LC cells in the odd-numbered horizontal display lines charge therein the negative data voltages supplied from the (i+1)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+1)-th data line during the (N+1)-th frame period. The fourth LC cells in the odd-numbered horizontal display lines charge therein the positive data voltages supplied from the (i+2)-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the (i+2)-th data line during the (N+1)-th frame period. In FIG. 14 , the reference numeral “PIX 13 ” denotes the third pixel electrodes formed in the third LC cells in the odd-numbered horizontal display lines, and the reference numeral “PIX 14 ” denotes the fourth pixel electrodes formed in the fourth LC cells in the odd-numbered horizontal display lines.
[0167] In the respective odd-numbered horizontal display lines LINE# 1 , LINE# 3 , . . . , and LINE#n−1, fifth and sixth LC cells in the odd-numbered horizontal display lines are disposed between the (i+2)-th data line and a (i+3)-th data line. The fifth LC cells in the odd-numbered horizontal display lines charge therein the negative data voltages supplied from the (i+3)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+3)-th data line during the (N+1)-th frame period. The sixth LC cells in the odd-numbered horizontal display lines charge therein the positive data voltages supplied from the (i+2)-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the (i+2)-th data line during the (N+1)-th frame period. In FIG. 14 , the reference numeral “PIX 15 ” denotes the fifth pixel electrodes formed in the fifth LC cells in the odd-numbered horizontal display lines, and the reference numeral “PIX 16 ” denotes the sixth pixel electrodes formed in the sixth LC cells in the odd-numbered horizontal display lines.
[0168] In The respective even-numbered horizontal display lines LINE# 2 , LINE# 4 , . . . , and LINE#n, first and second LC cells in the even-numbered horizontal display lines are disposed between the i-th data line and the (i+1) data line. The first LC cells in the even-numbered horizontal display lines charge therein the negative data voltages supplied from the (i+1)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+1)-th data line during the (N+1)-th frame period. The second LC cells in the even-numbered horizontal display lines charge therein the positive data voltages supplied from the i-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the i-th data line during the (N+1)-th frame period. In FIG. 14 , the reference numeral “PIX 21 ” denotes the first pixel electrodes formed in the first LC cells in the even-numbered horizontal display lines, and the reference numeral “PIX 22 ” denotes the second pixel electrodes formed in the second LC cells in the even-numbered horizontal display lines.
[0169] In the respective even-numbered horizontal display lines LINE# 2 , LINE# 4 , . . . , and LINE#n, third and fourth LC cells in the even-numbered horizontal display lines are disposed between the (i+1)-th data line and a (i+2) data line. The third LC cells in the even-numbered horizontal display lines charge therein the positive data voltages supplied from the (i+2)-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the (i+2)-th data line during the (N+1)-th frame period. The fourth LC cells in the even-numbered horizontal display lines charge therein the negative data voltages supplied from the (i+1)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+1)-th data line during the (N+1)-th frame period. In FIG. 14 , the reference numeral “PIX 23 ” denotes the third pixel electrodes formed in the third LC cells in the even-numbered horizontal display lines, and the reference numeral “PIX 24 ” denotes the fourth pixel electrodes formed in the fourth LC cells in the even-numbered horizontal display lines.
[0170] In the respective even-numbered horizontal display lines LINE# 2 , LINE# 4 , . . . , and LINE#n, fifth and sixth LC cells in the even-numbered horizontal display lines are disposed between the (i+2)-th data line and a (i+3) data line. The fifth LC cells in the even-numbered horizontal display lines charge therein the positive data voltages supplied from the (i+2)-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the (i+2)-th data line during the (N+1)-th frame period. The sixth LC cells in the even-numbered horizontal display lines charge therein the negative data voltages supplied from the (i+3)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+3)-th data line during the (N+1)-th frame period. In FIG. 14 , the reference numeral “PIX 25 ” denotes the fifth pixel electrodes formed in the fifth LC cells in the even-numbered horizontal display lines, and the reference numeral “PIX 26 ” denotes the sixth pixel electrodes formed in the sixth LC cells in the even-numbered horizontal display lines.
[0171] As can be seen from FIG. 14 , the second and third LC cells in the odd-numbered horizontal display lines and the first and fourth LC cells in the even-numbered horizontal display lines charge therein the data voltages with the same polarity which are supplied from the (i+1)-th data line. The polarity of the data voltages charged in the second and third LC cells in the odd-numbered horizontal display lines and the first and fourth LC cells in the even-numbered horizontal display lines is opposite to that of the data voltages charged in the first and fourth LC cells in the odd-numbered horizontal display lines and the second and third LC cells in the even-numbered horizontal display lines. The polarities of the data voltages charged in the first to fourth LC cells in the odd-numbered horizontal display lines and the first to fourth LC cells in the even-numbered horizontal display lines are reversed in a unit of horizontal 2-dot and vertical 1-dot. On the other hand, the polarities of the data voltages charged in the third to sixth LC cells in the odd-numbered horizontal display lines and the third to sixth LC cells in the even-numbered horizontal display lines are reversed in a unit of horizontal 1-dot and vertical 1-dot.
[0172] In the pixel array 10 shown in FIG. 14 , connection relations among the TFTs, the pixel electrodes, and the data lines will be described by exemplifying the first to sixth LC cells in the first horizontal display line LINE# 1 , and the first to sixth LC cells in the second horizontal display line LINE# 2 .
[0173] The first LC cell in the first horizontal display line LINE# 1 charges therein the data voltage supplied from the first data line D 1 . Successively, the second LC cell in the first horizontal display line LINE# 1 charges therein the data voltage supplied from the second data line D 2 . The first TFT T 11 in the first horizontal display line transmits the data voltage from the first data line D 1 to the first pixel electrode PIX 11 in response to the first gate pulse from the first gate line G 1 . The first pixel electrode PIX 11 charges the data voltage therein during about ½ horizontal period. A gate terminal of the first TFT T 11 is connected to the first gate line G 1 . A drain terminal of the first TFT T 11 is connected to the first data line D 1 , and a source terminal thereof is connected to the first pixel electrode PIX 11 . The second TFT T 12 in the first horizontal display line transmits the data voltage from the second data line D 2 to the second pixel electrode PIX 12 in response to the second gate pulse from the second gate line G 2 . The second pixel electrode PIX 12 charges the data voltage therein during about ½ horizontal period. A gate terminal of the second TFT T 12 is connected to the second gate line G 2 . A drain terminal of the second TFT T 12 is connected to the second data line D 2 , and a source terminal thereof is connected to the second pixel electrode PIX 12 .
[0174] The third LC cell in the first horizontal display line LINE# 1 charges therein the data voltage supplied from the second data line D 2 . Successively, the fourth LC cell in the first horizontal display line LINE# 1 charges therein the data voltage supplied from the third data line D 3 . The third TFT T 13 in the first horizontal display line transmits the data voltage from the second data line D 2 to the third pixel electrode PIX 13 in response to the first gate pulse from the first gate line G 1 . The third pixel electrode PIX 13 charges the data voltage therein during about ½ horizontal period. A gate terminal of the third TFT T 13 is connected to the first gate line G 1 . A drain terminal of the third TFT T 13 is connected to the second data line D 2 , and a source terminal thereof is connected to the third pixel electrode PIX 13 . The fourth TFT T 14 in the first horizontal display line transmits the data voltage from the third data line D 3 to the fourth pixel electrode PIX 14 in response to the second gate pulse from the second gate line G 2 . The fourth pixel electrode PIX 14 charges the data voltage therein during about ½ horizontal period. A gate terminal of the fourth TFT T 14 is connected to the second gate line G 2 . A drain terminal of the fourth TFT T 14 is connected to the third data line D 3 , and a source terminal thereof is connected to the fourth pixel electrode PIX 14 .
[0175] The sixth LC cell in the first horizontal display line LINE# 1 charges therein the data voltage supplied from the third data line D 3 . Successively, the fifth LC cell in the first horizontal display line LINE# 1 charges therein the data voltage supplied from the fourth data line D 4 . The fifth TFT T 15 in the first horizontal display line transmits the data voltage from the fourth data line D 4 to the fifth pixel electrode PIX 15 in response to the second gate pulse from the second gate line G 2 . The fifth pixel electrode PIX 15 charges the data voltage therein during about ½ horizontal period. A gate terminal of the fifth TFT T 15 is connected to the second gate line G 2 . A drain terminal of the fifth TFT T 15 is connected to the fourth data line D 4 , and a source terminal thereof is connected to the fifth pixel electrode PIX 15 . The sixth TFT T 16 in the first horizontal display line transmits the data voltage from the third data line D 3 to the sixth pixel electrode PIX 16 in response to the first gate pulse from the first gate line G 1 . The sixth pixel electrode PIX 16 charges the data voltage therein during about ½ horizontal period. A gate terminal of the sixth TFT T 16 is connected to the first gate line G 1 . A drain terminal of the second TFT T 12 is connected to the third data line D 3 , and a source terminal thereof is connected to the sixth pixel electrode PIX 16 .
[0176] The second LC cell in the second horizontal display line LINE# 2 charges therein the data voltage supplied from the first data line D 1 . Successively, the first LC cell in the second horizontal display line LINE# 2 charges therein the data voltage supplied from the second data line D 2 . The first TFT T 21 in the second horizontal display line transmits the data voltage from the second data line D 2 to the first pixel electrode PIX 21 in response to the fourth gate pulse from the fourth gate line G 4 . The first pixel electrode PIX 21 charges the data voltage therein during about ½ horizontal period. A gate terminal of the first TFT T 21 is connected to the fourth gate line G 4 . A drain terminal of the first TFT T 21 is connected to the second data line D 2 , and a source terminal thereof is connected to the first pixel electrode PIX 21 . The second TFT T 22 in the second horizontal display line transmits the data voltage from the first data line D 1 to the second pixel electrode PIX 22 in response to the third gate pulse from the third gate line G 3 . The second pixel electrode PIX 22 charges the data voltage therein during about ½ horizontal period. A gate terminal of the second TFT T 22 is connected to the third gate line G 3 . A drain terminal of the second TFT T 22 is connected to the first data line D 1 , and a source terminal thereof is connected to the second pixel electrode PIX 22 .
[0177] The fourth LC cell in the second horizontal display line LINE# 2 charges therein the data voltage supplied from the second data line D 2 . Successively, the third LC cell in the second horizontal display line LINE# 2 charges therein the data voltage supplied from the third data line D 3 . The third TFT T 23 in the second horizontal display line transmits the data voltage from the third data line D 3 to the third pixel electrode PIX 23 in response to the fourth gate pulse from the fourth gate line G 4 . The third pixel electrode PIX 23 charges the data voltage therein during about ½ horizontal period. A gate terminal of the third TFT T 23 is connected to the fourth gate line G 4 . A drain terminal of the third TFT T 23 is connected to the third data line D 3 , and a source terminal thereof is connected to the third pixel electrode PIX 23 . The fourth TFT T 24 in the second horizontal display line transmits the data voltage from the second data line D 2 to the fourth pixel electrode PIX 24 in response to the third gate pulse from the third gate line G 3 . The fourth pixel electrode PIX 24 charges the data voltage therein during about ½ horizontal period. A gate terminal of the fourth TFT T 24 is connected to the third gate line G 3 . A drain terminal of the fourth TFT T 24 is connected to the second data line D 2 , and a source terminal thereof is connected to the fourth pixel electrode PIX 24 .
[0178] The fifth LC cell in the second horizontal display line LINE# 2 charges therein the data voltage supplied from the third data line D 3 . Successively, the sixth LC cell in the second horizontal display line LINE# 2 charges therein the data voltage supplied from the fourth data line D 4 . The fifth TFT T 25 in the second horizontal display line transmits the data voltage from the third data line D 3 to the fifth pixel electrode PIX 25 in response to the third gate pulse from the third gate line G 3 . The fifth pixel electrode PIX 25 charges the data voltage therein during about ½ horizontal period. A gate terminal of the fifth TFT T 25 is connected to the third gate line G 3 . A drain terminal of the fifth TFT T 25 is connected to the third data line D 3 , and a source terminal thereof is connected to the fifth pixel electrode PIX 25 . The sixth TFT T 26 in the second horizontal display line transmits the data voltage from the fourth data line D 4 to the sixth pixel electrode PIX 26 in response to the fourth gate pulse from the fourth gate line G 4 . The sixth pixel electrode PIX 26 charges the data voltage therein during about ½ horizontal period. A gate terminal of the sixth TFT T 26 is connected to the fourth gate line G 4 . A drain terminal of the sixth TFT T 26 is connected to the fourth data line D 4 , and a source terminal thereof is connected to the sixth pixel electrode PIX 26 .
[0179] FIG. 15 is a circuit diagram illustrating a tenth embodiment of the pixel array 10 .
[0180] In FIG. 15 , the pixel array 10 is provided with data lines D 1 to Dm+1, gate lines G 1 to G 2 n intersecting the data lines D 1 to Dm+1, and TFTs T 11 to T 16 and T 21 to T 26 which switch current paths formed between the pixel electrodes PIX 11 to PIX 16 and PIX 21 to PIX 26 in LC cells and the data lines D 1 to Dm+1 in response to gate pulses. For the data voltages charged in the LC cells due to the pixel array structure in FIG. 15 , their polarities are reversed in a unit of horizontal 1-dot and vertical 1-dot.
[0181] The source drive ICs 12 output to the data lines D 1 to Dm+1 the data voltages of which the polarities are reversed by the column inversion scheme. The gate drivers 13 sequentially supply the gate pulses for the first to 2n-th gate lines G 1 to G 2 n . A first gate pulse is provided to the first gate line G 1 , and then second to 2n-th gate pulses are provided to the second to 2n-th gate lines G 2 to G 2 n.
[0182] During an N-th frame period, the source drive ICs 12 supply only positive data voltages for the odd-numbered data lines D 1 , D 3 , . . . , Dm−1 and Dm+1, and supply only negative data voltages for the even-numbered data lines D 2 , D 4 , . . . , and Dm. During a (N+1)-th frame period, the source drive ICs 12 supply only the negative data voltages for the odd-numbered data lines D 1 , D 3 , . . . , Dm−1 and Dm+1, and supply only the positive data voltages for the even-numbered data lines D 2 , D 4 , . . . , and Dm.
[0183] In the respective odd-numbered horizontal display lines LINE# 1 , LINE# 3 , . . . , and LINE#n−1, first and second LC cells in the odd-numbered horizontal display lines are disposed between an i-th data line and a (i+1)-th data line. The first LC cells in the odd-numbered horizontal display lines charge therein the negative data voltages supplied from the (i+1)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+1)-th data line during the (N+1)-th frame period. The second LC cells in the odd-numbered horizontal display lines charge therein the positive data voltages supplied from the i-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the i-th data line during the (N+1)-th frame period. In FIG. 15 , the reference numeral “PIX 11 ” denotes the first pixel electrodes formed in the first LC cells in the odd-numbered horizontal display lines, and the reference numeral “PIX 12 ” denotes the second pixel electrodes formed in the second LC cells in the odd-numbered horizontal display lines.
[0184] In the respective odd-numbered horizontal display lines LINE# 1 , LINE# 3 , . . . , and LINE#n−1, third and fourth LC cells in the odd-numbered horizontal display lines are disposed between the (i+1)-th data line and a (i+2)-th data line. The third LC cells in the odd-numbered horizontal display lines charge therein the negative data voltages supplied from the (i+1)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+1)-th data line during the (N+1)-th frame period. The fourth LC cells in the odd-numbered horizontal display lines charge therein the positive data voltages supplied from the (i+2)-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the (i+2)-th data line during the (N+1)-th frame period. In FIG. 15 , the reference numeral “PIX 13 ” denotes the third pixel electrodes formed in the third LC cells in the odd-numbered horizontal display lines, and the reference numeral “PIX 14 ” denotes the fourth pixel electrodes formed in the fourth LC cells in the odd-numbered horizontal display lines.
[0185] In the respective odd-numbered horizontal display lines LINE# 1 , LINE# 3 , . . . , and LINE#n−1, fifth and sixth LC cells in the odd-numbered horizontal display lines are disposed between the (i+2)-th data line and a (i+3)-th data line. The fifth LC cells in the odd-numbered horizontal display lines charge therein the negative data voltages supplied from the (i+3)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+3)-th data line during the (N+1)-th frame period. The sixth LC cells in the odd-numbered horizontal display lines charge therein the positive data voltages supplied from the (i+2)-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the (i+2)-th data line during the (N+1)-th frame period. In FIG. 15 , the reference numeral “PIX 15 ” denotes the fifth pixel electrodes formed in the fifth LC cells in the odd-numbered horizontal display lines, and the reference numeral “PIX 16 ” denotes the sixth pixel electrodes formed in the sixth LC cells in the odd-numbered horizontal display lines.
[0186] In The respective even-numbered horizontal display lines LINE# 2 , LINE# 4 , . . . , and LINE#n, first and second LC cells in the even-numbered horizontal display lines are disposed between the i-th data line and the (i+1) data line. The first LC cells in the even-numbered horizontal display lines charge therein the positive data voltages supplied from the i-th data line during the N-th frame period, and thereafter charge therein negative data voltages the supplied from the i-th data line during the (N+1)-th frame period. The second LC cells in the even-numbered horizontal display lines charge therein the negative data voltages supplied from the (i+1)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+1)-th data line during the (N+1)-th frame period. In FIG. 15 , the reference numeral “PIX 21 ” denotes the first pixel electrodes formed in the first LC cells in the even-numbered horizontal display lines, and the reference numeral “PIX 22 ” denotes the second pixel electrodes formed in the second LC cells in the even-numbered horizontal display lines.
[0187] In the respective even-numbered horizontal display lines LINE# 2 , LINE# 4 , . . . , and LINE#n, third and fourth LC cells in the even-numbered horizontal display lines are disposed between the (i+1)-th data line and a (i+2) data line. The third LC cells in the even-numbered horizontal display lines charge therein the positive data voltages supplied from the (i+2)-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the (i+2)-th data line during the (N+1)-th frame period. The fourth LC cells in the even-numbered horizontal display lines charge therein the negative data voltages supplied from the (i+1)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+1)-th data line during the (N+1)-th frame period. In FIG. 15 , the reference numeral “PIX 23 ” denotes the third pixel electrodes formed in the third LC cells in the even-numbered horizontal display lines, and the reference numeral “PIX 24 ” denotes the fourth pixel electrodes formed in the fourth LC cells in the even-numbered horizontal display lines.
[0188] In the respective even-numbered horizontal display lines LINE# 2 , LINE# 4 , . . . , and LINE#n, fifth and sixth LC cells in the even-numbered horizontal display lines are disposed between the (i+2)-th data line and a (i+3) data line. The fifth LC cells in the even-numbered horizontal display lines charge therein the positive data voltages supplied from the (i+2)-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the (i+2)-th data line during the (N+1)-th frame period. The sixth LC cells in the even-numbered horizontal display lines charge therein the negative data voltages supplied from the (i+3)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+3)-th data line during the (N+1)-th frame period. In FIG. 15 , the reference numeral “PIX 25 ” denotes the fifth pixel electrodes formed in the fifth LC cells in the even-numbered horizontal display lines, and the reference numeral “PIX 26 ” denotes the sixth pixel electrodes formed in the sixth LC cells in the even-numbered horizontal display lines.
[0189] As can be seen from FIG. 15 , the LC cells adjacent to each other in the vertical direction as well as the LC cells adjacent to each other in the horizontal direction charge therein the data voltages with the polarities opposite to each other. Therefore, the LC cells of the pixel array in FIG. 15 charge therein the data voltages of which the polarities are reversed in a unit of horizontal 1-dot and vertical 1-dot.
[0190] In the pixel array 10 shown in FIG. 15 , connection relations among the TFTs, the pixel electrodes, and the data lines will be described by exemplifying the first to fourth LC cells in the first horizontal display line LINE# 1 , and the first to fourth LC cells in the second horizontal display line LINE# 2 .
[0191] The first LC cell in the first horizontal display line LINE# 1 charges therein the data voltage supplied from the second data line D 2 . Successively, the second LC cell in the first horizontal display line LINE# 1 charges therein the data voltage supplied from the first data line D 1 . The first TFT T 11 in the first horizontal display line transmits the data voltage from the second data line D 2 to the first pixel electrode PIX 11 in response to the first gate pulse from the first gate line G 1 . The first pixel electrode PIX 11 charges the data voltage therein during about ½ horizontal period. A gate terminal of the first TFT T 11 is connected to the first gate line G 1 . A drain terminal of the first TFT T 11 is connected to the second data line D 2 , and a source terminal thereof is connected to the first pixel electrode PIX 11 . The second TFT T 12 in the first horizontal display line transmits the data voltage from the first data line D 1 to the second pixel electrode PIX 12 in response to the second gate pulse from the second gate line G 2 . The second pixel electrode PIX 12 charges the data voltage therein during about ½ horizontal period. A gate terminal of the second TFT T 12 is connected to the second gate line G 2 . A drain terminal of the second TFT T 12 is connected to the first data line D 1 , and a source terminal thereof is connected to the second pixel electrode PIX 12 .
[0192] The fourth LC cell in the first horizontal display line LINE# 1 charges therein the data voltage supplied from the third data line D 3 . Successively, the third LC cell in the first horizontal display line LINE# 1 charges therein the data voltage supplied from the second data line D 2 . The third TFT T 13 in the first horizontal display line transmits the data voltage from the second data line D 2 to the third pixel electrode PIX 13 in response to the second gate pulse from the second gate line G 2 . The third pixel electrode PIX 13 charges the data voltage therein during about ½ horizontal period. A gate terminal of the third TFT T 13 is connected to the second gate line G 2 . A drain terminal of the third TFT T 13 is connected to the second data line D 2 , and a source terminal thereof is connected to the third pixel electrode PIX 13 . The fourth TFT T 14 in the first horizontal display line transmits the data voltage from the third data line D 3 to the fourth pixel electrode PIX 14 in response to the first gate pulse from the first gate line G 1 . The fourth pixel electrode PIX 14 charges the data voltage therein during about ½ horizontal period. A gate terminal of the fourth TFT T 14 is connected to the first gate line G 1 . A drain terminal of the fourth TFT T 14 is connected to the third data line D 3 , and a source terminal thereof is connected to the fourth pixel electrode PIX 14 .
[0193] The second LC cell in the second horizontal display line LINE# 2 charges therein the data voltage supplied from the second data line D 2 . Successively, the first LC cell in the second horizontal display line LINE# 2 charges therein the data voltage supplied from the first data line D 1 . The first TFT T 21 in the second horizontal display line transmits the data voltage from the first data line D 1 to the first pixel electrode PIX 21 in response to the fourth gate pulse from the fourth gate line G 4 . The first pixel electrode PIX 21 charges the data voltage therein during about ½ horizontal period. A gate terminal of the first TFT T 21 is connected to the fourth gate line G 4 . A drain terminal of the first TFT T 21 is connected to the first data line D 1 , and a source terminal thereof is connected to the first pixel electrode PIX 21 . The second TFT T 22 in the second horizontal display line transmits the data voltage from the second data line D 2 to the second pixel electrode PIX 22 in response to the third gate pulse from the third gate line G 3 . The second pixel electrode PIX 22 charges the data voltage therein during about ½ horizontal period. A gate terminal of the second TFT T 22 is connected to the third gate line G 3 . A drain terminal of the second TFT T 22 is connected to the second data line D 2 , and a source terminal thereof is connected to the second pixel electrode PIX 22 .
[0194] The third LC cell in the second horizontal display line LINE# 2 charges therein the data voltage supplied from the third data line D 3 . Successively, the fourth LC cell in the second horizontal display line LINE# 2 charges therein the data voltage supplied from the second data line D 2 . The third TFT T 23 in the second horizontal display line transmits the data voltage from the third data line D 3 to the third pixel electrode PIX 23 in response to the third gate pulse from the third gate line G 3 . The third pixel electrode PIX 23 charges the data voltage therein during about ½ horizontal period. A gate terminal of the third TFT T 23 is connected to the third gate line G 3 . A drain terminal of the third TFT T 23 is connected to the third data line D 3 , and a source terminal thereof is connected to the third pixel electrode PIX 23 . The fourth TFT T 24 in the second horizontal display line transmits the data voltage from the second data line D 2 to the fourth pixel electrode PIX 24 in response to the fourth gate pulse from the fourth gate line G 4 . The fourth pixel electrode PIX 24 charges the data voltage therein during about ½ horizontal period. A gate terminal of the fourth TFT T 24 is connected to the fourth gate line G 4 . A drain terminal of the fourth TFT T 24 is connected to the second data line D 2 , and a source terminal thereof is connected to the fourth pixel electrode PIX 24 .
[0195] FIG. 16 is a circuit diagram illustrating an eleventh embodiment of the pixel array 10 .
[0196] In FIG. 16 , the pixel array 10 is provided with data lines D 1 to Dm+1, gate lines G 1 to G 2 n intersecting the data lines D 1 to Dm+1, and TFTs T 11 to T 14 and T 21 to T 24 which switch current paths formed between the pixel electrodes PIX 11 to PIX 14 and PIX 21 to PIX 24 in LC cells and the data lines D 1 to Dm+1 in response to gate pulses. For the data voltages charged in the LC cells due to the pixel array structure in FIG. 16 , their polarities are reversed in a unit of horizontal 1-dot and vertical 2-dot.
[0197] The source drive ICs 12 output to the data lines D 1 to Dm+1 the data voltages of which the polarities are reversed by the column inversion scheme. The gate drivers 13 sequentially supply the gate pulses for the first to 2n-th gate lines G 1 to G 2 n . A first gate pulse is provided to the first gate line G 1 , and then second to 2n-th gate pulses are provided to the second to 2n-th gate lines G 2 to G 2 n.
[0198] During an N-th frame period, the source drive ICs 12 supply only positive data voltages for the odd-numbered data lines D 1 , D 3 , . . . , Dm−1 and Dm+1, and supply only negative data voltages for the even-numbered data lines D 2 , D 4 , . . . , and Dm. During a (N+1)-th frame period, the source drive ICs 12 supply only the negative data voltages for the odd-numbered data lines D 1 , Dm−1 and Dm+1, and supply only the positive data voltages for the even-numbered data lines D 2 , D 4 , . . . , and Dm.
[0199] In the respective odd-numbered horizontal display lines LINE# 1 , LINE# 3 , . . . , and LINE#n−1, first and second LC cells in the odd-numbered horizontal display lines are disposed between an i-th data line and a (i+1)-th data line. The first LC cells in the odd-numbered horizontal display lines charge therein the positive data voltages supplied from the i-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the i-th data line during the (N+1)-th frame period. The second LC cells in the odd-numbered horizontal display lines charge therein the negative data voltages supplied from the (i+1)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+1)-th data line during the (N+1)-th frame period. In FIG. 16 , the reference numeral “PIX 11 ” denotes the first pixel electrodes formed in the first LC cells in the odd-numbered horizontal display lines, and the reference numeral “PIX 12 ” denotes the second pixel electrodes formed in the second LC cells in the odd-numbered horizontal display lines.
[0200] In the respective odd-numbered horizontal display lines LINE# 1 , LINE# 3 , . . . , and LINE#n−1, third and fourth LC cells in the odd-numbered horizontal display lines are disposed between the (i+1)-th data line and a (i+2)-th data line. The third LC cells in the odd-numbered horizontal display lines charge therein the positive data voltages supplied from the (i+2)-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the (i+2)-th data line during the (N+1)-th frame period. The fourth LC cells in the odd-numbered horizontal display lines charge therein the negative data voltages supplied from the (i+1)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+1)-th data line during the (N+1)-th frame period. In FIG. 16 , the reference numeral “PIX 13 ” denotes the third pixel electrodes formed in the third LC cells in the odd-numbered horizontal display lines, and the reference numeral “PIX 14 ” denotes the fourth pixel electrodes formed in the fourth LC cells in the odd-numbered horizontal display lines.
[0201] In The respective even-numbered horizontal display lines LINE# 2 , LINE# 4 , . . . , and LINE#n, first and second LC cells in the even-numbered horizontal display lines are disposed between the i-th data line and the (i+1) data line. The first LC cells in the even-numbered horizontal display lines charge therein the positive data voltages supplied from the i-th data line during the N-th frame period, and thereafter charge therein negative data voltages the supplied from the i-th data line during the (N+1)-th frame period. The second LC cells in the even-numbered horizontal display lines charge therein the negative data voltages supplied from the (i+1)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+1)-th data line during the (N+1)-th frame period. In FIG. 16 , the reference numeral “PIX 21 ” denotes the first pixel electrodes formed in the first LC cells in the even-numbered horizontal display lines, and the reference numeral “PIX 22 ” denotes the second pixel electrodes formed in the second LC cells in the even-numbered horizontal display lines.
[0202] In the respective even-numbered horizontal display lines LINE# 2 , LINE# 4 , . . . , and LINE#n, third and fourth LC cells in the even-numbered horizontal display lines are disposed between the (i+1)-th data line and a (i+2) data line. The third LC cells in the even-numbered horizontal display lines charge therein the positive data voltages supplied from the (i+2)-th data line during the N-th frame period, and thereafter charge therein the negative data voltages supplied from the (i+2)-th data line during the (N+1)-th frame period. The fourth LC cells in the even-numbered horizontal display lines charge therein the negative data voltages supplied from the (i+1)-th data line during the N-th frame period, and thereafter charge therein the positive data voltages supplied from the (i+1)-th data line during the (N+1)-th frame period. In FIG. 16 , the reference numeral “PIX 23 ” denotes the third pixel electrodes formed in the third LC cells in the even-numbered horizontal display lines, and the reference numeral “PIX 24 ” denotes the fourth pixel electrodes formed in the fourth LC cells in the even-numbered horizontal display lines.
[0203] As can be seen from FIG. 16 , the polarities of the data voltages charged in the LC cells adjacent to each other in the vertical direction are reversed in a unit of 2-dot (or LC cell), and the polarities of the data voltages charged in the LC cells adjacent to each other in the horizontal direction are reversed in a unit of 1-dot. Therefore, the LC cells of the pixel array in FIG. 16 charge the data voltages of which the polarities are reversed in a unit of horizontal 1-dot and vertical 2-dot (2×1 dots).
[0204] In the pixel array 10 shown in FIG. 16 , connection relations among the TFTs, the pixel electrodes, and the data lines will be described by exemplifying the first to fourth LC cells in the first horizontal display line LINE# 1 , and the first to fourth LC cells in the second horizontal display line LINE# 2 .
[0205] The second LC cell in the first horizontal display line LINE# 1 charges therein the data voltage supplied from the second data line D 2 . Successively, the first LC cell in the first horizontal display line LINE# 1 charges therein the data voltage supplied from the first data line D 1 . The first TFT T 11 in the first horizontal display line transmits the data voltage from the first data line D 1 to the first pixel electrode PIX 11 in response to the second gate pulse from the second gate line G 2 . The first pixel electrode PIX 11 charges the data voltage therein during about ½ horizontal period. A gate terminal of the first TFT T 11 is connected to the second gate line G 2 . A drain terminal of the first TFT T 11 is connected to the first data line D 1 , and a source terminal thereof is connected to the first pixel electrode PIX 11 . The second TFT T 12 in the first horizontal display line transmits the data voltage from the second data line D 2 to the second pixel electrode PIX 12 in response to the first gate pulse from the first gate line G 1 . The second pixel electrode PIX 12 charges the data voltage therein during about ½ horizontal period. A gate terminal of the second TFT T 12 is connected to the first gate line G 1 . A drain terminal of the second TFT T 12 is connected to the second data line D 2 , and a source terminal thereof is connected to the second pixel electrode PIX 12 .
[0206] The fourth LC cell in the first horizontal display line LINE# 1 charges therein the data voltage supplied from the second data line D 2 . Successively, the third LC cell in the first horizontal display line LINE# 1 charges therein the data voltage supplied from the third data line D 3 . The third TFT T 13 in the first horizontal display line transmits the data voltage from the third data line D 3 to the third pixel electrode PIX 13 in response to the second gate pulse from the second gate line G 2 . The third pixel electrode PIX 13 charges the data voltage therein during about ½ horizontal period. A gate terminal of the third TFT T 13 is connected to the second gate line G 2 . A drain terminal of the third TFT T 13 is connected to the third data line D 3 , and a source terminal thereof is connected to the third pixel electrode PIX 13 . The fourth TFT T 14 in the first horizontal display line transmits the data voltage from the second data line D 2 to the fourth pixel electrode PIX 14 in response to the first gate pulse from the first gate line G 1 . The fourth pixel electrode PIX 14 charges the data voltage therein during about ½ horizontal period. A gate terminal of the fourth TFT T 14 is connected to the first gate line G 1 . A drain terminal of the fourth TFT T 14 is connected to the second data line D 2 , and a source terminal thereof is connected to the fourth pixel electrode PIX 14 .
[0207] The second LC cell in the second horizontal display line LINE# 2 charges therein the data voltage supplied from the second data line D 2 . Successively, the first LC cell in the second horizontal display line LINE# 2 charges therein the data voltage supplied from the first data line D 1 . The first TFT T 21 in the second horizontal display line transmits the data voltage from the first data line D 1 to the first pixel electrode PIX 21 in response to the fourth gate pulse from the fourth gate line G 4 . The first pixel electrode PIX 21 charges the data voltage therein during about ½ horizontal period. A gate terminal of the first TFT T 21 is connected to the fourth gate line G 4 . A drain terminal of the first TFT T 21 is connected to the first data line D 1 , and a source terminal thereof is connected to the first pixel electrode PIX 21 . The second TFT T 22 in the second horizontal display line transmits the data voltage from the second data line D 2 to the second pixel electrode PIX 22 in response to the third gate pulse from the third gate line G 3 . The second pixel electrode PIX 22 charges the data voltage therein during about ½ horizontal period. A gate terminal of the second TFT T 22 is connected to the third gate line G 3 . A drain terminal of the second TFT T 22 is connected to the second data line D 2 , and a source terminal thereof is connected to the second pixel electrode PIX 22 .
[0208] The fourth LC cell in the second horizontal display line LINE# 2 charges therein the data voltage supplied from the second data line D 2 . Successively, the third LC cell in the second horizontal display line LINE# 2 charges therein the data voltage supplied from the third data line D 3 . The third TFT T 23 in the second horizontal display line transmits the data voltage from the third data line D 3 to the third pixel electrode PIX 23 in response to the fourth gate pulse from the fourth gate line G 4 . The third pixel electrode PIX 23 charges the data voltage therein during about ½ horizontal period. A gate terminal of the third TFT T 23 is connected to the fourth gate line G 4 . A drain terminal of the third TFT T 23 is connected to the third data line D 3 , and a source terminal thereof is connected to the third pixel electrode PIX 23 . The fourth TFT T 24 in the second horizontal display line transmits the data voltage from the second data line D 2 to the fourth pixel electrode PIX 24 in response to the third gate pulse from the third gate line G 3 . The fourth pixel electrode PIX 24 charges the data voltage therein during about ½ horizontal period. A gate terminal of the fourth TFT T 24 is connected to the third gate line G 3 . A drain terminal of the fourth TFT T 24 is connected to the second data line D 2 , and a source terminal thereof is connected to the fourth pixel electrode PIX 24 .
[0209] As described above, according to this document, the polarity of the data voltages charged in the LC cells connected to the same data line is controlled to be the same, thereby it is possible to reduce power consumption in the source drive ICs and also make uniform an amount of data charged in each LC cell. Thus, according to this document, it is possible to prevent degradation in image quality such as brightness unevenness, color distortion, or the like resulting from the unevenness of the amount of data charged due to the inversion method in the related art, and to reduce power consumption in the source drive ICs by reducing the number of polarity inversion for the data voltages. In addition, according to this document, it is possible to reduce the number of the data lines and the channels of the source drive ICs by the use of the TFT connection relation where the LC cells adjacent to each other in the horizontal direction share one data line with each other.
[0210] Although embodiments have been described with reference to a number of illustrative embodiments thereof, it should be understood that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the scope of the principles of this disclosure. More particularly, various variations and modifications are possible in the component parts and/or arrangements of the subject combination arrangement within the scope of the disclosure, the drawings and the appended claims. In addition to variations and modifications in the component parts and/or arrangements, alternative uses will also be apparent to those skilled in the art. | A liquid crystal display includes according to an embodiment a display panel provided with a plurality of data lines, a plurality of gate lines intersecting the data lines, liquid crystal cells arranged in a matrix, and TFTs disposed at the intersections of the data lines and the gate lines; source drive ICs configured to supply data voltages to the data lines, wherein polarities of data voltages are reversed by a column inversion scheme; and a gate driver configured to sequentially supply gate pulses for the gate lines, wherein polarities of the data voltages charged in the liquid crystal cells in the display panel are reversed in dot unit. | 6 |
BACKGROUND OF THE INVENTION
Medication in solid form such as tablets, pills, capsules or the like are sometimes dispensed to patients in dispensers having blister packages therein which include individually sealed blisters or compartments designed to hold a single dose of medication. Such packages permit the handling of only a single dose of medicine at a time and minimize the risk of contamination of the tablet, pill or capsule. Other dispensers do not include blister packages. Such dispensers are exemplified by various forms.
For example, U.S. Pat. No. 2,971,683, issued Feb. 14, 1961, discloses a dispenser which in one form is circular and includes a number of compartments for tablets or pills. An outlet opening or aperture is included in a portion of the dispenser and as the dispenser is rotated, a pill is dispensed through the opening as each compartment is positioned over the opening. In another form, the pills are retained in compartments which are in line in a sheet and as the sheet is moved to place the compartments in line with an outlet opening, the pills are dispensed.
U.S. Pat. No. 3,199,489, issued Aug. 10, 1965, discloses a container for medicament in the form of pills and which are to be administered at specific intervals. The pills are retained in a circular configuration and are dispensed by pressing out through an easily tearable foil.
U.S. Pat. No. 4,384,649, issued May 24, 1983, discloses a medicament dispensing package including a blister pack and cover and an outer shell wherein the blister pack has multiple pockets for receiving medicament, and the outer shell has means for sealing the cover around the pocket of the blister pack. The package is reusable and the blister pack is disposable.
U.S. Pat. No. 4,660,991, issued Apr. 28, 1987, discloses a dispenser for storing and signaling the time for taking drugs. The dispenser includes an electrical push button which acts on the blister pockets in the direction of ejection. Each blister pocket has a corresponding electrical push button.
U.S. Pat. No. 3,504,788, issued Apr. 7, 1970, discloses a three component package including a press through packet or blister pack, a tray to support the packet and an outer sheath to protect the packet and tray.
U.S. Pat. No. 3,630,171, issued Dec. 28, 1971, discloses a tablet dispenser including a parallel series of columns of tablets. The number of columns being equal to the number of medicament doses to be dispensed within a specified time period.
U.S. Pat. No. 4,905,866, issued Mar. 6, 1990, discloses a device for dispensing pills in successive order. The pills are retained in a single row in the desired successive order and a pill ejector is arranged for incremental movement in one direction along the dispenser. When the pill ejector is adjacent to a pill, a bendable member is displaced to push the pill out of a blister type package and through an opening in the rear of the dispenser.
SUMMARY OF THE INVENTION
Disclosed is a reusable dispensing package for dispensing medication in the form of tablets, pills, capsules or the like in a predetermined sequence. In one embodiment, the dispenser comprises a hinged container into which is placed a disposable blister pack containing the medicament. The cover of the dispenser includes a double "S" race which contains a spring-loaded button or plunger. The blister package includes a plurality of spaced apart blisters for containing the medication and the base portion of the dispenser includes a plurality of spaced apart openings coextensive with the blisters in the blister package. As the button is moved around the double "S" shaped race in the cover of the dispenser, at each corner, it is in line with a blister containing a drug, tablet or pill, for example. Hence, when the plunger is depressed, it releases the tablet or pill from the blister. This enables the patient to keep track of the number of tablets or pills which have been dispensed so that the proper number are taken daily, for example. Moreover, the dispenser is particularly useful for arthritic patients who have difficulty opening a tamper proof container generally used for dispensing medication. With the dispenser as described, simply pressing the plunger releases the desired tablet or pill, while at the same time, maintaining the tamper proof feature of the dispenser.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be better understood by referring to the accompanying drawings in which:
FIG. 1 is an isometric representation of an embodiment of a dispenser pack in accordance with the invention;
FIG. 2 is a plan view of the dispenser pack when viewing the inside of the cover and the inside of the base;
FIG. 3 is a plan view of the opened dispenser pack when viewing the top of the cover and the outside of the base;
FIG. 4 is a cross-sectional view of a portion of the dispenser pack as viewed along the lines 4--4 of FIG. 3;
FIG. 5 is a side elevational view of the dispenser pack when in the closed position;
FIG. 6 is an end cross-sectional view as viewed along the lines 5--5 of FIG. 5 and illustrating the plunger positioned over a blister in the blister pack; and
FIG. 7 is an exploded view of a spring-loaded embodiment of the plunger.
DETAILED DESCRIPTION OF THE INVENTION
The dispenser of the present invention includes a race having a plurality of intersecting tracks which, for example, can be in the shape of an "S" sawtooth, square, parallelogram, hexagon, and the like. The intersection of the tracks form a stop for the plunger as it is moved along the race, each of the intersections being in alignment with a tablet or pill retained within the dispenser. At each intersection, the plunger can be depressed to release a tablet or pill.
For purposes of description, the invention is described with reference to a dispenser including a double "S" shaped race.
Referring to FIG. 1 an embodiment of the dispenser pack (10) of the present invention is illustrated. The dispenser pack (10) comprises a container (11) including a cover (12) and a base portion (13). Disposed within the base portion (13) is a disposable blister package (14) including a plurality of spaced apart blisters (15) for receiving and containing the medication (16). The cover (12) includes a double "S" shaped race (17) including corners (18). The base portion (13) includes a plurality of spaced apart openings (21) which are coextensive with the blisters (15) in the blister package (14) and the corners (18) in the double "S" shaped race (17) disposed within the cover (12). As illustrated, a hinge (22) joins the cover (12) and the base portion (13) but if desired the cover (12) and base portion (13) can be separate and adapted to fit together.
In the embodiment shown, the cover (12) includes a latch (24) which fits into the notch (25) of the base portion (13). The opposed latch extensions (26) in the base portion (13) allow for easier opening of the latch (24) by the user, especially a user who may be physically impaired.
The double S shaped race 17 in the cover 12 includes a defined corner 18 which has a partial radius 19 on the outside of the corner and a small partial radius 20 on the inside of the corner to form a detente. The detente receives the plunger 30 and assures that it is positioned over the tablet or pill to be dispensed.
As best illustrated in FIGS. 1 and 6, a plunger (30) is positioned within the double "S" race (17) in the cover (12) and is moveable therein. In the embodiment illustrated, the plunger (30) is biased by means of a spring (33) mounted on the shaft (31) of the plunger (30). An oversize knob 34 is illustrated in the embodiment shown. Oversizing of the knob 34 assures easy contact with a broad surface for maximum impact area by a user, and in particular, assures greater potential for impact results by an arthritic patient. In the embodiment illustrated, the base portion (13) includes a ridge (35) around the periphery thereof to form a space (37) underneath the dispenser pack (10) to receive the tablet (16) when it is released from the blister (15) in the blister package (14).
In use, when it is desired to release a tablet (16) from the dispenser pack (10), the plunger (30) is positioned at a corner (18) in the double "S" shaped race (17) in the cover (12). As the plunger (30) is depressed, the button portion (32) of the plunger (30) contacts the blister (15) in the blister package whereby the blister (15) is ruptured and the tablet (16) drops through the opening (21) in the base portion (13), dropping into the space (37) underneath the container (11) where it can be retrieved.
Although this invention has been described with respect to specific embodiments, the details of these embodiments are not to be construed as limitations. Various equivalents, changes and modifications may be made without departing from the spirit and scope of this invention, and it is understood that such equivalent embodiments are part of this invention. | A reusable dispensing package is provided for dispensing medication in the form of tablets, pills, capsules or the like, in a predetermined sequence, the package includes a hinged container into which is placed a disposable blister pack containing the medicament, the container having a spring-loaded button or a plunger attached thereto which is moved around the cover of the dispenser and when depressed releases a tablet or pill from the blister. | 8 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation application of U.S. patent application Ser. No. 09/544,484, now U.S. Pat. No. 6,327,406 filed Apr. 7, 2000, which is a divisional application of U.S. patent application Ser. No. 09/276,015, now U.S. Pat. No. 6,146,713 filed Mar. 25, 1999, which are incorporated herein by reference.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT Not Applicable
BACKGROUND OF THE INVENTION
The present invention is directed generally to communication networks and systems. More particularly, the invention relates to optical WDM systems and optical components employing Bragg gratings, and methods of making Bragg gratings for use therein.
Optical communication systems transmit information by generating and sending optical signals corresponding to the information through optical transmission fiber. Information transported by the optical systems can include audio, video, data, or any other information format. The optical systems can be used in telephone, cable television, LAN, WAN, and MAN systems, as well as other communication systems.
Information can be optically transmitted using a broad range of frequencies/wavelengths, each of which is suitable for high speed data transmission and is generally unaffected by conditions external to the fiber, such as electrical interference. Also, information can be carried using multiple optical wavelengths that are combined using wavelength division multiplexing (“WDM”) techniques into one optical signal and transmitted through the optical systems. As such, optical fiber transmission systems can provide significantly higher transmission capacities at substantially lower costs than electrical transmission systems.
One difficulty that exists with WDM systems is that the various signal wavelengths often have to be separated for routing/switching during transmission and/or reception at the signal destination. In early WDM systems, the wavelength spacing was limited, in part, by the ability to effectively separate wavelengths from the WDM signal at the receiver. Most optical filters in early WDM systems employed a wide pass band filter, which effectively set the minimum spacing of the wavelengths in the WDM system.
Diffraction gratings were proposed for use in many transmission devices; however, the use of separate optical components in free space configurations were cumbersome and posed serious problems in application. Likewise, etched optical fiber gratings, while an improvement over diffraction gratings, proved difficult to effectively implement in operating systems.
The development of holographically induced fiber Bragg gratings has facilitated the cost effective use of grating technology in operating optical transmission systems. In-fiber Bragg gratings have provided an inexpensive and reliable means to separate closely spaced wavelengths. The use of in-fiber Bragg grating has further improved the viability of WDM systems by enabling direct detection of the individually separated wavelengths. For example, see U.S. Pat. No. 5,077,816 issued to Glomb et al.
Holograpically written optical fiber Bragg gratings are well known in the art. See, for instance, U.S. Pat. Nos. 4,725,110 and 4,807,950, which are incorporated herein by reference. Holographic gratings are generally produced exposing an optical waveguide, such a silica-based optical fiber or planar waveguide, to an interference pattern produced by intersecting radiation beams, typically in the ultraviolet frequency range. The intersecting beams can be produced interferometrically using one or more radiation sources or using a phase mask. For examples, see the above references, as well as U.S. Pat. Nos. 5,327,515, 5,351,321, 5,367,588 and 5,745,617, and PCT Publication No. WO 96/36895 and WO 97/21120, which are incorporated herein by reference.
Bragg gratings provide a versatile means of separating wavelengths, because the wavelength range, or bandwidth, over which the grating is reflective as well as the reflectivity, can be controlled. Initially, however, only relatively narrow bandwidth, low reflectivity Bragg gratings could be produced using holographic methods.
It was soon found that the sensitivity of the waveguide to ultraviolet radiation and the resulting bandwidth and reflectivity could be greatly enhanced by exposing the waveguide to hydrogen and its isotopes before writing the grating. Hydrogenation of the fiber was originally performed as a high temperature annealing process. For example, see, F. Ouellette et al., Applied Physics Letters, Vol. 58(17), p. 1813, (4 hours at 400° C. in 12 atm. of H 2 ) or G. Meltz et al., SPIE International Workshop on Photoinduced Self-Organization in Optical Fiber, May 10-11, 1991, Quebec City, Canada, paper 1516-18 (75 hours at 610° C. in 1 atm. H 2 ). It was later found that the hydrogenation could be performed at lower temperatures ≦250° C. with H 2 pressures ≧1 atm., if a sufficient length of time is permitted for hydrogen to get into the fiber. See U.S. Pat. No. 5,235,659 and its progeny.
While low temperature hydrogenation takes longer to perform, presumably due, at least in part, to slower hydrogen diffusion rates, it provides benefits that typically offset the time penalty. For example, the low temperature hydrogenation generally does not damage polymer coatings that are typically used to protect the optical fiber cladding and core. Also, there are fewer safety issues with handling hydrogen at lower temperatures and pressures.
Although low temperature hydrogenation is effective for introducing hydrogen into the fiber, the gratings written into the fiber must still be annealed at higher temperatures to stabilize the reflectivity of the grating. See U.S. Pat. Nos. 5,235,659 and 5,620,496. One technique that may increase grating stability written in low temperature hydrogenated fiber is described in OFC'99 PostDeadline Paper PD20 (1999) (“PD20”). In PD20, low temperature hydrogenated fiber was exposed to a uniform UV beam prior to writing grating to vary the fiber structure. In addition, the fiber was low temperature annealed at 125° C. for 24 hours before writing the grating to drive off at least some of the hydrogen from the fiber. The high reflectivity gratings that were written in the low temperature annealed fiber did not vary significantly, when exposed to a subsequent low temperature anneal at 125° C.
A shortcoming of writing Bragg gratings in hydrogen loaded fiber is that the fiber is more difficult to splice. Therefore, splicing efficiencies are decreased and increased processes must be put into place to ensure proper handling of the fiber. High temperature annealing of the fiber to remove hydrogen is limited to only portions of the fiber in which the coating has been removed to write the grating. In techniques that do not require the coating to be removed, annealing of the grating is also limited to temperatures that do not damage the coatings.
The prominent role assumed by holographically induced Bragg gratings in fiber and other waveguide optical components and systems requires that improved techniques for the production of Bragg gratings be continually developed. Likewise, the improvements in Bragg grating technology will further provide for the continued development of increasingly flexible, higher capacity, and lower cost optical systems.
BRIEF SUMMARY OF THE INVENTION
The apparatuses and methods of the present invention address the above need for improved Bragg grating production techniques and optical components and systems that include the Bragg gratings. Optical components and transmission system of the present invention includes at least one Bragg grating prepared in accordance with the present invention. In various embodiments, Bragg grating of the present invention are provided to stabilize optical signal and/or pump sources, perform selective filtering in transmission and/or receiving, and other grating based applications as may be known in the art.
Methods of the present invention include selectively hydrogenating one or more selected sections of an optical waveguide in general, and particularly optical fiber. Selective hydrogenation can be performed by selectively establishing local conditions in a first environment conducive to introducing greater quantities of hydrogen into selected sections than into non-selected sections, which are maintained in a second environment. The extent of selective hydrogenation and the hydrogen concentration difference between selected and non-selected section of the waveguide is a function of the temperature, pressure, and time of exposure established in the first and second environments.
In various embodiments of the present invention, the local temperature in the first environment is elevated to increase the rate of hydrogen ingress into the selected section of the waveguide. Increased ingress rates can be achieved by maintaining the local concentration of hydrogen in the first environment, while applying locally elevated temperatures. The local concentration in the first environment can be maintained at elevated temperatures by configuring a hydrogenation device to include a substantial portion of its volume within the first environment. Alternatively, a compartmentalized hydrogenation device can be used to vary the environmental conditions in the first and second environments within the device. Compartmentalized devices can provide for varying the pressure, hydrogen concentration and/or exposure time in the first and second environments.
The difference between the local concentration and temperature along the sections of fiber and the length of exposure generally determines the relative extent of hydrogenation. In various embodiments, the hydrogenation device can be configured such that the heated volume of the first environment proximate to the selected section represents greater than 90% of the total device volume. Increasing the heated volume percentage and/or the local temperature will increase the difference in hydrogenation between the selected section and the remainder of the fiber.
Selective hydrogenation can be performed over a wide temperature range. The methods are not limited to low temperatures to prevent damage to the fiber coating, because high temperature selective hydrogenation can be limited to only those sections in which the coating will be removed to write the grating.
It is desirable to perform selective hydrogenation at temperatures in excess of 250° C., because the exposure time can be decreased by several orders of magnitude compared to low temperatures. In addition, high pressures, e.g. >200 atm., can be employed to further decrease the exposure time by increasing hydrogen concentration in the device. As such, higher throughput can be achieved and hydrogenation devices do not have to remain charged with hydrogen for extended periods of time.
An additional benefit of high temperature selective hydrogenation is that many coatings are easier to remove following exposure to elevated temperatures. The removal of the coating to write the grating also facilitates high temperature annealing to increase the long term stability of the grating characteristics.
In addition, the second environment can be controlled to produce varying levels of hydrogenation in the non-selected sections of the waveguide. In fact, extremely low hydrogen concentrations can be achieved in the non-selected when high temperature selective hydrogenation is used, because of the short exposure times. Therefore, the non-selected sections of the fiber can be spliced more easily than traditional methods, which leads to further efficiency increases.
Accordingly, the present invention addresses the aforementioned needs for improved Bragg grating production methods to increase the efficiency and capacity of optical components and communication systems without commensurate increases in the cost of optical components. These advantages and others will become apparent from the following detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
Embodiments of the present invention will now be described, by way of example only, with reference to the accompanying Figures wherein like members bear like reference numerals and wherein:
FIG. 1 depict optical components and systems of the present invention; and,
FIGS. 2-3 depict exemplary hydrogenation devices of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
The-operation of optical systems 10 of the present invention will be described generally with reference to the drawings for the purpose of illustrating embodiments only and not for purposes of limiting the same. As used herein, the term “information” should be broadly construed to include any type of audio signal, video signal, data, instructions, etc. that can be transmitted as optical signals. Also, the term “hydrogen” is meant to include atomic and diatomic hydrogen, H and H 2 , respectively, as well as hydrogen isotopes, such as deuterium.
Generally, the optical system 10 includes at least one optical transmitter 12 in optical communication with at least one optical receiver 14 via an optical transmission waveguide 16 , such as optical fiber, as shown in FIG. 1 . Each transmitter 12 is configured to transmit information via one or more information carrying wavelengths λ i,k that be combined into a wavelength division multiplexed (“WDM”) optical signal. The transmitter 12 may include one or more coherent or incoherent optical sources 18 , such as semiconductor and fiber lasers, and associated electronic control circuitry and optics, i.e. lens 20 , as is known in the art.
The wavelength emitted by the optical sources 18 can be stabilized or established using Bragg gratings 22 to form an internal and/or external laser cavity. For example, distributed feedback (“DFB”) and Bragg reflector (“DBR”) lasers, and other lasers can include Bragg gratings 22 in both the laser cavity and the external cavity. Likewise, Bragg grating 22 can be used to select wavelengths from broadband sources, such as light emitting diodes. The optical source 18 can be directly modulated with information to be transmitted, or an external modulator 24 can be used to modulate the information onto an optical carrier wavelength provided by the source 18 . Alternatively, the external modulator 24 can be replaced with an optical upconverter to upconvert a modulated electrical carrier onto an optical wavelength different than the optical carrier wavelength emitted by the optical source 18 .
The receiver 14 can include Bragg gratings 22 in demultiplexers 26 and/or filters 28 to separate one or more wavelengths from a wavelength division multiplexed (“WDM”) optical signal. The receiver 14 can be configured to coherently or directly detect the selected wavelengths depending upon the system 10 .
In addition, the transmitter 12 , receivers 14 , as well as other components, can be wavelength tuned to provide additional flexibility in the system 10 . Wavelength tuning can be performed by varying the reflective wavelength of the Bragg gratings 22 using techniques such as those described in U.S. Pat. No. 5,007,705, and other techniques as is known in the art.
Similarly, the Bragg gratings 22 can be used in a multiplexers 30 for combining multiple optical signals and possibly to spectrally shape the optical signals. Bragg gratings 22 can also be employed in optical switches 32 , including optical routers and cross-connects, to switch, add, or drop signal wavelengths between optical paths. The optical switches 32 can be further configured to serve as an add and/or drop device 34 . Combiners 36 and distributors 38 , such as couplers and circulators, deployed in various combinations in the add/drop device 34 to provide for wavelength reuse, as may be appropriate and is known in the art.
The system 10 may include one or more optical amplifiers, such as rare earth, i.e., erbium, or other doped fiber, Raman pumped fiber, or semiconductor, to optical regenerate optical signals in the waveguide 16 . Bragg gratings 22 can be used to wavelength stabilize optical pump power provided by a pump laser 42 , as well as to gain flatten the amplified signal wavelengths in gain flattening filters 44 . Dispersion compensating devices or amplified spontaneous emission “ASE” filters 46 including Bragg gratings 22 can be used in the system 10 .
Bragg gratings 22 of the present invention are produced by selectively hydrogenating one or more selected sections of a waveguide 48 . The waveguide 48 can include various waveguide structures in which holographic gratings can be written, such as planar or fiber waveguides. The waveguides 48 in which the Bragg gratings 22 are holographically written can be the same or different geometry and/or composition as the transmission waveguides 16 . Specific examples with respect to selectively hydrogenating optical fiber are provided to more fully explain the invention and not to limit the same.
FIGS. 2 and 3 provide exemplary embodiments of selective hydrogenation devices 50 of the present invention. The devices 50 are generally configured to facilitate the establishment of multiple environments within the device 50 . For example, one or more hot zones 50 H and one or more cool zones 50 C can be provided within the device 50 .
One of more waveguides 48 are inserted into the device 50 with first sections of the waveguide 48 to be selectively hydrogenated are within the hot zones 50 H . Likewise, second sections that are to be hydrogenated to a lesser extent are positioned within the cool zones 50 C . A first environment can be established to facilitate hydrogenation on the waveguide within the hot zone 50 H , whereas, a second environment can be established to facilitate a different level of hydrogenation within the cool zone 50 C .
In various embodiments of the present invention, the local temperature in the first environment is elevated to increase the rate of hydrogen ingress into the selected section of the waveguide. Increased ingress rates can be achieved by maintaining the local concentration of hydrogen in the first environment, while applying locally elevated temperatures. The local concentration in the first environment can be maintained at elevated temperatures by configuring a hydrogenation device to include a substantial portion of its volume within the first environment. The change in concentration within the first environment at elevated temperature is proportional to the percentage of the total volume within the first environment. Therefore, it is generally desirable to provide as much of the total volume in the first environment as possible. For example, if the volume in the first environment is ten times greater than volume in the second environment, the local concentration in the first environment at 300° C. will decrease less than ˜10% relative to the second environment at ambient temperatures.
The amount of hydrogen available to hydrogenate the waveguide 48 is directly proportional to the hydrogen pressure introduced in the hydrogenation device 50 . Therefore, increasing the hydrogen pressure in the device 50 can reduce the hydrogenation time. High pressure hydrogen devices 50 and corresponding sources 52 are available to allow hydrogen pressure exceeding 3000 psi to be introduced into and maintained in the devices 50 . While high pressure hydrogen presents an increased safety concern, the time in which the device 50 must be maintained under pressure are substantially decreased.
It is noted that selective hydrogenation was performed using commercial hydrogen tanks as the source 52 , which are typically charged at 3000 psi±gage error for delivery. Selective hydrogenation can be performed at higher or lower pressures depending upon available hydrogen sources 52 and the time available to perform the selective hydrogenation.
It will be appreciated that different environment can be established within the hot and cool zones to produce different hydrogenation levels, or hydrogen concentrations, within the waveguide 48 in each zone. Also, the cool zones 50 C can be actively heated or cooled depending upon the desirable levels of hydrogenation.
It may also be desirable to bring the sections of small dimensioned waveguides 48 into thermal contact with the walls of the device 50 in the cool zones 50 C . Thermal contact will allow more precise and efficient temperature control of the waveguides 48 in the cool zone 50 C . Alternatively, the device 50 can be configured such that one environment is established within the device and only that section of the waveguide 48 to be selectively hydrogenated is within the device 50 .
The device 50 shown in FIG. 2 can be tubular in design with a cross-sectional geometry appropriate for the waveguide(s) 48 to be selectively hydrogenated. The cross-sectional shape of the device 50 also depends on the system pressure at which the hydrogenation will be performed. A circular cross-section for the device 50 is generally suitable for high pressure hydrogenation methods.
In the operation of the device 50 , the waveguide 48 is placed into the device 50 , such that sections to be selectively hydrogenated are placed within one of the hot zones 50 H . The device 50 is sealed and the air within the device 50 is evacuated and/or purged with a gas that will not substantially affect the waveguide 48 , such as nitrogen. Hydrogen can be used to purge the device 50 , although it is generally desirable to use a less expensive purge gas. The hydrogen and purge gases are introduced from a gas source 52 through a valve 54 into the device and a second valve is provided to remove the gases. Conditions in the first and second environments are established for a requisite period of time to perform the selective hydrogenation. Following the selective hydrogenation the device is cooled, the system pressure and temperature are lowered to ambient, if necessary, and the waveguides 48 are removed from the device 50 .
It will be appreciated that the hydrogen and purge gases can be recycled as may be appropriate. Recycling becomes a greater economic concern when expensive hydrogen isotopes, such as deuterium are used.
The embodiment shown in FIG. 2 can result in a substantial linear distance between the hot zones and the cool zones. Given the small volumes associated with the cool zone, additional temperature control over the cool zone may not be required, if ambient cool zone temperatures are acceptable. In fact, it may be possible to place additional lengths of fiber on a spool 56 to facilitate fiber loading into the device 50 without multiple exposures substantially affecting the additional fiber on the spool 56 .
A thermal and/or pressure barrier 58 can be used to segregate the hot and cool zones and/or high and low pressure zones in the device 50 , such as shown in FIG. 3 . Fiber sections that are to be selectively hydrogenated are passed through the barrier 58 into the hot zone 50 H , while the rest of the fiber 48 remains in the cool zone 50 C .
The thermal barriers 48 can be fabricated using any appropriate insulating materials, such as alumina, zirconia and other suitable materials. When the barrier 48 is configured as a pressure boundary, selective hydrogenation can be performed by varying the pressure, hydrogen concentration, and exposure time, in addition to or in lieu of the temperature.
In the hot zone 50 H , a heat exchanger 60 can be provided to introduce heat Q into the device 50 . The temperature in the hot zone 50 H can be monitored using thermocouples and the heat exchanger 60 controlled to maintain a desired temperature as is known in the art. It may also be desirable to provide additional heat exchangers 60 to maintain a desired temperature in the cool zones 50 C of the device 50 , as well as any zone interface regions.
The precise conditions at which the selective hydrogenation is performed depend upon the desired characteristics in the Bragg grating to be written into the waveguide 48 , the production requirements, and the capabilities of the skilled artisan. A number of examples are provided to provide an appreciation of the value of the significant parameters.
Bragg gratings can be written using the various techniques set forth in the above references. The precise technique used to write the gratings 22 may depend upon the characteristics of the grating 22 . The gratings 22 can be written using a stationary apparatus and laser with a beam size sufficiently large to write the entire grating at one time. Alternatively, scanning apparatuses can be employed to control the length, reflectivity, reflective wavelengths, and/or other characteristics of the gratings. For example, the grating characteristics can be controlled by providing relative movement, either at a constant or varying rate, unidirectional or dithering, between the waveguide 48 and the interference pattern.
The Bragg grating 22 can be annealed to groom and stabilize the grating characteristics, such as bandwidth and reflectivity, and center reflective wavelength. Generally, the gratings 22 are annealed at a sufficiently high temperature, i.e., 300° C., to ensure stable grating characteristics. Annealing will generally reduce the bandwidth and reflectivity of the grating and vary the reflective wavelength. Therefore, it may be desirable to write the Bragg gratings such that the desired grating characteristics will be achieved upon annealing.
An embodiment of the device 50 was constructed using 316 stainless steel tubing and Swagelok™ fittings, as generally shown in FIG. 2, but without the fiber source/spool 56 . Selectively hydrogenation of various fiber types, including Ge and Ge/B doped fibers, was performed with the cool zone 50 C exposed to ambient temperatures without additional control and the conditions shown in the table below. Bragg gratings 22 were written into the fiber using a scanning UV beam having a wavelength of 244 nm and phase mask using conventional techniques as previously described.
Bragg gratings written in the unhydrogenated fiber and fiber exposed to the ambient second environment had a 0.28 nm bandwidth at −1 dB from the center wavelength. Whereas, Bragg gratings written in the fiber that was selectively hydrogenated at 300° C. and ˜3000 psi had increased reflective bandwidths for all first (heated) to second (unheated) environment volume ratios tested. For example, Bragg gratings written in fibers that were selectively hydrogenated at 300° C. and ˜3000 psi in devices having heated to unheated volume ratios of 1:20 and 2:1. The gratings written in the selectively hydrogenated fiber had reflective bandwidths of 1.1 nm and 2.2 nm, respectively at −1 dB. Similar results were achieved for selectively hydrogenation was performed for 15 and 30 minutes.
Depending upon the temperature and time conditions selected to perform the hydrogenation, it may be necessary to mark the section that is to be hydrogenated. This is not necessary in the prior art, because the entire fiber was hydrogenated to essentially the same concentration. An additional benefit of selectively hydrogenating is that at temperatures that affect the coating on the fiber, such as by turning it brown, the selectively hydrogenated section can be easily identified by temperature induced coating variations.
As indicated by the above results, selective hydrogenation can shorten the hydrogenation time by an order of magnitude or more compared with prior art processes. The increased throughput that can be achieved using the present invention can result in substantial savings in terms of facility and staffing requirements. Those of ordinary skill in the art will appreciate that numerous modifications and variations that can be made to specific aspects of the present invention without departing from the scope of the present invention. It is intended that the foregoing specification and the following claims cover such modifications and variations.
As indicated by the above results, selective hydrogenation can shorten the hydrogenation time by an order of magnitude or more compared with prior art processes. The increased throughput that can be achieved using the present invention can result in substantial savings in terms of facility and staffing requirements. Those of ordinary skill in the art will appreciate that numerous modifications and variations that can be made to specific aspects of the present invention without departing from the scope of the present invention. It is intended that the foregoing specification and the following claims cover such modifications and variations. | Apparatuses, systems, and methods are disclosed for providing optical communications. Bragg grating used in the optical components and systems of the present invention are produced by selectively hydrogenating one or more selected sections of an optical waveguide in general, and particularly optical fiber. Selective hydrogenation can be performed by selectively establishing local conditions in a first environment conducive to introducing greater quantities of hydrogen into selected sections than into non-selected sections, which are maintained in a second environment. The extent of selective hydrogenation and the hydrogen concentration difference between selected and non-selected section of the waveguide is a function of the temperature, pressure, and time of exposure established in the first and second environments. | 6 |
RELATED APPLICATION DATA
[0001] This application claims priority to U.S. Provisional Application Ser. No. 60/774,435, filed Feb. 17, 2006, and U.S. Provisional Application Ser. No. 60/855,025, filed Oct. 27, 2006.
FIELD OF THE INVENTION
[0002] This invention relates generally to methods for reducing undesired components, such as contaminants, from foodstuffs such as alcoholic beverages.
RELATED ART
[0003] Foodstuffs such as beverages often contain various components which are undesireable. These components may be naturally occurring, may be additives, or may be contaminants. For example, sulfites are added to various foodstuffs including beverages for various reasons, including for stabilizing food colors and acting as preservatives to prevent spoilage due to bacteria and fungi. Sulfites are commonly found in alcoholic beverages such as wines. Wines may include up to about 3 ppm (parts per million) sulfur dioxide produced during yeast metabolism. In addition, during wine production, up to about 30 ppm of sulfites may intentionally be added. Similarly, beer and other alcoholic beverages may contain significant quantities of sulfites and other sulfur derivatives originating from metabolites and due to deliberate addition during production.
[0004] Unfortunately, some individuals are highly sensitive to certain foodstuff components such as sulfites. Such individuals may have allergic reactions upon ingesting sulfite containing foods or beverages, ranging from discomfort such as headaches to death in very severe cases.
[0005] U.S. government regulations have stringent standards regarding the level of sulfites in consumables. However, there is still a considerable industrial need to continue the use of sulfites as color stabilizers and preservatives. For individuals who are sensitive to sulfites, improved methods for reducing sulfites in alcoholic beverages are highly desirable.
[0006] The safety of such individuals would be enhanced together with their enjoyment of products that are generally available to the public.
SUMMARY OF THE INVENTION
[0007] The invention comprises methods and apparatus for removing or reducing certain components of foodstuffs.
[0008] In accordance with one embodiment of the invention, a sulfite removing/reducing additive or material is associated with a sulfite containing foodstuff, such as an alcoholic beverage. The additive may be located in a container containing the beverage, such as by dropping or releasing a caplet, capsule or other form of the material into the container. Alternatively, the material may be associated with a spout, cap, container lid or the like and the beverage may be placed into contact with the material.
[0009] The invention also comprises various sulfite removing/reducing materials or additives. According to one embodiment of the invention, an ion exchange resin is configured with a strongly basic counter-ion such as a quaternary anion. The strongly basic anion is exchanged with a hydroxyl group to create an ion exchange resin providing hydroxyl functionality. When the ion exchange resin having hydroxyl functionality contacts a sulfite containing foodstuff, such as a beverage, the sulfites are entrained in the ion exchange resin, and the sulfite level of the foodstuff is substantially reduced.
[0010] According to another embodiment of the invention, an ion exchange resin is configured with a strongly basic counter-ion and the basic counter-ion is exchanged with a weak acid anion such as bicarbonate, carbonate, acetate, phosphoric, carboxylates and the like. The ion exchange resin having the weak acid anion functionality may be contacted with a sulfite containing foodstuff, such as beverage. The sulfites may be entrained in the ion exchange resin, and the sulfite level of the beverage may be substantially reduced.
[0011] The methods and devices of the invention may be utilized to remove or reduce other components, such as contaminants, from foodstuffs such as beverages.
[0012] The foregoing and other articles, features, and advantages of the invention will be apparent from the following more detailed description of the preferred embodiments of the invention. The various features may be utilized or claimed alone or in any combination.
DETAILED DESCRIPTION
[0013] In the following description, numerous specific details are set forth in order to provide a more thorough description of the present invention. It will be apparent, however, to one skilled in the art, that the present invention may be practiced without these specific details. In other instances, well-known features have not been described in detail so as not to obscure the invention.
[0014] One or more embodiments of the invention comprise methods and apparatus/devices for removing or reducing one or more components of foodstuffs. These components may be contaminants, additives, or naturally occurring substances or elements. The invention has particular applicability to the removal or reduction of sulfites in foodstuffs such as alcoholic beverages.
[0015] In the context of this disclosure, the term “sulfites” as used herein includes the salts of sulfurous acids (M 2 S 2 O 3 ), acid-sulfites or bisulfites (MHSO 3 ), sulfur dioxide (SO 2 ), metabisulfites (M 2 S 2 O 5 ), hydrosulfites (M 2 S 2 O 4 ), combinations thereof and the like, wherein M represents a cationic counter-ion comprising one or metals or non-metals such as ammonium and derivatives thereof.
[0016] The methods and apparatus described herein may reduce the level of sulfites in currently available foodstuff products to substantially lower levels acceptable to individuals who are sensitive to ingestion of sulfites. Of course, the amount of sulfites may be lowered to any pre-determined level, but economic considerations in combination with the needs of allergy-susceptible individuals may favor less stringent methods.
[0017] The term “alcoholic beverage” includes any ethanol containing liquid such as wine, beer, whiskey and the like. Though the description provided herein is primarily with reference to alcoholic beverages, the methods and apparatus described herein may also be utilized in conjunction with a variety of foodstuffs other than alcoholic beverages, such as non-alcoholic beverages or other items to be ingested.
[0018] In one embodiment of the invention, a sulfite removing or reducing additive or material is placed into contact with a sulfite containing foodstuff, such as a beverage. Various embodiments of sulfite removing or reducing additives or materials are described in more detail below. These additives may be solid or semi-solid.
[0019] In one embodiment, one or more sulfite removing or reducing additives are associated with an alcoholic beverage, whereby the additive entrains at least a portion of sulfites contained in the beverage. In one embodiment, the additive may be formed into a caplet or located in a capsule (or other container) so as to provide a specific size or dose of additive. The additive may be added directly to the desired beverage, such as by dropping the additive into a container containing the beverage (such as a wine bottle) or into a glass, which contains (or is to contain) the beverage.
[0020] In one embodiment, the additives might be associated with the packaging of the beverage. For example, one or more caplets or capsules may be placed into a package, which is attached to the container containing the beverage. The “dose” of the additive may be predetermined for the specific volume of the beverage in the container and/or the sulfite content of the beverage. Upon preparing to consume the beverage, a consumer may utilize the associated additive by opening the container and then placing the additive into contact with the beverage before its consumption.
[0021] The additive might also be formed into or associated with an item, which is placed into contact with the beverage, such as an ornamental object. The object might be a stir-stick.
[0022] The additive might otherwise be placed into contact with the beverage. For example, a portion of a container (such as a lid or cork or a bottom portion of the container) may comprise one or more sulfite removing or reducing additives. Of course, the additives may be located in any portion of the container. The additives may be located in a portion of the lid separated by a permeable membrane or may comprise a portion of the lid. In use, an individual might invert the container to assure contact between the container's fluid contents and the additive prior to consuming the fluid contents. In other embodiments, when a cork or lid of the container is removed, the additive may be released into the container into contact with the beverage.
[0023] In yet another embodiment, a beverage may be placed into contact with the additive along a flow path of the beverage. For example, a beverage in a first container may be discharged into one or more intermediary containers configured to reduce sulfite levels and then returned to the first container or another container prior to consumption of the beverage.
[0024] In an exemplary embodiment, at least a portion of the additives may comprise one or more ion exchange resins. By way of example, weakly basic anion exchange resins may include DOWEX™ 66 or DOWEX™ 77 manufactured by The Dow Chemical Company, U.S.A. DOWEX™ 66 and DOWEX™ 77 comprise a styrene DVB (divinyl benzene polymer) macro porous matrix including tertiary amine group functionality. The styrene DVB matrix comprises styrene cross-linked with divinyl benzene. It will be appreciated that the matrix may be any suitable polymer configured with a counter-ion. Weak anion exchange resins may be effective in reducing predominantly acidic sulfites, but not sulfites in their salt form. When the salt form of sulfites are present, a fluid may initially be de-cationized (that is the metal or non-metal counter-ion may be replaced with an acid group) with a strong acid cation exchange resin such as DOWEX™ 88 followed by treatment with a weakly basic anion exchange resin as discussed above. DOWEX™ 88 comprises a styrene DVB (divinyl benzene polymer) macro porous matrix including sulfonic acid group functionality. Of course any weakly basic and strongly acidic ion exchange resins may be suitably utilized.
[0025] In another exemplary embodiment, a strongly basic anion exchange resin such as DOWEX™ 22 may be utilized to reduce sulfites in a beverage. DOWEX™ 22 comprises a styrene DVB (divinyl benzene polymer) macro porous matrix including quaternary amine group functionality. In an embodiment of a DOWEX™ 22 ion exchange resin, the quaternary amine group functionality may be initially exchanged with hydroxyl group. The quaternary amine group may comprise trimethyl ammonium, poly (acrylamido-N-propyltrimethylammonium chloride) or any other suitable quaternary amine. The hydroxyl group of the ion exchange resin may be exchanged for sulfite anions thereby permitting entrainment sulfites in the ion exchange resin when the ion exchange resin contacts the sulfite containing fluid (alcoholic or non-alcoholic beverage). In operation, sulfite anion levels may be substantially reduced in the beverage.
[0026] In another embodiment of a DOWEX™ 22 ion exchange resin, the quaternary amine group functionality may be initially exchanged with bicarbonate anion (HCO 3 − ). The bicarbonate group of the ion exchange resin may be exchanged for sulfite anions thereby permitting entrainment sulfites in the ion exchange resin when the ion exchange resin contacts the sulfite containing fluid. Excess bicarbonate remaining in the fluid may degas as carbon dioxide (CO 2 ), and the fluid may subsequently achieve a slightly acidic pH as is well understood. Since the level of sulfites in most consumable beverages is very low (less than about 30-70 parts per million), an increased acidity of the fluid would be imperceptible in use.
[0027] In yet another embodiment, the quaternary amine group functionality of DOWEX™ 22 ion exchange resin may be initially exchanged with carbonate anion (CO 3 2− ). When carbonate group of the ion exchange resin exchanges for sulfite anions thereby entraining sulfites in the ion exchange resin on contact with sulfite containing fluids, any insoluble carbonates may precipitate out, while soluble carbonates will remain in solution. Again, since the level of sulfites in most consumable beverages is very low any precipitates would be imperceptible.
[0028] It will be appreciated that any weak acid anion such as bicarbonate, carbonate, acetate, phosphoric, carboxylate and combinations thereof, and the like may exchange out quaternary bases of DOWEX™ 22 ion exchange resins (or any other ion exchange resin having a quaternary base functionality). Furthermore, ion exchange resins may be suitably sized to provide greater contact area and more efficient ion exchange capability.
[0029] The method and apparatus of the invention may be utilize to remove or reduce other components from a foodstuff. For example, a similar method and apparatus might be utilized to remove or reduce tannins (polyphenols), histamines or other components/contaminants from wine. Of course, the additive which is utilized in such a method or apparatus might vary, depending upon the particular components to be reduced/removed.
[0030] While the invention has been particularly shown and described with reference to preferred embodiments thereof, it will be understood by those skilled in the art that the foregoing and other changes in form and details may be made therein without departing from the spirit and scope of the invention. | A method of removing or reducing a component of a foodstuff is disclosed. One method utilizes an ion exchange resin configured with a strongly basic counter-ion such as a quaternary amine. The strongly basic anion may be exchanged with a second anionic group such as hydroxyl, or a weak acid anion such as bicarbonate, carbonate, acetate, phosphoric and carboxylate to create an ion exchange resin comprising substantially a second group functionality. Sulfite containing beverages such as wines, beers, whiskeys or non-alcoholic beverages may be contacted with the ion exchange resin having the second group functionality to entrain a substantial quantity of the sulfites in the ion exchange resin and reduce the sulfite level of the beverage. | 2 |
FIELD OF THE INVENTION
The present invention relates to the field of packaging, and particularly to packages designed to be hooked onto displays. More particularly, the display is a cardboard packaging having a hooking lug provided with a hooking opening and a box having two openings aligned with the hooking opening.
BACKGROUND OF THE INVENTION
Cardboard boxes with hooking lugs are well known in the art of packaging. They are generally produced by gluing a box to a sheet of cardboard serving as a hooking lug. Packages have also been proposed which are formed from a single cardboard blank, such as the one depicted in FIGS. 8 and 9, for example, in which the hooking lug is formed by bonding two end panels to each other. This type of packaging, though easy to produce, has the drawback of having its largest dimension disposed horizontally when it is hooked onto a display. When such boxes are disposed on a display, they can easily be shifted when the display is knocked and, owing to their low height in relation to their width, they resume their original position only with difficulty.
Cardboard boxes have also been proposed with hooking lugs; the openings of said boxes being aligned with the respective hooking lug. This embodiment, similar to the box described in U.S. Pat. No. 4,106,615 and depicted in FIGS. 10 and 11, consists of a traditional box, one of whose flaps has been converted to form a hooking lug and whose opposite flap has been enlarged and convened to become a tucked-in lug. This type of packaging requires special equipment for its closure.
Another type of boxes, such as disclosed in DE 4,322,555 has been proposed. Said document describes boxes similar to those depicted in FIG. 1 and 2. However, for boxes of relatively small sizes, a carded box of such a type could be easily hidden. Consequently, there is a need for packages of relatively larger sizes than the box in order to prevent shoplifting. A solution to such a packaging has been contemplated in DE-U-9211017 wherein a conventional box is attached to a larger hooking flap through an intermediate flap in order to locate said box in a central opening of said hooking flap. The problem with the boxes proposed in said document resides in the fact that they are difficult to be industrially manufactured since the box has to be fill n before passing through the aperture of the carded flap.
SUMMARY OF THE INVENTION
One object of the present invention aims to produce a packaging with a hooking lug from a single blank having been printed on a single side and whose opening are provided with four flaps and are aligned with the hooking lug; the container being smaller than the packaging.
Another object of the invention aims to produce a packaging whose openings have a traditional form with four flaps, so as to be able to use conventional equipment. In packaging of this type, the two lateral flaps are used to square the box, one of the other flaps acts as a flat support to receive the glue and the other flap enables the box to be closed and displayed. The packaging needs to be able to be delivered in a practically flat form and it must be easy to use. Furthermore, automation of its filling and closing must be easy to achieve.
For ecological reasons, it is advantageous to be able to produce such a packaging from cardboard.
The objects of the invention are achieved with a blank for a cardboard box with a hooking lug in which: on the one hand the box has a width L1, a height H1 and a depth P, the height H1 of the box being the largest dimension of said box, and on the other hand the hooking lug has a height H2 and a width L2 larger than L1 and is provided with a hooking opening, the largest dimension of the box being practically aligned with the hooking opening of the hooking lug. This blank comprises:
a first panel, having a width L2 and a height H3 at least equal to the sum of the height H1 of the box and the height H2 of the hooking lug, consisting of a first part adapted to receive the box and a second part adjacent to said first part provided with a hooking opening and designed to form the hooking lug, said first panel serving to define the size of the packaging,
connected to the first part of the first panel by a side parallel to the height of the box, a first auxiliary panel of height H1 and width equal to a first size less than the difference between the width of the first panel and the width of the box,
hinged to said first auxiliary panel by the side opposite said first panel, a second panel of height H1 and width P serving as a lateral panel of the box, this second panel being provided, on the two opposing sides of dimension P, with two flaps designed to at least partially close the opening in the box,
hinged on the side of the second panel opposite the first auxiliary panel, a third panel with the width L1 and height H1 of the box, this third panel being provided, on the two opposite sides of dimension L1, with two flaps designed to at least partially close the openings of the box,
hinged on the side of the third panel opposite the second panel, a fourth panel of width P and height H1, practically identical to the second panel, this third panel being provided, on the two opposite sides of dimension P, with two flaps designed to at least partially close the openings of the box,
hinged on the side of the fourth panel opposite the third panel, a fifth panel, of height H1 and width L1, substantially identical to the third panel, serving as gluing lug to connect the side of the fourth panel opposite the third panel to the first part of the first panel at said first predetermined distance from the edge of said first panel connected to said auxiliary panel so as to form a practically parallelepiped box having, at each opening, flaps designed to totally close the box,
hinged on the second part of the first panel defining the hooking lug, a flap with a size equal to said second part and designed to be folded over and glued to said second part so as to form the hooking lug, this flap comprising an opening corresponding to the opening arranged in the second part,
hinged on the first part of the first panel, opposite the first auxiliary panel, a second auxiliary panel of height H1 and width equal to a second size so that the sum of said first size and said second size is equal to the difference between the width of the first panel and the width of the box, said auxiliary panel being designed to be folded over and glued to said first part,
hinged along the width of the first part of the first panel opposite the second part, a flap having a width equal to that of the first panel and a height equal tot he difference between the height H3 and the sum of the height H1 of the box and the height H2 of the hooking lug.
BRIEF DESCRIPTION OF THE DRAWINGS
Other advantages of the invention will emerge from a reading of the description that follows, given with reference to the accompanying drawing in which:
FIGS. 1 and 2 depict a blank known in the prior art and the packaging obtained by means of this blank;
FIG. 3 depicts a second embodiment according to the invention;
FIG. 4 is a perspective view of a packaging obtained by means of the blank depicted in FIG. 3;
FIGS. 5 to 7 depict diagrammatically the various key steps in transforming the blank depicted in FIG. 3 so as to obtain the packaging depicted in FIG. 4;
FIGS. 8 and 9 depict respectively a blank known in the prior art and the packaging obtained by means of this blank;
FIGS. 10 and 11 depict respectively another embodiment of a blank known in the prior art and the packaging obtained by means of this blank.
DESCRIPTION OF THE PREFERRED EMBODIMENT
As can be seen in FIG. 4, the invention sets out to provide a box 50 provided with a hooking lug 11 and whose openings 52a, 52b are aligned with the hooking lug 12. According to the invention, the rear panel has dimensions greater than the dimensions of the box.
As can be seen in FIG. 3, the box is formed from a single cardboard blank 10. The blank has a series of panels hinged on each other. A first panel 12, serving as a rear panel, has a first part 12a whose height H1 is at least equal to the height of the box and whose width L2 is larger than the width L1 of the box an a second part 12b whose height H2 corresponds to the height of the hooking lug 11. The hooking lug is provided with a hooking opening 13 whose shape is usually that of an isosceles triangle and whose apex is directed towards the adjacent side. This opening serves to hook the box onto a display.
A lateral auxiliary panel 24c is hinged on the first part 12a of the rear panel 12 in line with the final position of the box on the first panel 12. Said flap has a height equal to the height H1 of the box and has a width of a first size depending on the final position of the box on the first panel 12. Said first dimension is less than the difference between the width L2 of the first panel and the size L1 of the box.
The blank has a second panel 14 which serves as a lateral panel of the box and which is hinged on the first part of the first panel 12. Said second panel 14 has a length H1 which corresponds to the height of the box. The width P of this second panel 14 is equal to the depth of the box. This panel 14 is provided, on its two facing sides, with two flaps 14a and 14b designed to cover at least partially the respective opposite openings of the box.
Hinged on the side of the second panel 14 opposite the first panel 12 there is a third panel 16 which serves as a front panel for the box. The third panel has a length H1 equal to the height of the box and a width L1 equal to the width of this box. The third panel is provided, on its two facing sides, with two flaps 16a and 16b designed to cover the respective opposite openings of the box. In the embodiment depicted, the flaps 16a and 16b cover practically the whole of the corresponding opening 52a, 52b.
A fourth panel 18 is hinged on the side of the third panel opposite the second panel. This fourth panel is identical to the second panel. This panel 18 is provided, on its two facing sides, with two flaps 18a and 18b designed to at least partially cover the respective opposite openings of the box.
A fifth panel 20 is connected to the side of the fourth panel opposite the third panel 16. This fifth panel has a length equal to the height H1 of the box and a width L1 equal to the width of this box. The fifth panel is provided, on its two facing sides, with two flaps 20a and 20b designed to cover the respective opposite openings of the box. In the embodiment depicted, the flaps 20a and 20b cover practically the whole of the corresponding opening 52a, 52b.
The rear panel 12 is provided with additional flaps which enable the whole packaging to have the same texture and colouring as the box. A flap 24a is hinged on the first part 12a of the rear panel 12. This flap 24a has a length equal to the width L2 of the first panel and its width is equal to the dimension separating the bottom of the box from the bottom of the first panel. A lateral flap 24b disposed in line with the final position of the box is hinged on the first part of the rear panel 12 opposite the auxiliary panel 24c. This flap 24b has a length equal to the height H1 of the box and a width of a second size equal to the distance separating the box from the lateral edge of the packaging 10. The sum of said second size and said first size is equal to the difference between the width L2 of the rear panel and the width L1 of the box. The blank also has a flap 22 hinged on the second part 12b of the rear panel 12 and of the same size as this hinged on the second part 12b of the rear panel 12 and of the same size as this second part so as to be able to cover it and be glued thereto. The flap 22 and the second part cooperate so as to define the hooking lug 11. The flap 22 has a hooking opening whose shape and position correspond to the hooking opening 13. Advantageously, the flap 22 is hinged along the outer edge of width L2 of the second part 12b of the first panel 12. It is evident that the flap 22 can be connected to the second part of the rear panel 12 by a side other than that depicted in FIGS. 1 or 3, for example as depicted in FIG. 10, It is evident that flap 24a could be provided with a size equal to the width H1 of the box with flaps 24b and 24c having a longer length which extends up to the end of rear panel 12.
Reference will now be make to FIGS. 5 to 7, in order to comprehend the production of the box for the purpose of its delivery flat for subsequent use. As can be seen in FIG. 5, the flaps 22 and 24a are glued and then folded over onto the first rear panel 12. In a second operation, depicted in FIG. 6, the blank, folded and glued, is used again to produce the other folds. The area of the rear panel 12 not covered by the flaps 22 and 24a is coated with glue and the flap 24b is folded onto the rear panel 12. At the same time, the panels 18 and 20 are folded along the scoring existing between the panel 18 and the panel 16. Then, as indicated in FIG. 7, all the panels 14, 16, 18, and 20 superimposed by the previous folding are folded along the scoring existing between the rear panel 12 and the panel 24c so as to glue the panels 24c and 20 to the rear panel 12. The packaging is then distributed to the user who can, by means of conventional machines, unfold the packaging to obtain a box, close one of the openings with four flaps, insert the product to be sold into a box and close the other opening with four flaps.
It is evident that the box can be centered with respect to the rear panel as described with reference to FIGS. 1 to 4. However, the widths of the flaps 24a, 24b, and 24c enable the box to be situated at the desired location for the first part 12a of the rear panel 12. | The invention relates to packaging. The invention is able to be used to produce cardboard boxes (50) having, on the one hand, two openings (52a, 52b) each provided with four flaps designed to close off the corresponding openings and, on the other hand, a hooking lug (22) provided with a hooking opening (13) substantially aligned with the two openings. The size of the package being defined by the size of the rear panel. The blank used to obtain the package could be printed on one side only. | 1 |
This application claims priority to provisional patent application Serial No. 60/371,756 filed Apr. 11, 2002 now abandoned.
BACKGROUND OF THE INVENTION
The invention relates to a process and machinery (Preheaters and Recycling Machine) for accurately heating, milling/profiling, handling and placement to grade of 100% Hot In-place Recycled (HIR) asphalt mixed with various types of rejuvenating fluids, liquid polymers and aggregates, with or without the addition of new, virgin asphalt (produced by a standard asphalt plant). The asphalt pavement is heated and softened by two or more Preheaters, physically scarified by one or more sets of carbide cutters (rakes), profiled and collected by mills, measured and mixed with rejuvenating fluid, polymer liquid (if required) and washed aggregate (if required) in a pug mill. The type, and amount of additives required to 100% HIR asphalt pavement is specified by pre-engineering using core samples taken from the asphalt pavement at regular intervals.
The 100% HIR of asphalt pavement is achieved by the addition of rejuvenator fluid, liquid polymers (if required) and washed aggregate (if required). Rejuvenator fluid must be accurately metered, as too much rejuvenator fluid will cause the recycled asphalt to bleed (rejuvenator fluid rising to the surface) softening the compacted surface. Too little fluid will not restore flexibility back into the recycled asphalt.
Liquid polymers such as Latex are added to increase the performance of the 100% recycled asphalt (Superpave specifications) by increasing flexibility while reducing rutting and cracking over a wider operating temperature range.
Adding aggregate (typically washed sand) during the 100% HIR process will modify the asphalt's physical properties and the air void ratio (percentage of air entrenched in the asphalt and generally specified at between 3-5%).
Adding rejuvenating fluid alone to the recycled asphalt will generally reduce the air-void ratio while adding washed sand tends to increase the air-void ratio. Adding aggregates that contain dust (unwashed) will generally reduce the air void ratio. Pre-engineering determines the correct specification and application rates for rejuvenating fluid, polymer liquid and aggregate. The Recycling Machine is designed with modular pin-on attachments for increased flexibility.
SUMMARY OF THE INVENTION
The present invention has a wide range of processing capabilities. For example, it can be used in, among others, the following applications:
1. 100% HIR: The old asphalt pavement is heated by a plurality of Preheaters to soften the asphalt for processing by the Recycling Machine. The final Preheater may be fitted with carbide cutters, asphalt collection blades (rake assembly) and an aggregate distribution system. The old asphalt is physically scarified by carbide cutters (rakes), profiled and collected by mills, measured and mixed with rejuvenating fluid, polymer liquid (if required) and washed aggregate (if required) in a pug mill. In one embodiment of the present invention, as described below, the asphalt from the heated surface does not need to be lifted. The type and amount of additives required to 100% HIR asphalt pavement is specified by pre-engineering using core samples taken from the asphalt pavement at regular intervals.
The 100% HIR of asphalt pavement is achieved by the addition of rejuvenator fluid, liquid polymers (if required) and washed aggregate (if required). Liquid polymers such as Latex are added to increase the performance of the 100% recycled asphalt (Superpave specifications) by increasing flexibility while reducing rutting and cracking over a wider operating temperature range.
Adding aggregate (typically washed sand) during the 100% HIR process will modify the asphalt's physical properties and the air void ratio (percentage of air entrenched in the asphalt and is generally specified at between 3-5%). The 100% recycled asphalt is placed to grade as a single course (layer) by a standard paving screed (attached to the Recycling Machine).
The Recycling Machine can be equipped with an optional front asphalt hopper/variable speed chain slat conveyor, truck pusher bar, variable speed central belt conveyor and electronic belt scale and conveyor hopper/diverter valve. A surge bin/vertical elevator, auger/divider/strike off blade, and screed assembly are also provided. The Recycling Machine's mills, pug mill, auger/divider/strike off blade and screed assembly, process and place the 100%, recycled asphalt. When equipped with the optional equipment, the Recycling Machine's on-board computer meters the new asphalt, which may be stored in a hopper, into the surge bin/vertical elevator, auger/divider/strike off blade and screed assembly for startup. The optional equipment also allows the Recycling Machine to perform the 100% HIR Remix method.
2. 100% HIR (Remix): In this application, the old asphalt pavement is heated by three or more Preheaters to soften the asphalt for processing by the Recycling Machine. The final Preheater may be fitted with carbide cutters, asphalt collection blades (rake assembly) and an aggregate distribution system. The Recycling Machine can be equipped with a front asphalt hopper/variable speed chain slat conveyor, truck pusher bar, variable speed central belt conveyor and electronic belt scale, conveyor hopper/diverter valve, surge bin/vertical elevator, auger/divider/strike off blade, and screed assembly. New asphalt is delivered from the hot mix plant by highway dump trucks and discharged into the Recycling Machine's hopper. The Recycling Machine's on-board computer meters the new asphalt (stored in the hopper) proportionally (approximately 10% to 15% by weight of the asphalt being 100% recycled) on to the central belt conveyor. A hopper/diverter valve diverts the new asphalt into the surge bin's vertical elevator. The vertical elevator is positioned in the 100% processed asphalt's windrow to continuously pickup asphalt. The processed asphalt and the metered, new asphalt are blended at the vertical elevator and delivered to the surge bin. The new asphalt may also be diverted directly on to the 100% recycled asphalt (windrow) exiting the pug mill.
3. 100% HIR (Integral Overlay): In this application, the old asphalt pavement is heated by a plurality of Preheaters to soften the asphalt for processing by the Recycling Machine. The final Preheater may be fitted with carbide cutters, asphalt collection blades (rake assembly) and an aggregate distribution system. The Recycling Machine is equipped with a front asphalt hopper/variable speed chain slat conveyor, truck pusher bar, variable speed central conveyor, shuttle conveyor, primary asphalt distribution auger/divider/strike off blade, secondary asphalt distribution auger and primary/secondary screed assemblies. New asphalt is delivered from the hot mix plant by highway dump trucks and discharged into the Recycling Machine's front hopper. The Recycling Machine's mills, pug mill, primary auger/divider/strike off blade and screed assembly, process and place the 100% recycled asphalt. The Recycling Machine's on-board computer meters the new asphalt (stored in a hopper) via the central conveyor and shuttle conveyor to the secondary asphalt auger and screed assembly and if required, to the primary auger/divider/strike off blade and primary screed assembly. The new asphalt is placed by the secondary screed assembly on top of the 100% recycled asphalt (being laid to grade by the primary screed assembly) resulting in a hot, thermal bonding between the two layers. The 100% recycled and new asphalt is not mixed together, as in the Remix method. Both the primary and the secondary screed assemblies feature a novel grade control system used to place the asphalt to grade while also controlling the depth differential (generally 0.5 to 1 inch) of the asphalt laid between the two screed assemblies.
A standard, asphalt-paving machine used in the industry is designed to lay hot, plant mix asphalt delivered from the asphalt plant by dump trucks. The paving machines are either rubber tire or track driven machines. Neither type has any hydraulic suspension to raise and lower the paving machine's mainframe. The asphalt is generally dumped into the front hopper of the paving machine where it is conveyed rewards by two, independently controlled, slat conveyors. The conveyed asphalt drops into two, independently driven, variable speed, hydraulically driven augers. The left auger receives asphalt from the left conveyor and the right auger from the right conveyor. The augers convey asphalt out from the center of the paving machine to the ends of the screed's extensions. Electronic level sensors are attached to the ends of the left and right side extension screeds to control the speed of the independently driven augers and conveyors. If the level of asphalt drops in one or both of the extension screeds, the auger(s) and conveyor(s) will increase in speed, delivering more asphalt. The level of asphalt (head of material) should be maintained across the complete width of the screed assembly. Generally the asphalt will be to the height of the auger's drive shafts (half full) with the augers slowly turning (without stopping) while conveying asphalt to the screed's extensions. Behind the two augers is the screed assembly, which is responsible for spreading (laying) the hot asphalt to a specific depth and grade. The screed assembly consists of the main screed and a left and right extension screed. The main screed is fixed in width while the extension screeds can be hydraulically extended or retracted as the paving machine is operating, thereby altering the paving width. The screed is attached to the paving machine's mainframe by screed tow arms that reach forward to behind the front hopper. The screed tow arms are attached to the paving machine's mainframe by the left and right side tow points. The tow points can be pinned into position for manual control. A skilled operator uses crank handles at either side of the screed to adjust the screed's angle of attack. The screed allows more asphalt to flow under its plate (screed rises) when its angle of attack is increased (front of the screed plate is higher than the rear) and visa versa. For automated control of the screed, the left and right crank handles are locked into position. Hydraulically raising or lowering the screed arm's tow points controls the screed's angle of attack. Raising a tow point will increase the angle of attack and visa versa. The automatic grade control sensors that control the tow points are mounted to the rigid tow arms and sense the asphalt's grade using averaging beams, joint matcher, string lines or a non-contact, sonic sensor beams. The averaging beams and the joint matcher make physical contact with the asphalt's surface and are towed by the paving machine, generally one on either side. The string line is a long string or wire that is erected using surveying equipment. The paving machine uses the string line as a fixed, reference grade. The mounting position of the sensors can be adjusted (distance from the tow point) to control the response of the system. Generally the screed's reaction to grade deviations needs to be slow to produce a smooth riding, asphalt surface. The sensors should be mounted closer to the tow point to achieve a slow, smooth reaction. Mounting the sensor closer to the screed's pivot point (away from the tow point) speeds up the reaction time and is better suited to joint matching applications. For surfaces where the right hand averaging beam cannot practically be used due to obstructions, poorly graded shoulders, curbs, etc., an electronic slope sensor, attached to the main screed can be substituted in place of the right averaging beam and sensor. The slope sensor allows the percentage of grade to be electronically adjusted while the paving machine is processing. For accurate grade and slope control Topcon's Paver System Four or Five together with their Smoothtrack® 4 Sonic Tracker II™ averaging beams are highly recommend. Attached to each of the screed's tow arms is an aluminum beam fitted with four (non-contacting) sonic sensors that electronically average the surface's grade. Topcon's electronic Slope Sensor is mounted to the screed assembly. The Sonic Trackers and the Slope Sensor work together to determine the screed's position relative to the desired grade and generate correction signals that are used by the Recycling Machine's on-board computer to hydraulically control the screed arm's tow points. To produce a quality, asphalt surface that meets all engineering specifications requires considerable operator skill, knowledge and equipment capable of properly performing the work. Consistency is one of the keys when producing a quality; asphalt surface and the following major points should be followed when laying new asphalt with a paving machine or 100% recycled asphalt with a recycling machine with attached screed(s):
a. Processing should be continuous with no stops. Stopping the screed assembly allows it to settle into the hot asphalt, causing depressions. Stopping for too long a period causes the asphalt in front of the screed assembly to cool, resulting in the screed assembly rising when forward travel is resumed.
b. The processing speed should remain as consistent as possible. An increase in speed will cause the screed assembly to rise while a decrease will cause the screed assembly to sink.
c. The temperature of the asphalt in front of the screed assembly (head) should remain consistent. If the temperature drops the screed assembly will rise and visa versa.
d. The asphalt in front of the screed assembly should remain at a consistent level, across the complete width of the main screed and the screed's extensions. An increase in asphalt level will cause to screed assembly to rise while a decrease will cause it to sink.
The cold planer (milling machine or grinder) is generally a heavy, high-powered machine fitted with a large diameter, cutting drum. Attached to the cutting drum are replaceable carbide teeth and holders. The cold planer is designed to mill to grade, asphalt and concrete surfaces. The carbide cutters are generally sprayed with water, which is used for cooling and dust control. The milling drum discharges the milled product on to a high capacity, rubber conveyor belt that delivers the material to a fleet of waiting dump trucks to be hauled away. The cutting drum's depth of cut (width is fixed) is manually or automatically controlled. Automatic grade control is generally accomplished by using the same sensors as the paving machine; however, long averaging beams are not generally used. More common, is the fixed string line, single sonic sensor on each side or Topcon's Smoothtrack® 4 Sonic Tracker II™ averaging beam on each side. The automatic grade control sensors on the cold planer automatically control the cutting drum's depth by raising or lowering the machine's mainframe to which the drum is attached. Three or four hydraulically activated legs (struts) are fitted with hydraulically driven tracks are used to propel the machine. The struts also turn to provide steering and raise and lower to provide the necessary grade control. The automatic grade control sensors that control the struts are mounted to the mainframe (generally close to the centerline of the cutting drum) and sense the asphalt's grade using left and right side sonic sensors. For surfaces where the right hand sensor cannot practically be used due to obstructions, poorly graded shoulders, curbs, etc., an electronic or hydraulic slope sensor, attached to the mainframe can be substituted in place of the right sensor. The slope sensor allows the grade (percentage) to be electronically adjusted while the planing machine is milling material.
Prior 100% HIR recycling machines have systems designed to process and lay 100% recycled asphalt to grade using a standard, asphalt-paving screed. Recycling machines fitted with an attached screed have had major problems with the varying amount of processed, recycled asphalt, which collects in front of the screed assembly, especially when milling to grade (averaging the high and low areas). Milling to grade causes the volume of recycled asphalt to vary as high and low areas of pavement are milled. High sections increase the amount of asphalt being processed, while low sections require supplemental asphalt, to make up any deficiency. The only way, until now, that the amount of asphalt in front of the screed assembly could be controlled was by manually increasing the angle of attack (raising) of the screed assembly to release excess asphalt, or reduce the angle of attack (lowering) to collect asphalt. Manual, operator adjustment of the screed assembly generally results in bumps and an inconsistent grade of the finished asphalt surface (mat). Others have tried to resolve the problem by removing the screed assembly from the recycling machine. The recycling machine (less screed) either conveys the heated, recycled asphalt into a standard paving machine positioned under the rear of the recycling machine, or leaves a windrow of hot asphalt on the milled asphalt's surface, which is picked up by a windrow conveyor attached to the paving machine. The front hopper of the paving machine stores any excess asphalt when not required by the screed assembly.
The following problems arise when the screed assembly is removed from the recycling machine:
a. Increased costs: A paving machine and windrow conveyor must be purchased and operated in addition to the recycling machine. Shipping both units requires a trailer as the units are not self transportable.
b. Reduced asphalt temperature: The temperature of the recycled asphalt contained in the windrow drops the further the windrow conveyor and paving machine are positioned from the recycling machine. Heat is also lost at the windrow conveyor and paving machine as the hot asphalt is handled. Low asphalt temperatures cause the screed assembly to tare the mat (open surface). This also causes a problem with final mat compaction during rolling. Asphalt meeting Superpave specifications generally requires higher temperatures to be maintained behind the screed assembly with the steel drum roller operating as close to the screed assembly as practicably possible.
c. Increased segregation: Hot asphalt should always be moved as a mass to prevent segregation. The windrow conveyor and paving machine increase the handling operations of the hot asphalt, causing the larger aggregate to separate (segregate) and tumble to the sides, causing marks in the finished mat. Asphalt meeting Superpave specifications generally uses a larger size aggregate than conventional asphalt. Segregation will become a greater problem with the larger aggregates.
d. Increased pollution and increased equipment train length: The windrow conveyor opens up the hot, asphalt windrow as the asphalt is conveyed upwards into the paving machine's front hopper. Excessive smoke (natural byproduct of hot asphalt) is produced (if the asphalt is at the correct temperature) causing a problem to the paving machine's operators. Asphalt meeting Superpave specifications will cause even greater problems with smoke due to the higher temperatures.
e. Safety: Safety is an issue when processing with an open windrow. It is quite common for automobiles to try and cross the heated windrow, only to become stuck in 200 to 300+ Deg F. asphalt. Animals have seriously burnt their feet, as have humans with open footwear! Recycling machines with an attached screed assembly do not suffer from the above problems, as there is no open windrow.
The following problems have, until now, prevented current 100% HIR systems and machines from producing quality, recycled asphalt that meets pre-engineered specifications:
1. Inconsistent heating of the asphalt pavement to the proper depth required for 100% HIR.
2. Inconsistent smoothness when milling with 100% HIR machines.
3. Inconsistent smoothness and surface defects, caused by asphalt handling problems when using an attached screed assembly using 100% HIR machines.
4. Inconsistent ratio of new asphalt to 100% recycled asphalt when using the Remix method.
5. Inability to process asphalt around utility structures and obstructions.
6. Inaccurate and inconsistent application of liquid additives.
7. Inaccurate and inconsistent application of additional aggregate.
8. Improper mixing of rejuvenator fluid, washed aggregate and reworked asphalt.
9. Inability to remove moisture from the reworked asphalt.
10. Inconsistent depth differential between the 100% recycled asphalt and the new asphalt when using the Integral Overlay method.
The present invention solves the above-mentioned problems.
1. Inconsistent heating of the asphalt pavement to the proper depth required for 100% HIR
A critical step in the 100% HIR of asphalt pavement is getting the heat down into the asphalt to a depth (2″ or more) that will produce an average temperature that is hot enough to properly process the asphalt, without damaging the asphalt. Experience has shown that different mixes of asphalt absorb heat at different rates. For instance, asphalt with the addition of steel mill slag absorbs heat at a much different rate than asphalt with the addition of asbestos or rubber. The amount of moisture contained in the asphalt also plays an important part in the way that heat is absorbed with high percentages reducing the heating efficiency. When asphalt is not heated to sufficient depth, the following problems will occur:
The milling equipment will fracture the aggregate (stone) in the asphalt, degrading the asphalt's physical structure.
Insufficient moisture will not be driven out of the asphalt, in the form of steam, preventing the proper coverage and bonding of liquid additives to the asphalt's aggregate.
The effective mixing of additives (aggregate and rejuvenator fluid) will be reduced due to the asphalt not flowing correctly in the mills and pug mill.
The screed assembly will tear the finished mat due to low asphalt temperatures.
If the asphalt is over heated (generally the top surface) and the heat does not penetrate to the required depth, the following problems will occur:
The surface of the asphalt will be chard (burnt), causing degradation of the asphalt's asphalt cement (AC) content and high levels of pollution, caused by fire and smoke.
The added rejuvenator fluid and polymer liquids will be degraded when they make contact with the overheated asphalt as the light fluid fractions will flash off (evaporate).
If the asphalt is inconsistently heated, to a sufficient depth, all of the above problems will occur, plus the screed assembly will sink and climb with the change in the asphalt's temperature. Cold asphalt will make the screed climb (raise) while overheated asphalt will cause the screed to sink. Both conditions will cause grade and surface smoothness problems.
It can be seen that the temperature of the asphalt is critical to the 100% HIR process.
The present invention is able to maintain a consistent temperature through the use of, among other things, a temperature sensor in the pug mill which is designed to measure the final temperature of the asphalt leaving the pug mill (windrow). In addition, the pug mill's discharge (100% recycled asphalt) is formed into a lightly compacted windrow by a parallelogram ski that measures the volume and temperature of the asphalt. An on-board computer monitors the windrow's temperature and makes small adjustments to the forward processing speed, set by the operator. A decrease in the asphalt's temperature will cause a slight decrease in forward processing speed, allowing the Recycling Machine's (and the Preheaters) heater boxes greater time to heat the asphalt to the required depth. An increase in the asphalt's temperature will cause a slight increase in forward processing speed, allowing the Recycling Machine's heater box less time to heat the asphalt surface. The final temperature (pug mill discharge) of the 100% recycled asphalt will be fairly consistent, as the on-board computers attached to the three or more Preheaters and the Recycling Machine automatically monitor and control the complete heating process.
For manual operation, (each Preheater under its own on-board computer control) the Preheaters are equipped with electronic ground speed and asphalt, surface temperature monitoring and control. Each Preheater is set to track a preset (asphalt surface) heat range. The Preheaters and the Recycling Machine, monitor the temperature before, during and after the heater boxes. The Preheater's front and rear heat sensors measure the asphalt surface's heat differential, across the heater box and control the amount of heat by turning on and off the individual, electronically controlled burners. Heat sensors in each burner monitor and control each individual burner, while flame detectors shut down burners when flame (caused by crack filler or painted lines) is detected.
The Preheaters and the Recycling Machine may also be linked by wireless control (Ethernet). Satellite communication may also be used to replace the wireless control system. Each machine may also be fitted with a satellite Global Positioning System (GPS). The Recycling Machine and Preheater's on-board GPS computers will allow all of the machines to self steer and maintain the correct spacing (in relation to the Recycling Machine) for proper heat transfer to the asphalt. Data for the on-board GPS computers will be determined by a pickup truck, fitted with a mechanical, center lane guide and GPS sensor(s) positioned at the center of the truck. Two sensors will be used to provide greater accuracy. The pickup truck will be driven down the road (mechanical center lane guide positioned over center of road) prior to processing, with the GPS sensors readings being recorded into a portable computer fitted with a removable disk or a memory card (Zip or flash). The data will be downloaded into all of the machine's on-board computers. The truck can also be equipped with a metal detection boom with left and right side, hydraulically operated extension booms. A series of metal detectors are attached to the booms and detect iron utility structures in the asphalt's surface. The extension booms are hydraulically moved in and out to follow the width of the asphalt surface to be recycled. Electronic position sensors (LVDT) measure the position of the boom's extensions. The GPS computer records and stores the location of all iron structures. The Recycling Machine and the Preheaters will also be fitted with GPS sensors. The sensors may be fitted to the front and the rear of Recycling Machine and the Preheaters. The on-board computers compare the machine's actual position, to the stored position, recorded by the pickup truck's sensors. The on-board, computers monitor the Preheater's spacing and monitors and controls the steering (front and rear) when the automatic steering mode is selected. All GPS equipped machines are programmed to steer accurately down the center of the lane, not the center of the road. The Recycling Machine's processing width can be varied, while in operation, therefore the operators can process varying lane widths on both sides of machine. For safety reasons the machine operators can override the GPS control system at any time.
For large areas or straight-line work, a laser beam can be used to automatically guide (self-steer) the pickup truck in a straight line. Once the data has been stored to disk or memory and downloaded in to each machine's on-board computer, each pass is programmed at a selected width from the last pass. It is also possible to use the on-board GPS system fitted to each machine to program the coordinates directly, rather than using the data obtained by the pickup truck GPS system.
The GPS's metal detection readings are used by the final Preheater (unit ahead of the Recycling Machine) and the Recycling Machine's GPS and on-board computers to automatically raise and lower the rake/blades assemblies, extension mills, main mill and the pug mill, preventing damage to the sub-assemblies and iron utility structures. All machines fitted with the GPS system will also be equipped with sonic sensors mounted at the front of the machines. An operator warning horn will sound if an obstruction, such as an automobile is detected. The machine is programmed to stop when a minimum distance is reached.
The wireless data transmission will allow all of the machines to communicate with each other, providing accurate and efficient heating.
The system can be designed to operate under the following parameters:
All Preheaters and the Recycling Machine will be under their own control until processing speed and control has been established and stabilized.
The Recycling Machine (master) will control the spacing of the Preheaters (slaves) using wireless, GPS or satellite control.
The lead Preheater will produce as much heat as possible without damaging the asphalt's surface.
All other Preheaters following the lead Preheater will regulate their heat output based upon the temperature of the asphalt's surface ahead and behind (heat differential) their heating elements (boxes). Each Preheater is designed to produce as much heat as possible without damaging the asphalt's surface.
The final Preheater is equipped with a rake scarification/blade collection system and aggregate distribution bin, controlled by the Preheater's on-board computer. The aggregate bin must be occasionally filled with aggregate by a wheel loader. Space must be provided not only for the wheel loader, but also for the dump trucks discharging asphalt into the front hopper of the Recycling Machine. This necessitates the final Preheater being controlled by the operator (taken out of automatic control). All of the Preheaters ahead of the final Preheater will automatically move ahead once the final Preheater has reached a preset distance from the Preheater ahead (positions monitored by the on-board GPS systems). As the Preheaters move ahead their heating output will automatically increase (if possible) due to the increase in the heat differential across their heating elements (boxes). Once the aggregate bin has been filled or the dump truck has been released, the final Preheater is returned to automatic control. All of the Preheaters will slow down, allowing the Recycling Machine to catch up. The heating output of the Preheaters is automatically reduced during the catch up period due to the decrease in the heat differential across their heating elements (boxes), thereby preventing overheating of the asphalt.
The Recycling Machines heating system is designed to fine-tune the asphalt's final temperature before the asphalt is processed by the rake scarification and milling systems. The heating system is programmed to operate at 50% or less of its heating capacity (50% or less of the electronically controlled burners on the main heater box turned on). When the final Preheater is fitted with a rake scarification/blade collection system and aggregate bin the Recycling Machine's heating system must produce enough heat to remove any remaining moisture in the aggregate without degrading the asphalt. The scarifying process breaks the asphalt's surface, limiting the amount of heat that can be applied. The average temperature of the heating system can be set and controlled by the on-board computer. Individual, electronic burners will maintain this average by regulating their heat output. Infrared sensors monitor the asphalt's temperature, ahead of the heating system. The mill's grade control shoes (located behind the heating system) are fitted with heat thermocouples that monitor the temperature of the asphalt's surface, ahead of the rakes and mill assemblies. This temperature information, together with the pug mill's discharge (windrow) temperature and the operator's input for the base processing speed, controls the actual processing speed of the Recycling Machine. For instance, the operator has set the base_processing speed to 20 feet per minute, based upon information displayed upon his monitor (screen). The on-board computer is programmed to monitor key operating parameters such as Preheater/Recycling Machine's asphalt processing temperature differentials and the Recycling Machine's engine percentage load factor and will display a recommended base processing speed. The temperature of the asphalt in the windrow has been programmed at a set point of 320° F. The thermocouples on the grade shoes are reading 550° F. and the heating system is operating at 50% of its output. As the windrow temperature increases to 325° F. and the mill's grade shoes average temperature increases to 560° F. the Recycling Machine's actual processing speed increases automatically. The Recycling Machine's on-board computer will also send information by wireless or GPS to all of the Preheater's on-board computers to speed up their forward travel speed. When the Preheaters are at 100% of their heating capacity and the temperature differential across their heating systems begins to increase to a preset, set point, it signals that the train is getting to the point of going too fast for the asphalt to properly absorb heat. The Recycling Machine's on-board computer monitors all of the Preheater's temperature differentials (via wireless or satellite link) and will start to slow down its processing speed and the Preheaters, allowing more time for the asphalt to absorb the heat. The infrared temperature sensors in front of the Recycling Machine's heater box can instantly turn the heating system up to 100% capacity if the asphalt's temperature reaches a preset minimum set point. This can occur when the final Preheater's aggregate distribution system deposits a higher percentage of aggregate when its grade profiling system traverses a high section in the asphalt's surface. The increased volume of aggregate (generally washed, damp sand is used to modify the asphalt's air void ratio) will reduce the asphalt's surface temperature and the extra heat will be required to drive out the excess moisture and bring the aggregate up to the proper temperature. The temperature drop could also be the result of the Preheater's rake scarification/blade collection system (set to scarify at 2 inches or more) releasing large quantities of moisture (steam) out of the heated asphalt. The Recycling Machine's heating system is designed to operate at 100% of its heating output (all of the electronically controlled burners turned on), once the processing speed reaches a pre-set limit (around 22 feet per minute). 100% heating capacity is also used if the asphalt's temperature at the rear of the final Preheater heating system suddenly drops to a minimum temperature, set point when operating at below 22 feet per minute. If the temperature behind the final Preheater does not return to its normal operating temperature range within 10 feet, the Recycling Machine's on-board computer (using data obtained from the final Preheater by wireless or satellite transmission) will slow the Recycling Machine and Preheaters down using the GPS. This electronic monitoring, transmission and control loop is continuously repeated, providing maximum heating efficiency and processing speed.
2. Inconsistent smoothness when milling with 100% HIR machines:
The accuracy of the milled surface (grade) and the accurate placement of asphalt on to the milled surface determine the smoothness of the compacted, asphalt mat. If either one is incorrect the riding quality (smoothness) will be reduced. The present invention is fitted with two types of on-board, computer controlled, automatic grade control systems that monitor pavement grade to automatically control all of the milling and screed assembly operations:
a. Full, mainframe grade control: For asphalt surfaces requiring the accurate milling and placement of asphalt (highway and airport runways) a novel grade and slope control system has been developed. When using full, mainframe grade control, the mills and screed arm tow points are mechanically, electronically or hydraulically locked to the grade of the Recycling Machine's mainframe. The system can utilize Topcon's Paver System Four or Five together with their Smoothtrack® 4 Sonic Tracker II™ (non-contact) averaging beam(s) or mechanical averaging beam(s) on one or both sides of the Recycling Machine's rear end. All of the mechanical averaging beams are attached and towed by the Recycling Machine's mainframe while Topcon's Smoothtrack® 4 Sonic Tracker II™ averaging beam(s) are fixed to the mainframe as they do not have to be towed. All of the beams longitudinal track the asphalt's surface. The longer the beam the greater the averaging effect. Topcon's Smoothtrack® 4 Sonic Tracker II™ averaging beams are preferred as they do not make contact with the asphalt's surface, thereby eliminating marking (scuffing) of the previously finished mat and can also be used on the curb side (right) of the Recycling Machine. They also provide increased accuracy and easier setup/operation. The mechanical averaging beams use electrical or hydraulic sensors (attached to the Recycling Machine's rigid main frame) to sense the grade (position) of the beam. Wands or arms attached to the sensors make physical contact with the beams or travelling string line (string line attached to the beam). Whichever sensor system is used, the Recycling Machine's grade (mainframe) is controlled as explained in the following example. The Recycling Machine's rear, left side axle and mainframe begin to sink (lower) in grade, compared to the left side averaging beam's grade (the Recycling Machines right side grade remains on grade). The grade control system will signal for hydraulic oil to be sent to the left, rear axle's, hydraulic leveling cylinder (attached between the mainframe and the rear axle assembly). The left hydraulic cylinder extends and tilts the mainframe, keeping the mainframe on grade. The electronic or hydraulic sensor automatically stops the hydraulic oil supply to the left hydraulic cylinder as the mainframe is raised back to match the averaging beam's grade. The grade of the frame has to change to produce input into the sensors; however, this change in grade is small and has little or no effect on the final grade of the asphalt's surface. The right hydraulic leveling cylinder is under the control of the right averaging beam and sensor. For surfaces where the right hand, mechanical averaging beam cannot practically be used due to obstructions, poorly graded shoulders, curbs, etc., the electronic slope sensor (located at the rear end of the Recycling Machine's mainframe) can be substituted in place of the right averaging beam and sensor. The slope sensor allows the percentage of grade to be electronically adjusted while the Recycling Machine is processing. Topcon's Smoothtrack® 4 Sonic Tracker II™ averaging beams together with Topcon's frame mounted electronic slope sensor allow averaging on both sides or cross slope to be specified. To allow the above grade and slope control system to operate the Recycling Machine is designed with a hydraulic, three-point suspension system that lifts and lowers both ends of the Recycling Machine's mainframe as well as tilting it. Two hydraulic cylinders per axle assembly are attached between the mainframe and front and rear axle assemblies. The two front cylinders (front axle assembly) are hydraulically connected in parallel, while the rear axle's hydraulic cylinders are individually controlled, thus forming a three-point suspension system. The front and rear axle assemblies are fitted with hydraulic wheel motors and rubber tires, inflated with dry nitrogen to high pressures to prevent the tire's side walls from deflecting which would have a negative effect on grade control. Both axle assemblies can steer 40 degrees in both directions, providing accurate steering. The rear tires contact the heated asphalt's surface, milled by the main and extension mills (located ahead of the rear axle). The front axle assembly follows the original, heated asphalt's surface and is free to oscillate when working on uneven surfaces. Grade changes will cause the front axle assembly and to some degree the front of the mainframe to rise and fall, however, this has little effect on the rear end of the mainframe due to the frame's long length. As noted above, input from the left and/or right side averaging beams or the left side averaging beam and electronic slope sensor are used to control the operation of the two individual hydraulic cylinders attached between the rear of the mainframe and the rear axle assembly. The Recycling Machine's mainframe is said to be “locked to grade” by the sensors. The extension mills and the main mill are raised and lowered in relation to the mainframe by four, individual (left and right) hydraulically operated sliding struts, controlled by four automatic grade control sensors. When utilizing full, mainframe, grade sensing, the mills automatic grade control sensors sense the mainframe's position. Fine adjustments can be made to the depth of cut by adjusting each, individual sensor. This is desirable when setting the cutting depth between the extension mills and the main mill. The screed arm's tow points can be locked mechanically (pinned) to the mainframe.
The screed is attached to the screed tow points (left and right side of the recycling machine) by pivoting, rigid arms. The tow points can be pinned into position for manual control by a skilled operator who uses crank handles at either side of the screed assembly to adjust the screed's angle of attack. The screed assembly allows more asphalt to flow under its plates (screed assembly rises) when its angle of attack is increased (front of the screed's plates higher than the rear) and visa versa. For automated control of the screed assembly, the left and right crank handles are locked into position. Hydraulically raising or lowering the tow points controls the screed assembly angle of attack. Raising a tow point will increase the angle of attack and visa versa. The automatic grade control sensors that control the tow points are mounted to the rigid screed arms and sense the asphalt's grade using Topcon's Smoothtrack® 4 Sonic Tracker II™ averaging beams, mechanical averaging beam(s), joint matcher or string lines. The mounting position of the sensors can be adjusted (distance from the tow point) to control the response of the system. When the mechanical averaging beams (towed) are used the screed arm's sensors, sense of the same averaging beams used by the Recycling Machine's mainframe grade control sensors. The right hand, screed tow point can be controlled by using a second electronic slope control, attached to the screed. Generally the mainframe and the screed assembly would both be operating with individual, electronic slope controllers. A major advantage of using the automatic grade controls to control the screed assembly tow points (even though the mainframe is locked to grade already) is due to the influence of varying, asphalt levels (in front of the screed assembly), travel speed, asphalt density and heat. Example: If the Recycling Machine is (fitted with mechanical averaging beams on both sides) slowed for traffic, the screed assembly will tend to sink (less asphalt flow under the screed plates) whereas the mainframe will remain at grade as the rear axle's wheels are tracking a solid, milled asphalt surface. The automatic grade sensors mounted on the screed's tow arms will sink with the screed assembly, however, the mechanical averaging beam's grade remains consistent. As the sensors sink they signal and control the hydraulic oil flow into the tow point's cylinders, raising the tow points, which increases the screed assemblies angle of attack, resulting in a consistent grade. Other recycling machines have manual adjustments on the mills for depth control or have automatic grade controls fitted to the mills with very short skis or pans. The problem with both systems is in following the original, uneven surface grade causes the mills to profile to the original grade, rather than averaging the grade as in the case of the long averaging beams. For example: A utility trench, stretching transversely across the complete width of the asphalt pavement has settled (depression) by 2 inches. The short grade skis or pans attached to the mills will follow in and out of the depression causing the mills to cut to the same profile. This depression will show up in the finished mat as a depression, after final rolling. The long averaging skies, by comparison, would hardly notice the same depression. Finally, if the milled grade is continuously varying (up and down) then the recycling machine's and/or the paving machine's wheels or tracks are following the undulating grade, causing their automatic grade controls to work harder while controlling the screed assembly grade. It is interesting to note that the grade of the asphalt being laid by any screed assembly, if the automatic grade controls are set properly, will remain very consistent, even with an undulating, milled base surface. However, during final compaction of the asphalt by the rollers, the finished mat will follow, to a degree, the profile of the undulating, milled base surface, thereby producing a mat with poor smoothness characteristics.
b. Left and right side averaging skies for the extension mills and the main mill: For secondary roads, city streets and asphalt surfaces where full, mainframe grade averaging is not practicable using long, mechanical averaging beams, the recycling machine is equipped with left and right side skis, or optional, averaging skis. The skis are located ahead of the extension and main mills. The two averaging ski assemblies contact the heated, unprocessed asphalt (original grade) and are manually adjustable in width, allowing setup for various processing widths. The extension mills (left and right side) are hydraulically adjustable in width and crown while the main mill, located behind the extension mills is of fixed width. The left ski automatically controls the grade (depth of cut) of the left extension mill and the left side of the main mill. The right ski controls the grade of the right extension mill and right side of the main mill. The left and right ski assemblies are connected by a jointed, cross beam to which various attachments, used to contact the heated asphalt surface, can be added. In its simplest form, two sliding shoes (the shoes contact the heated surface) are mounted to the cross beam and follow the profile of the asphalt's surface, generally in the wheel ruts created by traffic, as this is generally the smoothest part of the surface on badly rutted asphalt. In its most complex form two sets of shoes (one on either side of the Recycling Machine) are attached to the cross beam by pivoting beams, allowing the transverse surface across the asphalt to be averaged. Left and right extension beams are attached (when space permits) to the jointed, cross beam, allowing the shoes to reference the surface to the left and right of the Recycling Machine. The left side shoe(s) can be replaced by wheels attached to averaging beams, running in line (longitudinally) with the Recycling Machine and on the asphalt surface processed on the previous pass. The wheels are used to prevent marking of the previously finished mat. This allows the mills to profile to the grade of the previously finished surface. Shoes can also be used if wheels are not required. The mill's grade control system can transversely or longitudinally average the asphalt surface, providing far greater accuracy than simple, shorts shoe sensors, mounted directly on to the extension and/or main mill. The left and right side of the grade control cross beam are attached by two pivoting links to the left and right side, sensor control stations that house the hydraulic (electronic are optional) grade control sensors. The left, sensor control station controls the left extension mill and left side of the main mill, while the right, sensor control station controls the right side of the mills. Both the extension mills and main mill are raised and lowered by four (two for the extension mills, two for the main mill) hydraulically operated, sliding struts attached to the machine's mainframe. The sliding struts on the extension mills attached between the Recycling Machine's mainframe and the extension mill's mainframe. The left and right side extension mills are attached to the extension mill's mainframe by hydraulic cylinders, allowing the extension mills to pivot (crown), independently to the extension mill mainframe. The sliding struts for the main mill attach directly to the main mill's mainframe. Attached to each sliding strut is a manually adjustable height screw, which the grade control sensors touch (sense). Each grade control sensor (attached to the sensor control station) monitors the position of the height screws. The following example will explain the operation of grade correction for the right hand side. The Recycling Machine is entering an intersection with a raised section of asphalt pavement. The right hand averaging shoes (in contact with the heated asphalt surface) begins to rise, causing the sensor control station to rise. The two right hand, grade control sensors (attached to the sensor control station), move away from the sliding strut adjuster screws and supplies hydraulic oil to the hydraulic cylinders attached between the mainframe and the sliding struts. The sliding struts are automatically raised, moving the adjuster screws up to match the position of the sensor control station, cutting of the supply of hydraulic oil. The sliding struts/adjuster screws will always follow the position of the sensor control stations. Manual adjustment is provided to allow for fine adjustments to each individual strut to fine tune the milling height between the extensions and the main mill. Manually crowning of the left and right extension mill by the operator is possible without effecting the position of the sliding struts. This is desirable when working in city streets with poor grade, intersections, driveways and irregular curbs and/gutters. With this grade control system with both mills sensing the sensor control stations, any sliding strut can be manually raised or lowered, without effecting the other sensors. The left and right sensor control stations are mounted to the Recycling Machine's mainframe by a parallelogram linkage, which raises and lowers the grade control sensors in absolute alignment with the sliding struts. The sensor control stations are also attached to the mainframe by a hydraulic lift/damper cylinder. The function of the hydraulic lift/damper cylinder is to carry a percentage of the sensor control station, beam and averaging shoe's weight, preventing the shoes from sinking into the hot asphalt. The hydraulic lift/damper cylinder is also responsible for dampening the mechanical action of the grade system by restricting oil flow. The sensor control stations also incorporate flat springs for connection between the jointed, cross beam. The spring deflects if a sudden movement occurs as in the case of the shoes riding up and over a raised utility structure. The spring(s), working together with the hydraulic lift/damper cylinder prevent the sudden movement of the sensor control station(s), which in turn prevents the mills from suddenly raising, leaving a high section in the milled surface. The same applies if the shoes suddenly drop into a transverse depression, the spring deflects and the cylinder dampens. It is important to note that the rear wheels of the Recycling Machine follow the grade set by the main mill assembly.
3. Inconsistent smoothness and surface defects, caused by asphalt handling problems when using an attached screed using 100% HIR machines
As mentioned before (when discussing paving machines), producing a quality, asphalt surface that meets all engineering specifications requires considerable skill, knowledge and the proper equipment. Consistency is one of the keys, with the following innovations providing the consistency when 100% recycling with the Enviro-Pave Recycling Machine:
a. Processing should be continuous with no stops. Stopping the screed assembly allows it to settle into the asphalt, causing a depression. Weight transfer from the screed assembly to the Recycling Machine's mainframe has been tried and found to work, however when forward travel was resumed the screed assembly would still tend to sink. Two hydraulic cylinders (attached between the mainframe and screed assembly) are used to raise and lower the screed assembly. When processing, the two hydraulic cylinders are floating (oil can freely flow in and out of both ends of the cylinders). When forward travel must be stopped the cylinder's hydraulic float is cut off and oil is directed into one end of the cylinders (screed raise) at a pressure high enough to transfer weight from the screed assembly to the mainframe. Transferring weight prevents the heavy screed assembly from sinking into the mat. A time delay, controlled by the on-board computer has now been added, allowing the screed time to stabilize with asphalt flow as forward travel is resumed. This delay will be equal to one or more lengths of the screed's main plate.
b. The processing speed should remain as consistent as possible. An increase in speed will cause the screed to rise while a decrease will cause the screed to sink. An optical encoder, mounted to one of the rear axle assembly drive motors will provides the equivalent of cruise control by monitoring the drive wheel's RPM. The on-board computer will control the flow of hydraulic oil in the drive system to maintain a consistent speed. Varying loads on the Recycling Machine will have no effect on the processing speed.
c. The temperature of the asphalt in front of the screed (head) should remain consistent as noted in detail above.
d. The asphalt in front of the screed assembly should remain at a consistent level across the complete width of the screed and screed extensions. An increase in asphalt level will cause to screed to rise while a decrease will cause it to sink. Generally, recycling machines fitted with an attached screed assembly have had problems when the screed assembly carried too much asphalt. This resulted in the screed assembly becoming uncontrollable. It was also common for the screed operator to load the screed assembly with an excessive amount of asphalt as it gave a reserve of asphalt for when the screed's extensions suddenly became low in asphalt due to poor asphalt flow from the auger assembly. Carrying too much asphalt with the screed assembly also allowed the asphalt to stop moving at the screed's extensions, resulting in the asphalt losing temperature and sticking to the screed's face. The cold asphalt caused quality problems in the finished mat, if and when it passed under the screed's extensions.
The following innovations are designed to control the head (amount) and distribution of asphalt across the main screed and screed extensions while reducing material segregation:
A heated (automated heat control and propane burner) and insulated, asphalt surge bin and vertical elevator, located inside the rear end of the Recycling Machine's mainframe, automatically stores and releases hot asphalt to maintain a constant volume (head) of material in front of the screed assembly. The surge bin and vertical elevator are connected to the Recycling Machine's mainframe by two hydraulic cylinders. The surge bin discharges the stored, hot asphalt through two (left and right side), bottom discharging, rotary valves located above and in front of the auger/divider/strike off blade assembly, which is located in front of the screed assembly. The left rotary valve supplies the left auger while the right rotary valve supplies the right auger. An integral, vertical elevator picks up the excess, 100% recycled asphalt (not required by the screed assembly) from the windrow exiting the Recycling Machine's pug mill (mixing chamber) and elevates it up the front face of the elevator into the surge bin, for storage. The Recycling Machine's on-board computer automatically starts and stops the vertical elevator by measuring the pressure in the two hydraulic cylinders and the height of material exiting the pug mill by monitoring the pug mill's volume sensing ski. The hydraulic pressure is proportional to the weight of the asphalt in the bin. The surge bin's holding capacity is sufficient for continuous operation without having to add new asphalt and once full, provides enough stored asphalt for the start-up of the process before the Recycling Machine's windrow is established. Attached to the front side of the vertical elevator is a small hopper/diverter valve that can receive new asphalt from the optional front asphalt hopper/drag conveyor and the central conveyor. The hydraulically operated diverter valve allows new asphalt to be elevated by the vertical elevator into the surge bin for storage, or be discharged on to the windrow as additional material. Projects requiring additional asphalt include, shoulder widening, modification to existing grade or surfaces with a shortage of existing asphalt. Diverting new asphalt to the surge bin allows the bin to be filled at the beginning of the daily shift. Once the bin is initially filled recycled asphalt can be collected from the windrow for the remaining shift. This not only provides new asphalt, but also provides control over the startup procedure. The Recycling Machine's screed assembly is positioned over the asphalt's surface at the start of the new joint (the end of the previous joint). The screed assembly is set on to two starter spacers and the screed's cranks are nulled (neutralized) and set. The front asphalt hopper is filled with hot mix asphalt, delivered by truck from the asphalt plant. The variable speed drag chain conveyor (part of the front hopper) delivers the asphalt to the variable speed, central conveyor. The central conveyor (runs through the center of the machine) moves the asphalt to the hopper/diverter valve, attached to the surge bin's, vertical elevator. Asphalt is diverted to the vertical elevator and the surge bin is automatically filled to the correct level by monitoring the hydraulic pressure in the two surge bin support cylinders. The augers and surge bin's rotary valves are turned on to automatic, on-board computer control. The left and right augers will increase to maximum speed, as no asphalt is available to operate the two augers, electronic level sensors, located at the end of the screed's extensions. The surge bin's bottom discharging, rotary valves (left and right side) are automatically opened by sensing the speed of the individual augers, allowing asphalt to flow to the ends of the screed's extensions and the auger's electronic, level sensors. Once the screed's extensions are full of asphalt, the augers automatically slow down and stop, while the surge bin's rotary valves are automatically closed. As asphalt was flowing out of the surge bin's rotary valves the on-board computer was automatically replenishing the surge bin to a full state. Once full the on-board computer automatically stops the elevator by measuring the surge bin's hydraulic cylinders pressure. The hopper/diverter valve is fitted with an electronic sensor that controls the speed of the central conveyor. When the hopper is full the conveyor is stopped. Once the supply of asphalt to the screed assembly has been meet the Recycling Machine's processing equipment is put into operation and the machine moves forward, preventing the screed from settling. Asphalt is now diverted from the vertical elevator to the asphalt's surface to form a windrow of new material. As the diverter valve opens the electronic sensor detects the drop in the level of asphalt in the hopper/diverter valve and restarts the central conveyor and the front hopper's drag chain. The central conveyor (in this case a belt conveyor) is fitted with an electronic belt scale, used to measure the weight of asphalt being conveyed. The on-board computer is programmed to supply the correct amount of asphalt to form a windrow by monitoring the individual speed of the auger. Gradually, as the pug mill's discharge rate increase (greater volume of asphalt being processed), the on-board computer proportionally reduces the flow of new asphalt by monitoring the individual auger's speed, measuring the volume of material exiting the pug mill's, variable ski (asphalt volume measurement and the amount of weight on the conveyor belt's scale. When 100% HIR recycling is being conducted and new asphalt is not required after the initial startup period, the front hopper, belt conveyor and the hopper/diverter valve can be emptied by discharging and blending the asphalt automatically into the asphalt surge bin. The vertical elevator picks up the 100% recycled asphalt from the windrow while the new asphalt (delivered from the front asphalt hopper) is blended in the vertical elevator, preventing variations in the finished mat's surface texture. Generally the surge bin/vertical elevator are only required for 100% HIR once the process has been established. For asphalt surfaces requiring major grade corrections the front asphalt hopper and central conveyor can be used to automatically supplement and blend new asphalt into the process. In this case the on-board computer monitors the individual auger's speeds, measures the volume of 100% recycled asphalt exiting the pug mill's variable ski, the amount of weight on the conveyor belt's scale and the amount of asphalt stored in the asphalt surge bin/vertical elevator. The on-board computer will maintain the asphalt surge bin's level by scalping asphalt from the windrow, when processing volume is high and supplying new asphalt as processing volume decreases. An electronic temperature sensor monitors the new asphalt's temperature on the central belt conveyor and automatically discharges the conveyor (into the asphalt surge bin/vertical elevator) when the temperature drops to a minimum value. This situation is possible when new asphalt is not required over longer periods of time (the asphalt's grade has improved. The front asphalt hopper's discharge remains shut off as the conveyor discharges. The on-board computer always leaves sufficient space in the asphalt surge bin for the volume of asphalt carried by the conveyor. Temperature sensors also measure the temperature of the asphalt stored in the front asphalt hopper assembly. The asphalt tends to drop at a slower rate as the front hopper has an insulated bottom and sides. Also the asphalt retains heat better when stored in bulk. The Recycling Machine operator is visually warned when the temperature drops to a level requiring action. If new asphalt is not available to supplement the existing asphalt in the front hopper the on-board computer will automatically discharge the hopper by slowly restarting the hopper's discharge and the central belt conveyor, thereby delivering new asphalt to the rear hopper/diverter valve. The asphalt will be diverted to the heated windrow exiting the pug mill. The strike off blade, which is part of the auger/divider assembly, is designed to carry the excess amount of asphalt without effecting the operation of the screed assembly.
The screed auger/divide/strike off blade assembly, located in front of the screed assembly is responsible for conveying the heated asphalt windrow to all areas of the main screed and the screed extensions. The screed extensions (left and right side) are hydraulically extendable and are used to vary the paving width. The screed auger/divider/strike off blade assembly has two, independently controlled augers (left and right side) designed to split the hot, asphalt windrow and distribute asphalt to either end of the main screed and screed extensions. Individual auger speed is automatically controlled by industry standard, proportional, electronic level controls (paddles), located at either end of the screed's extensions. As the asphalt level (head) drops at one or either end of the screed's extensions the paddles signal the on-board computer to increase the auger(s) speed to convey more asphalt. As the asphalt is conveyed from the centrally located windrow the head of asphalt in front of the main/extension screed rises, raising the paddle(s) thereby slowing the auger(s). Generally both augers will be running at a continuous, slow speed, supplying a consistent flow of asphalt across the screed assembly. The screed auger/divider/strike off blade assembly can be hydraulically raised or lowered to adjust for varying depths of asphalt being process by the Recycling Machine. The operation of the screed auger assembly, described above, can be found on any paving machine and works well when laying thick lays of asphalt. It has not proved to be as successful when used with 100% HIR Recycling Machines laying 50 mm or less of recycled asphalt, particularly when working on slopes. Generally there has always been a problem splitting the asphalt windrow with just the screed auger assembly, especially when working on slopes. The high side of the screed extension (crown of the pavement) would generally be starved of asphalt. To overcome the problem the screed auger/divider/strike off blade assembly is fitted with a centrally mounted, hydraulically controlled, mechanical divider, designed to physically split the windrow and feed it into the left or the right auger (the auger requiring the greater amount of asphalt). The angle of the divider is controlled by the onboard computer and uses the left or right auger's speed as a reference. As the auger(s) speed increases beyond a preset speed (level of asphalt dropping in front main screed and/or either screed extension) the on-board computer turns the hydraulic divider, diverting a greater percentage of the asphalt windrow into the auger requiring asphalt (the auger with the greatest speed). The position of the divider is electronically monitored, allowing the divider to turn proportionally to the individual auger's speed. If both augers are rotating at the same speed the divider remains in the straight-ahead position. If the on-board computer determines that any auger's speed is still increasing (divided windrow is not providing enough asphalt to the speeding auger) the rotary discharge valve of the asphalt surge bin, located above the speeding auger is automatically opened, providing additional, heated asphalt. The additional asphalt continues to flow from the asphalt surge bin until the auger slows to a predetermined speed, where upon the rotary discharge valve is automatically closed. If the on-board computer determines that the speed of both augers are too high (lack of asphalt in the windrow and at the screed assembly) both of the asphalt surge bin's rotary valves are opened, thereby providing additional heated asphalt to both augers. The operation and control of the screed auger/divider/strike off blade assembly and the asphalt surge bin are designed to handle the heated asphalt in a slow and gentle manner so as to reduce segregation, heat loss and emissions. The asphalt surge bin automatically refills from the windrow when the volume of asphalt exceeds the volume required by the screed assembly, typically when milling through a high area of asphalt pavement. Attached to the front of the auger/divider is the manually adjustable strike off blades (left and right side). The blades functions as tunnels for the augers allowing asphalt to be conveyed more efficiently, without causing segregation. The strike of blades also limits the amount of asphalt that can physically reach the left and right side augers flights and also the screed assemblies front face. The two, strike off blades are adjustable in height and taper with the height of blades becoming greater towards the end of the augers, allowing more asphalt to flow under the blades towards the end of the augers. If a sudden surge of asphalt (highly unlikely due to the electronic control, larger asphalt surge bin and high capacity, vertical elevator) does occur when milling through a high section of asphalt, the auger/divider/strike off blade will carry the extra head of asphalt.
4. Inconsistent ratio of new asphalt to 100% recycled asphalt when using the remix method.
The general procedure used by other HIR recycling machines to introduce a percentage of new asphalt into the recycled asphalt (Remix) is to monitor the forward speed of the recycling machine. This procedure is not that desirable due to the fact that the volume of asphalt being recycled at any given time is constantly changing due to uneven surface grade and varying processing width, on variable width machines. The other problem is where the new asphalt is delivered for mixing with the recycled asphalt. which often results in the asphalt being dropped in front of the recycling machine's heating system. The problem with this approach is that the new asphalt is subjected to unnecessary heat, which rapidly deteriorates the new asphalt.
The following innovations allow the present invention to provide a true ratio between the 100% recycled and new asphalt without degrading the new asphalt.
The present invention is equipped with a front asphalt hopper/variable speed chain slat conveyor, truck pusher bar, variable speed central belt conveyor and electronic belt scale, conveyor hopper/diverter valve, surge bin/vertical elevator, auger/divider/strike off blade and screed assembly. The Remix process starts by using the same method as the 100% HIR process. The Recycling Machine's screed assembly is positioned over the asphalt's surface at the start of the new joint (the end of the previous joint). The screed assembly is set on to two starter spacers and the screed's cranks are nulled (neutralized) and set. The front asphalt hopper is filled with hot mix asphalt, delivered by track from the asphalt plant. The variable speed drag chain conveyor (part of the front hopper) delivers the asphalt to the variable speed, central conveyor. The central conveyor (runs through the center of the machine) moves the asphalt to the hopper/diverter valve, attached to the surge bin's, vertical elevator. Asphalt is diverted to the vertical elevator and the surge bin is automatically filled to the correct level by monitoring the hydraulic pressure in the two surge bin support cylinders. The augers and surge bin's rotary valves are turned on to automatic, on-board computer control. The left and right augers will increase to maximum speed, as no asphalt is available to operate the two augers, electronic level sensors, located at the end of the screed's extensions. The surge bin's bottom discharging, rotary valves (left and right side) are automatically opened by sensing the speed of the individual augers, allowing asphalt to flow to the ends of the screed's extensions and the auger's electronic, level sensors. Once the screed's extensions are full of asphalt, the augers automatically slow down and stop, while the surge bin's rotary valves are automatically closed. As asphalt was flowing out of the surge bin's rotary valves the on-board computer was automatically replenishing the surge bin to a full state. Once full the on-board computer automatically stops the elevator by measuring the surge bin's hydraulic cylinders pressure. The hopper/diverter valve is fitted with an electronic sensor that controls the speed of the central conveyor. When the hopper is full the conveyor is stopped. Once the supply of asphalt to the screed assembly has been meet the Recycling Machine's processing equipment is put into operation and the machine moves forward, preventing the screed from settling. Asphalt is now diverted from the vertical elevator to the asphalt's surface to form a windrow of new material. As the diverter valve opens the electronic sensor detects the drop in the level of asphalt in the hopper/diverter valve and restarts the central conveyor and the front hopper's drag chain. The central conveyor (in this case a belt conveyor) is fitted with an electronic belt scale, used to measure the weight of asphalt being conveyed. The on-board computer is programmed to supply the correct amount of asphalt to form a windrow by monitoring the individual speed of the auger. Gradually, as the pug mill's discharge rate increases (greater volume of asphalt being processed), the on-board computer proportionally reduces the flow of new asphalt by monitoring the individual auger's speed, measuring the volume of material exiting the pug mill's variable ski (asphalt volume measurement and the amount of weight on the conveyor belt's scale).
Once the windrow has been established by monitoring the flow of asphalt through the pug mill, the on-board computer automatically switches to its Remix program. The surge bin/vertical elevator is used to scalp off a percentage of 100%, recycled asphalt in the windrow. An adjustable (proportional) electronic sensor is used to set and control the scalping depth of the vertical elevator, allowing the elevator to follow the varying windrow's height. The belt conveyor and the front hopper's drag chain start supplying new asphalt to the hopper/diverter valve, allowing the two asphalt flows to blend together in the vertical elevator's slats. The central belt conveyor is fitted with an electronic belt scale, used to measure the weight of asphalt being conveyed. The on-board computer is programmed to calculate and control the correct amount of new asphalt being blended into the 100% recycled asphalt (10% to 15%). This is accomplished by measuring the volume of material exiting the pug mill's variable ski (material volume measurement and the amount of weight on the conveyor's belt scale. The variable speed, drag chain in the front hopper and the variable speed central, belt conveyor supplies the correct amount of new asphalt. The belt conveyor is designed to operate at a higher speed than the hopper drag chain, preventing spillage at the drag chain's discharge point on to the belt conveyor. The two conveyors are fitted with optical encoders to monitor the speed of both units, allowing the on-board computer to monitor and control the speed ratio between the two conveyors. As the amount of new asphalt increases or decreases, based upon the volume of asphalt being recycled the vertical elevators speed is proportional changed to pick up more or less recycled asphalt. This is possible as the inlet to the vertical elevator is always flooded (built up) with asphalt. The blend of recycled and new asphalt is delivered to the heated and insulated surge bin. The on-board computer, monitoring the weight of the bin will always try and maintain the bin at 50% of its capacity. This is achieved by automatically controlling the discharge flow from the surge bin's two, rotary valves, by monitoring the individual screed auger's speed (auger/divider/strike off blade assembly). The auger with the highest speed will receive proportional, more asphalt. By blending the new asphalt with a proportion of the 100% recycled asphalt (picked up from the windrow) in the surge bin/vertical elevator provides a little more mixing than would otherwise be possible if the hopper/diverter valve dumped asphalt directly on to the windrow. If the extra blending (mixing) is found not to be required then the asphalt can be diverted and dropped on to the 100% recycled asphalt's windrow. It should be noted that the augers do mix the asphalt as it is moved across the front face of the screed assembly. One might ask why not introduce the new asphalt onto the mills or the pug mill. Pre-engineering, using core samples, taken at regular intervals, determine how much rejuvenator fluid and/or polymer liquid must be added by the Recycling Machine and how much washed aggregate the final Preheater must add. Adding new asphalt would complicate the testing procedure.
5. Inability to process asphalt around utility structures and obstructions.
Utility structures and other obstructions have until now presented one of the greatest challenges to the HIR of asphalt, especially in city work. An example would be a utility structure located in the center of the lane being processed. To prevent damage to the Recycling Machine's carbide milling teeth (main and extension mills) and to the iron utility structure(s) located in the asphalt's surface, the mill(s) are lifted, leaving an unprocessed section of asphalt across the width of the lane. When dealing with utility structures and obstructions the following methods are typically used:
a. Ignore the problem. Raise the scarification and/or mill systems and let the screed assembly place recycled asphalt on top of the old asphalt. The result is a width of asphalt up to 1 m (3 ft.) or more in length (in the direction of travel) that has not been recycled (rejuvenated) to pre-engineered specifications. The section will not be compacted to the same degree as the recycled asphalt by the rolling equipment, thus leaving a bump in the mat (asphalt surface) of old asphalt
b. Raise the scarification and/or mill systems and use hand tools (rakes and shovels) to loosen the old asphalt. This is almost impossible without stopping the recycling machine and is dangerous to workers, as they must reach into the processing area of the machine. Recycling machines that have scarification systems that float over and around obstructions have been somewhat successful as the asphalt is loose enough to hand move (where possible) without stopping the Recycling Machine. The asphalt remaining on the heated surface mixes with the recycled asphalt, collected and stored in front of the screed assembly. The asphalt picked up by hand shovel is generally, thrown back into the mills for processing.
c. Before 100% HIR of the asphalt surface the area around the obstruction(s) is cold milled with a small milling machine. The milled asphalt is collected and removed and the surface is swept if processing is to be conducted at a later date. This works well, except that a reduction in the volume of material available for recycling occurs, resulting in new asphalt having to be added or a change in profile/grade at the time of recycling. Filling the cold milled sections with new virgin asphalt and compacting before recycling works well, but presents compaction problems (bump in surface) and in some cases, changes to the finished mat's surface texture. The major objection to this approach is the added cost, traffic delays and possible driving hazard due to the open, milled sections, if not paved immediately.
d. Recycling machines that produce a windrow of asphalt (screed assembly removed) for pickup by a windrow conveyor, attached to a standard paving machine have a greater opportunity to work around utility structures and obstructions. To date hand-tools, powered machines and even a hydraulic arm fitted with a blade, mounted to the windrow conveyor, scrape and collect the unprocessed asphalt. The hydraulic arm requires the windrow conveyor/paving machine to stop, marking the finished mat (the screed sinks into the asphalt surface due to it's own weight, vibration from the windrow conveyor and the operation of the hydraulic arm). Other problems exist when using a separate windrow conveyor and paving machine, i.e. increased costs, reduced asphalt temperature, increased segregation, increased pollution and increased equipment train length. In addition, the proper mixing of the old asphalt (asphalt scraped from the heated surface) does not take place as the old asphalt is generally placed on to the open windrow, throwing off the quality of the recycled asphalt contained within the windrow. Safety is another issue when processing with an open windrow. It is quit common for automobiles to try and cross the heated windrow only to become stuck in 250 to 300+ Deg F. asphalt. Animals have seriously burnt their feet, as have humans with open footwear! Recycling machines with an attached screed do not suffer from the above problems, as there is no open windrow.
The present invention scarifies and cleans around utility structures and obstructions without stopping the HIR Recycling Machine, allowing the scarified asphalt to be collected and properly mixed with additives:
The rake scarification/blade collection system fitted to the final Preheater (Preheater ahead of the Recycling Machine) and the Recycling Machine are identical. The blades are attached to the four, main rake, pivoting bodies, located behind the spring loaded, carbide cutters attached to the same bodies. When approaching a utility structure or obstruction (Preheater followed by the Recycling Machine) the Preheater's operator tilts the required, individual rake bodies, leaving the carbide cutters in the heated asphalt while at the same time lowering the trailing blades. Hydraulic force pushes the blades into the scarified surface 50 mm (2″) or more, scraping and collecting the heated asphalt. Once past the utility structure/obstruction, the blades are raised at a controlled rate (rate is adjustable and once set is automatic), releasing the collected asphalt in a 50 to 75 mm (2 to 3″) layer. Raising the blades does not effect the operation of the carbide cutters. Hand tools or a small two-wheel drive machine with adjustable blade, similar to a walk behind rotovator (without the rotor) are used (if required) for the final cleanup with the asphalt being spread on to the heated, scarified surface ahead or behind the area being scraped and cleaned. Plenty of space and time exists for this process as the Recycling Machine is generally trailing the Preheater by up to 9 to 12 m (30 to 40 ft.). The Recycling Machine's rake blades are available if further cleaning is required when approaching the same utility structure/obstruction using the same procedure as used by the Preheater. Raising the main mill on the Recycling Machine for utility structures/obstructions will automatically stop the flow of rejuvenator fluid to the main mill and the pug mill, preventing the fluid from reaching the milled, base surface, thereby eliminating eventual bleeding of the finished, compacted surface. When the main mill is manually raised for utility structures/obstructions, the on-board computer calculates and stores in it's memory the amount of rejuvenator fluid that would have been sprayed into the asphalt being recycled, if the main mill had not been raised. When the main mill is lowered (taken off manual control) into the heated surface (controlled again by the automatic grade/slope controls) it collects and feeds the asphalt into the pug mill for final mixing. Lowering of the main mill allows the rejuvenator fluid flow to commence. The stored (memory) amount of rejuvenator fluid, together with the required processing amount of fluid (determined by the pug mill) results in increased fluid flow required for the increased volume of asphalt at that particular section (rake scarified asphalt covered with a layer of asphalt collected by the rake blades). The ratio of rejuvenator fluid to asphalt being recycled remains consistent.
Blades are not required on the extension rakes as the extension mills are fully adjustable (raise/lower, in/out and tilt up/down) and can be used to cut and clean around most utility structures/obstructions in their path. The extension mills are fitted with a cutter blade at each outer end, providing cleaning to the edge of utility structures/obstructions and curbs and gutters. Final cleaning on each side of the Recycling Machine is easily accomplished with hand tools, even while moving.
The above, innovations allows any processing work required around utility structures and obstructions to be accomplished before the Recycling Machine recycles the old asphalt, rather than after recycling and result in the following advantages:
The old asphalt that has been moved from around utility structures, obstructions and sections across the asphalt's surface (where the mills can not be used) remains on the surface for 100% processing by the Recycling Machine.
The complete width of the asphalt can be checked and worked upon. This is not the case after the Recycling Machine has processed the asphalt as the wide (approximately 36″) windrow covers the center section of the width.
6. Inaccurate and inconsistent application of liquid additives.
While other 100% HIR equipment have systems designed to monitor and control the application of rejuvenator fluid into the reworked (recycled) asphalt, none appears to have the ability to monitor and control the application of liquid polymers together with rejuvenating fluid. Generally, recycling machines control the rejuvenator's application rate by monitoring the machines processing speed (distance traveled). Distance traveled, by itself, produces inaccurate and inconsistent results as the volume of asphalt being processed changes constantly as density, depth of cut, pavement profile and width of cut (machines with variable width heating, scarification and milling systems) all vary.
The problem is solved by a liquid distribution system using two or more positive displacement, diaphragm pumps. The pumps accurately meter light (unheated) and heavy (heated) rejuvenator fluids and liquid polymers. Ground speed sensing (distance traveled) and application rate (manually input into the on-board computer using pre-engineered data) together with asphalt volume sensing and temperature correction factors, provide accurate and consistent results, which are verifiable through laboratory testing.
7. Inaccurate and inconsistent application of the aggregate.
The present invention and methods often uses a plurality of Preheaters. Often three or more Preheaters are used, operating ahead of the AR Recycling Machine to soften the asphalt surface to a depth of 50 mm (2″) or more. The final Preheater is fitted with a rake/blade scarification/collection system and aggregate distribution system.
In prior processes, the machine's processing speed (distance traveled) is generally used to control the aggregate's distribution rate. Distance traveled, by itself, provides inaccurate and inconsistent application rates as the volume of aggregate being spread must be constantly changed as the volume of asphalt pavement being recycled constantly changes due to variations in processing depth (profile) and width.
The problem is solved by the present invention through the spreading washed aggregate (sand, small stone, steel mill slag etc.) directly on to the heated asphalt surface by an aggregate distribution bin (controlled and monitored by the onboard computer) attached to the final Preheater. Ground speed sensing and application rate (manual input into the on-board computer using pre-engineered data), together with proprietary width measurement (width of asphalt being processed) and asphalt surface profile sensing, provide accurate and consistent results, which are verifiable, through laboratory testing.
8. Improper mixing of rejuvenator fluid, washed aggregate and reworked (recycled) asphalt:
The amount of time available for mixing has until now, been inadequate to produce a homogeneous mix. To date the mixing of rejuvenator fluid and aggregates into the reworked asphalt is generally accomplished by one of the following methods:
a. The heated, milled asphalt is removed from the surface and conveyed to a pug mill on-board the recycling machine where mixing (rejuvenator fluid and aggregate) takes place as a continuous or batch process. The pug mill discharges the asphalt into the front hopper of a standard paving machine (attached to the recycling machine) or in front of the recycling machine's screed assembly for final placement and compaction. Aggregate segregation, loss of heat and emissions are all increased.
b. The recycling machine mills and collects the heated asphalt and aggregate (if added) while leaving it on the heated surface. The collected, milled asphalt/aggregate passes into an in-line pug mill or mixing auger. The pug mill or mixing auger discharge is generally unrestricted, resulting in reduced retention (less mixing) of the recycled asphalt and additives and increased segregation caused by the larger aggregate (stone) rolling down the windrow's sides.
c. Scarification systems (no mills, pug mill or other mixing devices) use cutters to penetrate into the heated asphalt's surface while aggregate and rejuvenator fluids are spread directly on to the heated asphalt. The only mixing that takes place is by the action of the cutters and to some degree, the action of the screed's distribution auger. Limited and inconsistent mixing result, as the scarified asphalt and additives are not collected and mixing by any mechanical apparatus.
The crown and curb (left and right) side, recycled asphalt, are not completely mixed together to form a homogeneous mix (only applies to processes where the asphalt is not removed from the surface). Dirty, curbside recycled asphalt will show up in the finished mat (asphalt behind the screed assembly) on the curbside section as discolored asphalt (dull, as the dirt/dust absorbs more of the asphalt's liquid). Sweeping the asphalt surface reduces the buildup of dirt and dust, but cannot remove it completely from the cracked or porous asphalt.
The fine aggregates contained in and added to the recycled asphalt remain behind the mill(s), mixing auger or pug mill (if fitted) as a fine layer on the milled surface. To obtain a homogenous mix, all of the reworked asphalt and additives require collection for mechanical mixing.
The following innovations found in the present invention increase the mixing and/or mixing time in the HIR Recycling Machine:
a. Three or more Preheaters, operating ahead of the HIR Recycling Machine softening the asphalt surface to a depth of 50 mm (2″) or more. The final Preheater is fitted with a rake/blade scarification/collection system and aggregate distribution system. The rake/blade system is the first of the processing equipment to break the heated asphalt's surface, releasing moisture (steam) and loosening the heated asphalt. The rake's carbide cutters form grooves 50 to 75 mm (2-3″) or more into which the washed aggregate (sand, small stone, steel mill slag etc.) falls. Spreading the damp aggregate on to a heated surface in a thin, ribbed layer not only allows any moisture to evaporate quickly, it also promotes greater mixing by the Recycling Machine's rakes, mills and pug mill. The deposited aggregate starts to absorb liquid asphalt from the heated asphalt (asphalt to be recycled) before being processed by the heating, milling and mixing stages.
b. The Recycling Machine's heating system (heater box) features flexible, stainless steel mesh skirts around the parameter of the heater box to retain heat. The skirts are also designed to touch (drag) the heated asphalt's surface. The front skirt spreads the aggregate (applied by the final Preheater) into a thin layer. The Recycling Machine's heater box gently applies additional heat to the spread aggregate and asphalt surface, thereby removing any remaining, trapped moisture. Excess moisture in any part of the mixing process will prevent the proper coating and adhesion of existing asphalt binders, additional rejuvenator fluid and polymer liquid to the aggregates contained in or mixed into the recycled asphalt. The rake/blade system attached to the Recycling Machine further mixes the added aggregate and heated asphalt before the milling/mixing stages.
c. The Recycling Machine's extension mill and main mill rotors (rotating carbide cutters) all feature shallow fighting designed to reduce the rotors material conveying efficiency. Attached to backside of the lighting are replaceable carbide cutting teeth and holders. The shallow lighting, together with the carbide cutters (rotating in a down-cut direction), causes the heated/milled asphalt to build up in front of the rotors rather than immediately being conveyed away. Rejuvenator fluid added at the main mill's rotor and aggregates distributed on to the heated asphalt surface, ahead of the 100% HIR Recycling Machine (by final Preheater) are continuously mixed by the main mill's carbide teeth. The main mill's material discharge is offset to one end of the rotor. The rotor provides premixing of the old (recycled) asphalt, rejuvenating fluid and aggregate before discharging into the offset front rotor of the pug mill.
d. The offset front rotor of the pug mill (receives material from the main mill's offset discharge) is equipped with carbide-faced paddles (two per arm) arranged in a spaced, spiral pattern. The spaced, spiral pattern reduces material conveying efficiency, increases dwell time and the mixing action of the recycled asphalt and additives. The spiral section of the pug mill's offset front rotor feeds the recycled asphalt and additives into the pug mill's mixing chamber. The offset front rotor is also equipped with carbide faced, paddles (two and four per arm), arranged in an alternating left and right hand pattern (located in the mixing chamber). The spiral section and the alternating paddle section of the offset front rotor receive rejuvenator fluid and if required, polymer additive. The recycling Machine's onboard computer automatically controls (stages) the application of rejuvenator fluid and liquid polymer. The main mill is the first to receive rejuvenator fluid followed by the pug mill's front rotor (spiral section) and finally the alternating paddle section of the pug mill's front rotor. Liquid polymer is only sprayed into the pug mill when rejuvenator fluid flow is established in the main mill and/or the pug mill. Staging the rejuvenator fluid's application to the processed asphalt's flow through the mills and pug mill provides increased mixing time, greater coverage and less chance of the fluid additives coming into contact with the milled, base surface. The pug mill's offset front rotor completely mixes the left and right (crown and curb) side asphalt while the pug mill's rear rotor completes the final mixing and discharge of the asphalt into a formed windrow. The pug mill's rear rotor (discharge rotor) diameter is greater than the front rotor and is equipped with carbide-faced paddles (two and four per arm) arranged in an alternating left/right hand pattern. The front and rear rotors do not intermesh, allowing the rotor speeds to be set individually for varying, asphalt specifications. Both design features increase the throughput of recycled asphalt and promote increased mixing/tumbling and moisture (steam) release.
e. An adjustable trip blade is located between the pug mill's front and rear rotor assemblies. The trip blade is the full width of the mixing chamber. The trip blade scrapes the milled, base surface, lifting any asphalt and additives missed by the front rotor assemblies paddles (the rotor paddles do not make contact with the milled base). As paddle tip wear increases the amount of asphalt missed would increase, reducing the mixing efficiency of the pug mill. Rejuvenator fluid (polymer additives were not tried) could not be sprayed into the prototype pug mill as the fluid would come into direct contact with the milled base surface in the mixing chamber and would not be collected and mixed by the rotor assemblies paddles. Bleeding of the finished mat (the width of the pug mill mixing chamber) resulted when using rejuvenator fluid. The trip blade improves mixing and allows rejuvenator fluid and polymer liquid to be sprayed directly into the pug mill's front rotor assembly. Competitive recycling machines fitted with a mixing auger or standard pug mill do not scrape the base surface in the mixing chamber or in the case of a mixing auger, the discharge section. The result is incomplete mixing, especially as rotating components wear. An external, single screw adjuster sets the trip blade's height. A hydraulic cylinder connects the trip blade to the screw adjuster. The hydraulic cylinder allows the trip blade to rotate if contact with a utility structure occurs, preventing damage to the trip blade and utility structure. The trip blade resets automatically.
f. The asphalt being discharged out of the pug mill is restricted through a variable (mechanical) opening (parallelogram ski) located behind the pug mill's rear rotor assembly. The ski is hydraulically adjustable for pre-load (vertical pressure exerted on to the asphalt windrow) and provides light compaction to the windrow and resistance to asphalt flow through the pug mill. The ski also measures the volume of asphalt exiting the pug mill and generates a proportional electronic signal used in calculating the required amount of rejuvenator fluid and polymer liquid to be added to the reworked (recycled) asphalt. Other recycling machines do not restrict the asphalt's flow to improve mixing or compact the windrow to reduce segregation.
g. Discharge from the pug mill's rear rotor is to the centerline of the Recycling Machine. Testing has shown that central discharging mills (not offset), even when used with an efficient in line pug mill or mixing auger (mixing on the milled surface) will not achieve complete crown and curbside mixing of the asphalt/additives into a homogeneous mix. The offset main mill's rotor assembly together with the pug mill's offset front rotor and rear rotor assemblies, completely mix the crown and curbside asphalt into a homogeneous mix.
h. Spring loaded (floating) blades located behind the extension mills, main mill and pug mill collect the fine aggregates and fluid additives by scraping the milled surface. The blades (replaceable) are adjustable in height to compensate for blade wear and carbide rotor teeth (replaceable) wear. The springs keep the blades forced down on to the milled surface and also provide protection against damage to iron utility structures by allowing the blades to ride up and over the utility structure. Scraping the milled, asphalt surface collects the finer aggregates and liquid additives, thereby producing a consistent and homogeneous asphalt mix. Other recycling machines generally use fixed blades or no blades, resulting in a remaining layer of fine aggregates and liquid additives on the milled surface. Liquid additives remaining in direct contact with the milled surface produce bleeding of the finished mat (streaks).
9. Inability to remove moisture from reworked asphalt
Moisture removal in prior systems is limited due to inadequate heat penetration, insufficient mechanical mixing and the lack of moisture extraction systems. The positive removal of moisture (steam) at the mills and pug mill or mixing auger is generally, not used.
Moisture removal in the present invention may be done in four stages:
a. Three or more Preheaters, operating ahead of the Recycling Machine softening the asphalt surface to a depth of 50 mm (2″) or more. The final Preheater is fitted with a rake/blade scarification/collection system. The rake/blade system is the first of the processing equipment to break the heated, asphalt surface, releasing moisture (steam) and loosening the asphalt without damaging the asphalt's larger aggregate. The rake's carbide cutters are hydraulically adjustable for down force (pressure compensated), are spring-loaded and mounted on pivoting frames, allowing the cutters to follow varying pavement profiles and scarify around iron utility structures. Penetration into the heated asphalt is generally deeper than the Recycling Machine's main and extension mill profiling depth. The Preheater's rake/blade carbide cutters loosen the asphalt, allowing the trapped moisture (steam) to release before further scarification, milling and mixing by the Recycling Machine's rakes, mills and pug mill.
b. The Recycling Machine's electronically controlled and monitored heating system produces convection and infrared heating and is used to drive off any remaining moisture in the added aggregate (damp, washed sand, deposited on to the heated asphalt by the final Preheater's aggregate distribution system). The Recycling Machine's rakes/blades are identical in design and operation to the Preheater's rakes/blades and produce further mixing of the aggregate into the heated asphalt. The rakes also cut deeper into the loosened asphalt, releasing more moisture in the form of steam.
c. Automatic grade/slope sensors control the depth of cut of the extension and the main mills. The mills mill and tumble the loosened, heated asphalt, mixing additives and releasing steam. A venturi (using the heater box blower air supply to create a negative air pressure) draws steam through the main mill's enclosed support frame, venting it to the top of the Recycling Machine.
d. The offset pug mill is fitted with a moisture extraction system. A venturi (as above) creates a negative air pressure in the pug mill's mixing chamber. The pug mill's front and rear rotors tumble and mix the restricted asphalt enclosed in the mixing chamber. The air extraction system reduces the moisture level in the reworked (recycled) asphalt by drawing off and venting the released steam to the top of the Recycling Machine.
10. Inconsistent depth differential between the 100% recycled asphalt and the new asphalt when using the integral overlay method.
Integral Overlay recycling machines have been around for many years. They are popular with contractors as the new asphalt can be used to hide the poorly recycled asphalt below and still produce a very good looking, new surface that generally stands up well over time. It is possible to hide all sorts of imperfections, as it is difficult to sometimes see the recycled surface as the secondary screed assembly is laying new material directly on to it. However, in prior systems and processes, three major problems are generally encountered:
a. The quality of heat produced by the preheaters and the recycling machine are incapable of producing a deep penetrating heat, without setting the asphalt's surface on fire.
b. The recycled asphalt could not be processed using pre-engineering specifications as the machine was manually operated with no on-board computers to monitor and control the recycling process.
c. The depth differential between the recycled asphalt and the new asphalt was inconsistent.
The following innovations of the present invention allow the Recycling Machine with Integral Overlay to 100% recycle existing asphalt while laying a high quality, new asphalt surface to grade, while meeting the smoothness tests.
The Recycling machine is equipped with the same, two grade control systems, as described earlier on.
The front asphalt hopper and central belt conveyor are the same as for 100% HIR method, except that a short, shuttle conveyor is used to supply new asphalt to the rear, secondary auger and screed assemblies. The level of asphalt in the secondary auger and screed assembly controls the asphalt's flow from the front hopper and central belt conveyor assemblies. A proportional, electronic sensor (located in the feed chute used to supply asphalt to the secondary auger) signals the on-board computer to speed up the front asphalt hopper's and central belt conveyor's discharge rate. The position of the shuttle conveyor can be manually, or, automatically controlled by the on-board computer allowing new asphalt (delivered by the central conveyor) to spill into the primary auger/divider/strike off blade assembly when insufficient recycled asphalt is available to maintain the correct head of asphalt in front of the primary screed assembly. The design of the shuttle conveyor allows new asphalt to be delivered to both the primary and secondary auger and screed assemblies at the same time.
The primary auger/divider/strike off blade is identical in operation and control, as described earlier on.
The primary and secondary screeds are attached to the Recycling Machine's mainframe by screed arms attached to a left and right side adjustable tow points in the same manner as described earlier. The only difference being the length of the screed arms used on the primary and secondary screeds.
The major difference is in the control of the primary and secondary screed's grade and slope control system. Both the primary and secondary screed arms are attached to the same tow point (one on either side of the machine,) which can either be pinned into position, or controlled by the automatic grade control system, as described earlier. Topcon's Smoothtrack® 4 Sonic Tracker II™ averaging beams and electronic slope sensor are again used, as described earlier, however the averaging beams and electronic slope control are only attached to the secondary screed's (rear screed) screed arms. The secondary screed assembly is allowed to float and features the same weight transfer system, as described earlier. The primary screed assembly requires no grade, or slope controls and is also allowed to float, but not to the same degree as the secondary screed assembly. The primary screed assembly senses the position of the secondary screed assembly through two, proportional, electronic or hydraulic sensors. The sensors are attached to the left and right side of the secondary screeds tow arms and sense the position of the left and right side of the primary screed's tow arms. The height of the sensor plates can be adjusted to set the height differential between the primary and the secondary screed assemblies, which is generally ½″ to 1½″. The two screed sensors send information to the on-board computer, which in turn, operates two hydraulic, 4 way proportional, directional control valves. The secondary screed assembly is the master while the primary is the slave and tries to match every move made by the secondary screed assembly (master). To accomplish this the primary screed assembly is attached to the Recycling Machine's mainframe by two identical, hydraulic cylinders, used to attach the secondary screed to the mainframe. The four hydraulic cylinder's prime function is to raise and lower both screed assemblies. The secondary screed assembly cylinders are allowed to float (move up and down freely) as all of the cylinder's hydraulic ports are connected to tank (return) when laying asphalt. The primary screed assembly cylinders are also allowed to float; however the hydraulic cylinder's ports are connected to tank through flow control valves. The system works in the following manner: At the start of the recycling operation the Recycling Machine is backed up to the previously finished joint that has been preheated. The secondary screed assembly is lowered on to starting blocks and the screed cranks are nulled out (neutralized) and set. The primary screed assembly is lowered on to the asphalt's surface and the screed cranks are nulled out and then given one turn up, to slightly raise the front of the screed's plates. This setting will allow the screed assembly to automatically rise when asphalt builds up in front of the screed. The machine operator places the Recycling Machine into automatic mode, allowing the on-board computer to monitor and control all of the automatically programmed operations. Asphalt is delivered from the front asphalt hopper, by the central conveyor to the shuttle conveyor. The shuttle conveyor supplies asphalt to the secondary screed augers. The augers feed the asphalt out to the ends of the secondary screed's extensions until the electronic asphalt sensors, attached to the screed extension's end plates stop the augers (the asphalt is at the correct level). Once the secondary auger and screed assemblies have been fully supplied with new asphalt the on-board computer moves the shuttle conveyor allowing new asphalt to spill into the primary auger/divider/strike off blade assembly. New asphalt will be delivered until the electronic asphalt sensors, attached to the primary screed extension's end plates stop the augers (the asphalt is at the correct level). At this position the secondary screed assembly is at a higher position than the primary screed assembly. The secondary screed's tow arm sensors are signaling the on-board computer to power the two proportional, directional control valves that send hydraulic oil to the primary screed's two hydraulic cylinders. The primary screed assembly is trying to be raised by hydraulic pressure, however this is not possible, as the hydraulic pressure is set at a low pressure, preventing the screed assembly from being raised. The operator then puts the processing equipment (scarification rakes, mills, pug mill, rejuvenator and heating system) into operation and moves the Recycling Machine briskly away, preventing the secondary screed from settling into the new asphalt while the primary screed assembly rises due to the asphalt in front of the screed assembly and also the limited hydraulic pressure trying to lift the screed. The front asphalt hopper will automatically provide new asphalt, on demand, to the primary and secondary screed assemblies. As the Recycling Machine starts to 100% recycle and rejuvenate the heated asphalt, as discussed previously, the primary auger/divider/strike-off plate begins to split and convey the windrow of 100% recycled asphalt, out to the primary screed's extensions. As the primary screed was rising, hydraulic oil was being forced out of the partially restricted cylinders through the cylinder's head end ports and flow control valves. The oil being supplied from the proportional valves (variable flow controlled by the sensor's outputs) to the rod end of the cylinders is also flowing through the rod end, flow control valves. The greater the flow of hydraulic oil from the proportional valves, the greater the differential in pressure across the flow control, valves. The screed sensors will eventually turn off the proportional valves when the primary screed assembly reaches the set point (differential height). The control of the system is to slowly change the forces working on the primary screed assembly, keeping it at the set, height differential. The sensors only respond when the primary screed tries to move away from the set differential. An example would be when the head of asphalt in front of the primary screed increases as the Recycling Machine mills through a high section. The primary auger/divider/strike off blade would hold back and control most of the mass, however there will be more asphalt reaching the screed (due to the pressure of the buildup), which will causes the screed to rise. When the reverse happens (lack of material), the screed will sink. As noted before the hydraulic pressure is too low to keep the screed raised and at the correct level. This is not a problem, as the secondary screed will continue to set the correct grade by laying a greater amount of new asphalt. This condition will rarely occur as the on-board computer monitors the primary auger/divider/strike off blade's individual auger's speeds and allows the shuttle conveyor to spill extra, new asphalt into the augers, maintaining the head of asphalt in front of the primary screed assembly. When using the Integral Overlay process, the primary screed assembly should be prevented from exceeding the height of the secondary screed. If this were allowed to happen, the 100% recycled asphalt would replace the new asphalt. To prevent the primary screed assembly from getting into this position the hydraulic pressure used for down force on the primary screed's hydraulic cylinders is set to a higher pressure than the pressure used to raise the screed assembly. This is possible as the Recycling Machine is heavy and will not by lifted by the pressure in the primary screed's hydraulic cylinders.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other features, objects and advantages of the present invention will become apparent from the following description and drawings wherein like reference numerals represent like elements in several views, and in which:
FIG 1 a side view of the 100% HIR Recycling Machine and Preheater in the working mode
FIG. 2 a side view of the 100% HIR Recycling Machine showing major sub-assemblies
FIG. 3 a side view of the Preheater showing major sub-assemblies
FIG. 4 a plan and end view of the Recycling Machine's heater box and suspension
FIGS. 5A, 5 B end views showing the Recycling Machine's heater box extension air supply pivot
FIGS. 6A, 6 B, 6 C front, cross-section and plan views of the Recycling Machine's electronic burner
FIG. 7 a plan view of Recycling Machine's main heater box and extension burner layout
FIG. 8 a side view of the Recycling Machine's offset boom and cab
FIG. 9 a plan view of the Recycling Machine's offset boom and cab
FIG. 10 an end view of the Recycling Machine's rear axle assembly
FIG. 11 a plan view of the Recycling Machine's front and rear axle assembly
FIG. 12 an end view of the Recycling Machine's front axle assembly in a tilted position
FIGS. 13A, 13 B side views of the Recycling Machine's grade control system for the main and extension mills
FIG. 14 a plan view of the Recycling Machine's grade control system for the main and extension mills showing the transversal, jointed cross beam
FIG. 15 a side view of the Recycling Machine's, mill grade control system
FIG. 16 an exploded side view of the Recycling Machine's, mill grade control system
FIG. 17 an end view of the Recycling Machine's, mill grade control standard two ski assembly
FIG. 18 an end view of the Recycling Machine's, mill grade control transverse averaging ski assembly
FIG. 19 a side view of the Recycling Machine's, mill grade control longitudinal averaging ski assembly
FIG. 20 a side view of the Recycling Machine's, mill grade control longitudinal averaging ski assembly with non-contact, sonic sensors
FIG. 21 an end view of the Recycling Machine's, mill grade control system with a single ski assembly and cross slope sensor
FIG. 22 a side view of the Recycling Machine's asphalt surge bin and vertical elevator
FIG. 23 an end view of the Recycling Machine's asphalt surge bin and vertical elevator
FIG. 24 a side view of the Recycling Machine's, hopper/diverter valve
FIGS. 25A, 25 B, 25 C side views of the Recycling Machine's, hopper/diverter valve shown in three modes of operation
FIG. 26 a side view of the Recycling Machine's auger/divider/strike-off blade assembly
FIG. 27 a plan view of the Recycling Machine's auger/divider/strike off blade assembly
FIG. 28 an end view of the Recycling Machine's auger/divider/strike off blade assembly
FIGS. 29A, 29 B plan views of the Recycling Machine's auger/divider/strike off blade assembly showing the divider in two positions
FIG. 30 a side view of the Recycling Machine fitted with a front asphalt hopper, central belt conveyor and asphalt surge bin/vertical elevator
FIG. 31 a simplified side view of the Recycling Machine fitted with a front asphalt hopper, central belt conveyor and asphalt surge bin/vertical elevator
FIG. 32 a side view of the Recycling Machine and front asphalt hopper assembly and central belt conveyor in the raised position
FIG. 33 a side view of the Recycling Machine and front asphalt hopper assembly and central belt conveyor in the lowered position
FIGS. 34A, 34 B, 34 C side views of the Recycling Machine's front asphalt hopper assemblies clip-on attachment frame and safety locks
FIG. 35 a side view of the Recycling Machine's central belt conveyor assembly
FIG. 36 a side view of the Recycling Machine's automatic belt tension assembly
FIGS. 37A, 37 B, 37 C a side, plan and end view of the Recycling Machine's rake scarification/blade collection assembly
FIG. 38 a side view of the Recycling Machine's rake scarification/blade collection assembly with a main rake/blade in the lowered position
FIG. 39 a side view of the Recycling Machine's rake scarification/blade collection assembly with a main rake/blade in the lowered position with the blade collecting asphalt
FIG. 40 a plan view of the Recycling Machine's rake scarification/blade collection assembly with a main rake/blade showing a utility structure
FIG. 41 a plan view of the Recycling Machine's extension mills, main mill and pug mill showing the flow of asphalt when processing
FIG. 42 an end view of the Recycling Machine's extension mills with one extension mill crowned
FIG. 43 an end view of the Recycling Machine's extension mill with spring loaded blade in the full down position
FIG. 44 an end view of the Recycling Machine's extension mill with spring loaded blade in the full up position
FIG. 45 an end view of the Recycling Machine's main mill
FIG. 46 a plan view of the Recycling Machine's main mill showing asphalt discharge
FIG. 47 an end view of the Recycling Machine's main mill with spring loaded blade in the normal working position and also the rejuvenator spray bar
FIG. 48 a schematic of the Recycling Machine's rejuvenator and supplemental liquid distribution system
FIG. 49 a plan view of the Recycling Machine's extension mills, main mill and pug mill showing the rejuvenator/liquid polymer spray bars
FIG. 50 a side view of the Recycling Machine's pug mill assembly
FIG. 51 an end view of the Recycling Machine's pug mill assembly
FIG. 52 a plan view of the Recycling Machine's pug mill showing the front and rear rotor assemblies
FIG. 53 a plan view of the Recycling Machine's pug mill showing the inlet and outlet of asphalt
FIG. 54 a side view of the Recycling Machine's pug mill with ski assembly at rest
FIG. 55 a side view of the Recycling Machine's pug mill with ski assembly in the raised position
FIG. 56 a end view of the Recycling Machine's pug mill with ski assembly at rest showing the electronic, rotary sensor
FIG. 57 a side view of the Recycling Machine's pug mill with trip blade
FIG. 58 a side view of the Recycling Machine's pug mill with trip blade in the tripped position
FIG. 59 a side view of the Recycling Machine's pug mill showing an exploded view of the trip blade
FIG. 60 a side view of the Recycling Machine's front asphalt hopper fitted with a metal detection boom assembly
FIG. 61 a plan view of the Recycling Machine's rake/blade and metal detection boom assembly
FIG. 62 an end view of the Preheater's aggregate distribution bin and width measuring system
FIG. 63 a side view of the Preheater's aggregate distribution bin
FIG. 64 a side view of the Preheater's aggregate distribution bin showing a spring loaded blade in the normal position
FIG. 65 a side view of the Preheater's aggregate distribution bin showing a spring loaded blade in the open position
FIG. 66 a side view of the Preheater's aggregate distribution bin and asphalt surface profile measuring system
FIG. 67 a side view of the Recycling Machine showing the major sub-assemblies used with the 100% HIR with Integral Overlay method
FIG. 68 a side view of the Recycling Machine's rear end showing the major sub-assemblies used with the 100% HIR with Integral Overlay method
FIG. 69 a side view of the Recycling Machine's rear end showing the primary and secondary screed assemblies and tow arms
FIG. 70 a cross section view of the Recycling Machine's secondary screed arm hydraulic cylinder
FIGS. 71A, 71 B side views of the Recycling Machine in the highway transportation mode
FIG. 72 a side view of the Recycling Machine's clip-on, front transportation stinger assembly retracted
FIG. 73 a side view of the Recycling Machine's clip-on, front transportation stinger assembly extended
FIG. 74 a side view of the Recycling Machine's clip-on, front transportation stinger assembly exploded
FIGS. 75A, 75 B side views of the Recycling Machine's clip-on, front transportation stinger showing the clip-on frame and safety latches
FIG. 76 a side view of the Recycling Machine's clip-on, rear transportation frame assembly
FIG. 77 a side view of the Recycling Machine's clip-on, rear transportation frame assembly in a forward position
FIG. 78 a side view of the Recycling Machine's clip-on, rear transportation frame assembly showing the safety latches
FIG. 79 a side view of the Recycling Machine with a clip-on, rear transportation frame and front asphalt hopper assembly in the highway transportation mode
FIG. 80 a side view of the Preheater with a clip-on, rear transportation frame and front stinger assembly in the highway transportation mode
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Set forth below is a description of what are currently believed to be the preferred embodiments or best examples of the invention claimed. Future and present alternatives and modifications to the preferred embodiments are contemplated. Any alternates or modifications in which insubstantial changes in function, in purpose, in structure or in result are intended to be covered by the claims of this patent.
FIGS. 1-3 show a Recycling Machine 1 configured for 100% HIR and a Preheater 2 (only one shown), both shown in the working mode. A plurality of Preheaters may be used within three or more Preheaters typically being located ahead of the Recycling Machine. The Preheaters are responsible for delivering deep, penetrating heat into the asphalt. Preheaters not fitted with a clip-on aggregate bin 21 and the rake/blade scarification/collection system 11 can be fitted with an optional thermal insulation blanket, around the edges (not shown) which is used to reflect heat into the heated asphalt surface and shield the asphalt from the cooling effects of wind. The final Preheater (shown ahead of the Recycling Machine) is fitted with an on-board computer-controlled, aggregate distribution bin and rake/blade scarification/collection system. Aggregate, such as washed sand is added in controlled proportions (determined by prior testing of the asphalt) and adjusts the air-void ratio and the structural properties of the recycled asphalt. It is also possible to add combinations of aggregates by premixing or by fitting more than one Preheater with aggregate distribution bins. The Recycling Machine and Preheaters are fitted with main heater boxes 4 . Attached to the main heater boxes are the left and right side hydraulically operated, extension boxes, which provide on the go, variable heating width adjustment. The fuel is clean burning propane and is mixed with pressurized air in individual, electronically monitored and controlled burner assemblies. The air pressure, burner operation, heat shutdown and emergency heat shutdown is monitored and controlled by the on-board computer for safety and efficiency. The burners produce infrared heat (stainless steel cones and underside stainless steel mesh glow red) and forced hot air to heat the asphalt. The burner flame is of the high swirl type (flat flame) and does not contact the asphalt's surface. The spacing of the machines allows the heat to soak (penetrate) into the asphalt. Close spacing provides high surface heat, but less depth of heat. Spacing the machines further apart, can in some conditions, increase the depth of heat into the asphalt, however, in windy, cold or damp conditions, reduced depth of heat can result. Insulation blankets are available (mounted behind the Preheaters) to reduce the heat loss to the atmosphere and increase the heat penetration into the asphalt. Electronic monitoring and control of the heater boxes on the Preheaters and Recycling Machine provides automatic heat control.
Preheater 2 is shown in FIGS. 1 and 3 fitted with the clip-on aggregate bin 21 and rake/blade scarification/collection system 11 , 12 and 13 . The mainframes 3 , on both machines are fabricated out of carbon rectangular steel tubing with the main tubes forming air plenums. Pressurized air, supplied by a hydraulically driven, variable speed centrifugal blower (monitored by an electronic pressure sensor) maintains the mainframe's 3 tubes (plenum) at a constant pressure. The on-board computer controls a hydraulic, variable displacement, piston pump (driven by the diesel engine) using information provided by the air plenum's electronic pressure sensor. The pump provides oil flow to the air blower's hydraulic drive motor. Air pressure remains constant as ambient temperature, air density, altitude or air demand (volume) change. Changes in air demand occur as the extension boxes are raised and lowered. Raising the extension boxes automatically cuts off the air supply, reducing the required blower volume. The Preheater's main heater box 4 attaches to the main frame 3 by eight equally spaced pivoting links 5 . The pivoting links allow the heater box to thermally expand while also allowing the mainframe 3 to structurally support the heater box 4 . The air supply to main heater box 4 from mainframe 3 is by four equally spaced, flexible hoses (not shown). As shown in FIG. 2, the Recycling Machine's main heater box 4 attaches to the mainframe 3 by four hydraulic cylinders and a suspension system 6 , allowing the heater box to raise/lower, tilt and side shift. Propane tanks 7 , on both of the machines are industry standard, mobile units fitted with fluid withdrawal from the tank bottom and vapor withdrawal from the top. Heated vaporizer(s) vaporize the liquid propane while a single stage regulator reduces the gas pressure for the burner's supply. Regulated vapor pressure (top of the propane tank) supplies the burners at a slightly higher pressure than set by the single stage regulator, thereby providing propane vapor discharge priority and reducing excessive tank pressure in high ambient temperatures. The Recycling Machine and Preheater both feature four wheel drive supplied by hydraulic, radial piston motors, driving wheels 8 while providing infinite speed in both directions. The drive wheels 8 steer 40 degrees to the left and right (front and rear) on both of the machines. Hydraulic booms 9 fitted to both machines allow the operators to move around the rear end of the machines for better viewing. The Preheater's boom allows a wheel loader to dump aggregate into the aggregate bin 21 with the boom swung completely to curb side for traffic safety. Cab 10 , attached to boom 9 are fitted on both machines and house the operator controls station (electronic) and machine monitoring readouts.
FIG. 2 illustrates the Recycling Machine's 1 sub-assemblies (described later, in detail) which comprise extension rakes 11 , main rakes 12 , rake blades 13 , extension mills 14 , main mill 15 , offset pug mill 16 , surge bin/vertical elevator 17 , auger/divider/strike-off blade 18 and screed/tow arms 19 . Stinger 20 hydraulically extends and retracts from the main frame 3 , reducing the Recycling Machine's length, while in the working mode. The Recycling Machine can also be fitted with an optional clip-on, front asphalt hopper with a 5 th wheel pin attachment. Either attachment allows towing by a highway truck tractor, without the removal of the front end, attachment. The Preheater's stinger 20 also allows towing by a highway truck tractor. The rear end of the Recycling Machine 1 and Preheater 2 mainframes 3 feature attachment tubes 22 allowing clip-on transportation frames (described in detail later) to be attached for highway transportation. The Recycling Machine and Preheater's sub-assemblies and/or clip-on attachments can be removed or left in-place for transportation. Attachments left in-place for transportations are also fitted with attachment tubes 22 as shown in FIG. 3 on the Preheater's aggregate bin 21 .
In summary, both machines feature a commonality of parts and systems, allowing for interchangeability of components for transportation, service and manufacturing.
The Recycling Machine's and the Preheater's heater boxes are basically the same in construction and operation, however, the Recycling Machine's heater box will be described in detail due to additional features, such as hydraulic raise/lower, tilt and side shift as shown in FIGS. 4 and 5. The Recycling Machine's heater box consists of the main box 30 and the left and right extension boxes 31 (only the R.H. one is shown on the plan view). The extension boxes are used to increase the heating width of the Recycling Machine as it is processing asphalt. FIG. 4 shows the plan and front view with the left extension in the raised (transport) position and the right extension in the lowered, heating position. The two extension boxes 31 are supported and pivot on frames (two) 32 . Frames 32 also supply air to the individually controlled, electronic burners 35 , located on both the main and the extension boxes while gas supply tubes 33 supply propane to the burners. The middle support frame 34 spans the three gas tubes 33 and provides support for the main box's top deck.
FIG. 5 shows the extension box's frame/air tube 36 in both the raised and lowered (heating) position. The stationary pivot 37 is attached (bolted) to the main box's frame 32 . Frame/air tube 36 and has two rectangular air passages (“A” and “B”) located in the rotating pivot. Passage “A” (rotating pivot) is connected to the burner's air supply tubes while passage “B” (rotating pivot) slides past passage “C” in the stationary pivot 37 . When the extension box 31 is in the raised position passage “C” is blocked. In the lowered (heating) position passages “B” and “C” are aligned, allowing air to flow into the extension frame's air supply tubes 36 through passage “A”. The stationary pivots 37 allow the extension boxes 31 to be raised and lowered by hydraulic cylinders 38 that are attached between the middle support frame 34 and the extension frame 36 and also provide automatic air control to the extensions, reducing air consumption, by shutting off the air supply when the burners are not required. Electronic sensors detect the extension box's 31 position. The on-board computer automatically cuts off the gas supplies when the boxes are raised 10 degrees from heating position. As noted above, the main heater and extension boxes are constructed from rectangular steel tubing. The tubing is used to distribute propane and air to the individual burners. Passing propane and air through the tubes reduces weight, plumbing complexity and increases the surface area on propane delivery system, allowing the propane to completely vaporize, particularly in cold weather. Preheaters have their heater boxes mounted through equally spaced links 5 attached to the mainframe. The mainframe provides the structural rigidity to the heater box. The heater box and mainframe are raised, lowered and tilted using the Preheater's front and rear axle's, hydraulic cylinders. The Recycling Machine's main heater box 30 and extension heater boxes 31 , are raised, lowered and tilted by four (two per side) individual, hydraulic cylinders 39 that are mounted to the support frame 40 and the sliding suspension tube 41 . The two left and the two right cylinders are hydraulically plumbed in parallel, allowing each side to be raised individually (tilt) or together. Cylinders 39 are in compression (rod being forced into the cylinder) when carrying the weight of the heater box and together with hydraulic counterbalance valves prevents the box from drifting down (anti-drift) which allows the height of the box to be set and maintained at any position. The sliding suspension tubes 41 are raised and lowered by hydraulic cylinders 39 and slide through the support frame 40 . The suspension tubes 41 are attached to frames (two) 42 through universal joints, allowing movement for tilt and misalignment. Two hydraulic cylinders 43 are attach between frame 32 and frames 42 . The hydraulically cylinders are connected in parallel and are equalized in hydraulic flow, allowing the frames 32 (attached to main heater box) to slide through frames 42 , side shifting the heater box for operation around tight bends or for offset heating. The frames 42 receive air from the Recycling Machine's mainframe 3 through four flexible hoses (not shown). The hoses function as a flexible joints and also weak links (fuses), protecting against the unlikely event of combustion blow back. The on-board computer, providing for safety and efficiency, controls the air/fuel mixture, as well as the ignition and shut down. The electronically monitored and controlled burners 35 receive their air supply from frames 42 and their gas supply from tubes 33 . The on-board computer automatically controls the air pressure. The electronically controlled burners 35 produce infrared heat, (stainless steel cones glow red) and hot forced air to heat the asphalt. The stainless steel mesh 44 (heated by burners 35 ), also produces infrared heat, while flexible stainless steel wire mesh skirts 45 , surround the perimeter of the heater boxes, containing the heated air. Ceramic fiber insulation 46 surrounds the burner cones and is packed between the mesh 44 and the heater boxes top deck. The burner's flame features a flat, high swirl pattern, with no flame contact with heated surface. The burners are non-adjustable (only for initial setup) and are set up to provide a blue flame for reduced emissions and greater fuel economy.
FIG. 6 show the individually controlled, electronic burner 35 and the stainless steel cone 47 . The burners 35 are attached to the heater box's top decks by studs and lock nuts, which are part of cone 47 . Heat resistant gaskets insulate the cones and burners from the deck, reducing the amount of heat transfer to deck's surface. Combustion air enters the burner through inlet 48 (“A”) and flows around air plenum housing 49 , and venturi tube 50 . Plenum “B” causes the air supply to continuously spin, due to the offset (tangential) inlet 48 (“A”). The spinning air is forced past vanes 51 in venturi tube 50 , which has a section of reduced area “C” near its outlet to increase the air's velocity. This increases combustion efficiency. The section of reduced area “C” creates a venturi, which increases the air's velocity and causes a pressures drop, at the propane's 360 degree, supply orifice “G”. Propane enters the burner at “D”, through collar 52 and passes down between the gas tube 53 and the retainer tube 54 and exits through holes “E”, filing the surge chamber in inner tube 55 . The venturi plate 56 and the inner tube 55 are spaced apart by stainless steel wires 57 , forming a 360-degree orifice “G”. The reduced area “C” increases the air's velocity and together with the spinning air and 360 degree propane supply, produce an efficient, clean flame that clings to the burner cone's 47 , inside wall. The propane is completely burnt within the top 4 inches of the cone 47 , causing the cone to glow and producing infrared heat. The heat of combustion provides additional heat and drives away any moisture from under heater boxes through the heater box's flexible side skirts. Thermocouples (not shown) positioned at various locations throughout the heater box's underside, monitor the heater box's heat output. Electronic flame detectors (not shown) monitor the asphalt's surface for local flame propagation. Each burner senses the surrounding heat at thermocouples 58 that is centrally located in the retainer tube 54 and attached to the burner cone 47 . The on-board computer receives information from each burner's thermocouples and controls the operation of the electrical gas valve 59 and the air control solenoid 60 . Solenoid 60 is attached to link 61 and together, rotates butterfly valve 62 , which in turn opens, or closes the air supply. Opening valve 59 allows propane (regulated at constant pressure) to flow through the tube 63 to trimmer valve 64 . Trimmer valve 64 is used for the initial setup of gas flow (air/fuel mixture). The burner's internal parts can be disassembled and cleaned by undoing the retainer nut 65 .
In addition, the temperature of each heater may be controlled by the use of pulsing the fuel provided to the burner. This may be done by pulsing the electrical gas valve 59 to open and close as desired or by using a variable control valve.
As shown in FIG. 7 the electronically controlled burners 35 feature left and right rotating air flows and are mounted to the heater boxes in a specific pattern, giving excellent heat coverage and heated air flow patterns. The main heater box is a two stage heating system. Under low heating requirements, (determined by the on-board computer) the main burners “A” and extension burners “C” (if extension (s) are energized) are operational. Gas supply to the “B” burners is shut-off by electrical gas valves 59 , however, the air supply remains on, providing cooling for the “B” burners. The on-board computer turns on the “B” burners when extra heat is required (as described in detail before). The onboard computer monitors each of the individual burner's thermocouples 58 and local flame detectors (not shown) and turns off the individual burner's gas supply when excessive, localized heat or flame is detected, such as crack filler or a paint lines flaring up. The solenoid 60 , link 61 and butterfly valve 62 shut off the air supply for re-ignition when the burner has automatically shut down. The electronic ignition system (not shown) fires the spark plug 63 , when the gas valve 59 turns on. The reduction of air (valve 62 closed) and the excess of propane gas produce a rich mixture at the orifice's 360 degree, discharge area “G”, allowing the spark plug 63 to ignite the propane rich mixture. Once the heater boxes have reached their operating temperature (burner cone 47 glowing) ignition will take place without the use of the spark plug, however, the plug still fires as an added margin of safety
FIGS. 8 and 9 show the (Reference FIG. 2) Recycling Machine's mainframe 3 and operators cab 19 and offset boom assembly 9 . This design allows not only the transportation frame to be attached easier, but also affords better access for the wheel loader when filling the aggregate bin. Pivot frame 70 is attached to the mainframe's top tube 22 on the left or the right hand side. Raising and lowering of the boom and cab assemblies is achieved by rotating pivot frame 70 around the mainframe's top cross tube 22 by hydraulic cylinder 71 . The boom height is restricted, preventing contact with power lines. Hydraulic counterbalance valves are fitted to the hydraulic cylinder 71 to prevent hydraulic drift. The boom's outer frame 72 is attached to the pivot frame 70 by pin 73 . The boom's outer frame 72 houses the inner, sliding tube 74 . The cab 19 is attached to the inner tube 74 by pivoting link 75 . The hydraulic cylinder 76 swings the boom and cab, allowing the operator to work from both sides of machine, while remaining out of way of screed operator and other ground personal. The hydraulic cylinder 77 slides the inner, sliding tube 74 through the outer frame 72 , extending the boom and cab. The Preheaters are fitted with a similar boom and cab assembly, the only difference being, a longer inner, sliding tube 74 . The boom's outer frame 72 is constructed to form a lower, enclosed channel 78 for the passage and protecting of the electrical and hydraulic hoses.
FIGS. 10, 11 and 12 show the Recycling Machine's front and rear axle assemblies and drive wheels 8 . The axle assemblies are hollow to create a passage 80 (area “A”). The passages or opening allow the passing of a central belt conveyor through both axles and a clip-on, hydraulic stinger/5 th wheel pin 20 (hooks up to a highway, truck tractor unit for self-transportation) to pass through the front axle FIG. 12 . The conveyor may be any conveying system known to those of skill in the art including, but not limited to, belts, chains, augers, slats, air-conveyance, liquid conveyance, and vibrating troughs. Both axles are raised and lowered by hydraulic cylinders 81 . The cylinders are attached to the front and rear axle's support frames 82 , both of which are attached to the Recycling Machine's mainframe 3 . The front axle's hydraulic cylinders are hydraulically connected in parallel, allowing the front axle's frame 83 to slide up and down the support frame 82 . The pivoting slider 84 (shown in tilted position) is attached to the support frame 82 by pin 85 and locates (prevents side to side movement while allowing the axle to tilt) the axle's frame 83 in support frame 82 . The slider also prevents the axle's frame 83 from bending in at its top section due to the natural bending moment when carrying the weight of the Recycling Machine. Hydraulic cylinders 81 are angled to help counter the bending forces on the axle's support frame 83 . Oil transfer between the hydraulic cylinders allows the front axle to tilt (follow ground surface) on the pivoting slider 84 without adversely effecting, the main frame's height. An electronic position sensor maintains the front axle's height position, relative to the position of pivoting slider 84 . This is used when lowering the front end of the Recycling Machine's mainframe (lower limit) and also prevents oil leakage in the hydraulic cylinders from causing the front end to settle over time. The electronic position sensor detects any relative change in height and signals the on-board computer to supply more or less hydraulic oil to the front cylinders, thereby raising or lowering the mainframe and cutting off the sensors signal. The rear axle assembly FIG. 10 slides up and down the pivoting slider 84 by the same manner as the front axle assembly. Oscillation of the pivoting slider 84 is around pin 85 allowing the mainframe 3 to be tilted in relation to the rear axle assembly. The rear axle's hydraulic cylinders 81 are operated individually by (hydraulic or electronic) automatic height controllers (two) or by the operator to control the mainframe's height and tilt (slope). Equal flow to both cylinders causes the rear axle's frame 83 to slide past the pivoting slider 84 causing the Recycling Machine's mainframe to raise or lower, but not tilt. Greater flow to one or the other cylinder causes the pivoting slider 84 to pivot around pin 85 , tilting the mainframe assembly. In normal operation it is the front axle assembly that automatically tilts (floats) due to the varying grade of the asphalt's surface, while the Recycling Machine's main frame stays level, due to the control of the rear axle's cylinders. Both of the pivoting sliders 84 are located below the mid-point of frames 82 to reduce the side-to-side movement of the front and rear axle frames 83 . This provides side clearance for the central conveyor. The automatic slope control systems as described in detail above can be used to control the Recycling Machine's mainframe cross slope. Individual control of the rear axle's hydraulic cylinders, together with the front axle's hydraulic cylinders connected hydraulically, in parallel, form a three-point suspension, allowing the mainframe to ride over uneven surfaces, thereby reducing stress in the mainframe. Machine operation is stable as the rear wheels are operating on a milled to grade surface, controlled by automatic grade controls. As mentioned earlier, the front axle's frame FIG. 12, 83 is designed to allow a centrally located conveyor and transportation stinger (5 th wheel pin, not shown) to pass through its center section 80 (area “A”) allowing the axle to raise, lower and tilt the mainframe. The rear axle's frame FIG. 10, 83 is configured to create a space which allows the pug mill's discharge (asphalt windrow) to pass under the frame (area “B”) and conveyor to pass over the top (area “A”). Future front clip-on units will be able to receive products consisting of granular, liquid or a mixture of both. Products will be metered and controlled by the on-board computer. Products will be conveyed to the rear of Recycling Machine for complete mixing by the main mill and/or the pug mill. The conveying of materials will be by chain conveyor, belt conveyor, auger, liquid, (wet line) or air conveyance. All conveying systems are designed to pass through the front axle and if required, the rear axle.
Both axles are fitted with steering hubs 86 , tag link 87 , and steering cylinders 88 . The steering hubs 86 pivot 40 degrees in both directions, around axle kingpins 89 , bushing 90 and thrust bearing 91 . The tag link 87 and steering cylinders 88 are mounted in a low position on the front axle, allowing the conveyor to pass. The rear axle has a high mounted tag link 87 and steering cylinders 88 , allowing the pug mill's windrow to pass under the axle's frame and the conveyor to pass through the top, center section. The four drive wheels 8 , are driven by low speed, high torque, radial piston, hydraulic motors 89 fitted with fail safe, spring applied, hydraulic pressure released, disc brakes. Speed and direction are infinitely variable. The combination of four-wheel drive, front and rear, 40 degrees wheel articulation (steering), in both directions, allow the Recycling Machine to work safely in hilly conditions and tight city work. One of the rear hydraulic motors 89 is fitted with an electronic ground speed encoder 92 , used by the on-board computer to calculate rejuvenator requirements and machine processing speed.
FIGS. 13-21 show the main and extension mill's grade control system. A left-hand 100 and right-hand ski assembly 101 are used to contact the heated, unprocessed asphalt (original grade) slightly ahead of the midway point of the Recycling Machine's long wheelbase, mainframe assembly 3 . The extension mill 14 and the main mill 15 are located slightly behind the midway point of the machine's wheelbase. The rear wheels are riding on the milled grade, while the front wheels are following the original grade. Even if the front end of the Recycling Machine's mainframe 3 is moving up and down on an uneven grade, there is little error introduced into the milled grade, due to the location of the grade ski assemblies 100 and 101 .
The main and the extension mill's grade control system is manually adjustable, allowing setup for various surface conditions and processing widths. The extension mills (left and right side) are hydraulically adjustable in width and crown, while the main mill, located behind the extension mills is fixed in width. The left ski assembly 100 automatically controls the grade (depth of cut) of the left extension mill and the left side of the main mill. The right ski assembly 101 automatically controls the grade of the right extension mill and the right side of the main mill. The left and right ski assemblies are connected by a jointed, cross beam 102 to which various attachments (used to contact the heated asphalt surface) can be attached. The rotating/sliding joint 103 is located at the mid-point of the crossbeam 102 , allowing the beam to rotate and expand in length as the left and right ski assemblies move up and down. Two sliding shoes 104 contact the heated asphalt. As shown in FIG. 16, shoes 104 attaches to pivot arms 105 allowing the shoes to pivot and follow the heated asphalt's surface. Pivot arms 105 attaches to flat springs 106 , which in turn attaches to the adjustable clamping brackets 107 . The flat springs 106 are used to prevent damage to the ski assemblies, if contact with a raised utility structure should occur. The springs are designed to bend and then spring back to their original position on hitting an obstruction. The clamping bracket 107 can be clamped on to the crossbeam 102 at any location. Generally the further out they are placed, the greater the accuracy (stability). Narrow spacing may be used when following wheel ruts in the asphalt's surface (created by traffic). Pins 108 attach the crossbeam 102 to the left and the right side tow arms 109 that are attached by pins 110 to the mainframe of the Recycling Machine 3 . The tow arms pivot on pins 110 , allowing the ski assemblies to follow the asphalt's surface. Movement (raising and lowering) of the left and right side ski assemblies is transferred into the pivoting link 111 , which is attached between the tow arms 109 and flat spring clamp 112 .
The flat spring 113 is clamped to the grade control station's frame 114 . The grade control station's frame 114 is attached to the Recycling Machines mainframe 3 by pivoting links 115 and hydraulic cylinder 116 . The pivoting links 115 form a parallelogram linkage allowing the grade control station's frames 114 to remain absolutely parallel to the mainframe when being raised or lowered by the grade ski assemblies. Attached to the grade control station's frames are the hydraulic (or optional electronic) sensors 117 and wands 118 that make contact with the adjustable height control screws 119 . Brackets 128 attach the height control screws 119 to the extension mill sliders 120 and main mill sliders 121 . Four individually controlled, hydraulic cylinders 122 attached between the Recycling Machine's mainframe 3 and the mill sliders 120 and 121 are used to hydraulically raise and lower the left and right side of the extension and main mills. The left, sensor control station operates the left extension mill and left side of the main mill, while the right, sensor control station operates the right side of the mills. Each grade control sensor 117 (attached to the sensor control station) and wand 118 monitors the position of the height screws 119 allowing the height of each sliding strut to be adjusted individually to the position of the grade control station's frame 114 .
FIG. 16 shows a close up, side view of the mill's grade control system. As the ski assemblies 100 and 101 are pulled along by the Recycling Machine's mainframe they follow the grade of the asphalt's heated surface, which raises or lowers the pivoting link 111 , spring clamp 112 , flat spring 113 and grade control station's frame 114 . The function of the hydraulic lift/damper cylinder 116 is to carry a percentage of the grade control station's frame, crossbeam and averaging ski assembly's weight, preventing the shoes 104 from sinking into the hot asphalt, which causes inaccurate reading. The amount of weight transferred by the cylinder 116 can be adjusted by varying the hydraulic pressure on the head end of the cylinder. The weight transfer pressure can be electronically switched in and out by the on-board computer. Increasing the hydraulic pressure will reduce the weight carried by the ski shoes 104 . The grade control station's frame movement must be dampened to prevent the mills from following major imperfection in the asphalt's surface. The hydraulic lift/damper cylinder 116 dampens the mechanical action of the grade system by restricting the cylinder's hydraulic, oil flow (similar to an automotive shock absorber). Adjustable hydraulic flow control valves are electronically switched in and out by the on-board computer when dampening is required. Dampening and weight transfer are both possible, at the same time. The hydraulic cylinder is also used to raise the complete grade system by increasing the hydraulic pressure on the head end of the cylinder. The flat spring 113 is designed to deflect if the ski assembly is suddenly pushed up by an obstruction or suddenly sinks due to a pothole or any other type of depression. The rate of the flat spring is adjustable by changing the outer pivot point of the spring by moving two pins 123 (located above and below the spring). To do this, a plurality of adjustment points 124 - 126 is provided to change the effective length of spring 113 . The spring is attached to the grade control station's frame 114 at point 127 . Moving the two pins 123 away from point 127 will increase the spring rate. In the dampening mode, the hydraulic lift/dampening cylinder restricts the movement of the grade control station causing the flat spring 113 to deflect. The hydraulic and mechanical adjustments provide a wide range of control for all operating conditions and ski attachments. The grade sensors 117 (hydraulic type shown) are attached the grade control stations. The wands 118 are attached to the grade sensor's rotating shaft and rest on the adjustable height screws 119 , which are attached by brackets 128 to the sliders 120 of the extension and 121 of the main mills. Any change in the position of the grade control stations will raise both sensors 117 causing the wands 118 to pivot (move away from their neutral position) on the adjustable height adjuster screws 119 and rotate the sensor shafts. The sensors send hydraulic oil to the individual hydraulic cylinders 122 , raising or lowering the extension and main mill assemblies. As the mills are raised or lowered the height adjuster screws 119 return the wands back to their neutral position, cutting off the hydraulic oil flow to the hydraulic cylinders. The mill grade control system also corrects for grade changes caused by the Recycling Machine's front axle assembly following the uneven grade of old asphalt surfaces. Changes to the mainframe's front height, in relation to the ski assemblies, will cause the mainframe to pivot around the rear axle's wheel centerline. The ski assemblies 100 and 101 , which are following the asphalt's surface, position the grade control station's frames 114 . The height adjuster screws 119 follow the mainframe's position (hydraulic cylinders 122 have not moved at this point) causing the wand's position to change, which in turn will hydraulically (cylinders 122 receive hydraulic oil from the hydraulic sensors 117 ) raise or lower the sliders, mills and height adjuster screws, again neutralizing the system. The height adjustment screws 119 allow manual adjustment to each individual mill slider to fine-tune the milling height between the extension mills and the main mill. The extension mills 14 (left and right side) feature manually, hydraulic crowning of the milling rotors. The machine operator can adjust the crown without effecting the position of the sliders, which control the depth of the extension and main mills.
For processing requiring greater milling accuracy the standard two ski assemblies shown in FIG. 17 can be replaced by the transversal averaging ski assemblies shown in FIG. 18 . Both assemblies are shown with one ski assembly riding over a 1.75″ bump. The standard ski would transmit an upward movement of 1.56″ into the tow arms 109 which would cause the 1.56″ of movement to be transmitted to the link 111 . The transversal averaging ski would reduce the upward movement to 0.82″ riding over the same bump, causing 0.82″ to be transmitted to link 111 . The wider the “A” dimensions the greater the averaging effect. Lowering the number transmitted to link 111 results in less movement of the mills in response to an aberration in the road surface. The sub beams 129 are attached to the jointed, crossbeam 102 by pivoting bracket 130 . When the width of processing allows, the length of the crossbeam 102 can be increased with plug-in extensions allowing the averaging skis to be moved further out from the Recycling Machine's longitudinal centerline, again improving the averaging effect.
As shown in FIG. 19, an additional embodiment of the invention includes longitudinal averaging ski assembly set up with the ski assemblies at a wide distance (“A”). This is only possible when the ski assemblies can be widened out to a width greater than the Recycling Machine's heater box, rake extensions and extension mills, such as multi-lane highways and airport runways. Adjustable brackets 131 attach the ski assemblies to longitudinal beam 132 that pivot around bracket 133 . The beam 132 can be increased in length by attaching plug-in extensions. It is also possible to attached longitudinal sub-pivoting beams together with four ski assemblies similar to the transversal setup but operating in the longitudinal axis. The ski assemblies can be replaced with wheel assemblies when operating on surfaces that could be marked by the ski assembly shoes 104 .
FIG. 20 shows another embodiment of the present invention where the mechanical longitudinal averaging ski assemblies are replaced with Topcon's Smoothtrack® 4 Sonic Tracker II™ non-contact, averaging beams (one on either side of the Recycling Machine). The longitudinal beam 132 is attached to the standard, jointed crossbeam 102 by fixed bracket 134 , which prevents beam 132 from pivoting. The non-contact sonic sensors 135 are attached to beam 132 . The hydraulic operation of the lift/damper cylinder 116 is controlled by Topcon's electronic control system. The hydraulic damper and pressure transfer system are not used in this application, as the hydraulic cylinder must operate in the standard, double acting mode. The mill's depth of cut is electronically set using the Topcon keypad. The electronic, sonic grade control system controls the oil flow to hydraulic cylinder 116 , which positively raises or lowers the grade control station's frames 114 , beam 132 and sensors 135 . The mills follow the position of the grade control station's frames.
FIG. 21 shows the standard, left-hand transverse ski assembly 100 (looking from the front of the Recycling Machine) attached to the jointed crossbeam 102 . Attached to the right side of the jointed crossbeam 102 is the electronic slope sensor 136 . Both the left-hand ski assembly 100 and the slope control 136 sensor are mounted as far away from each other as possible, increasing the slope sensor's accuracy due to the leverage effects. The left lift/damper cylinders 116 is set to operate on the damper and weight transfer control, while the right cylinder is set for double acting operation (dampening and weight transfer turned off). In operation, the left-hand ski follows the asphalt's surface, which in turn raises or lowers the left side of the crossbeam 102 . The left-hand tow arm 109 transfers this motion into the left grade control station as discussed previously. The slope control sensor 136 (set to one-degree slope, in the drawing) electronically monitors the angle of the crossbeam 102 . The slope sensor will pick up any change in angle and the electronic control system will control the oil flow into the right-hand cylinder 116 , returning the right-hand grade control station and crossbeam 102 back to the one-degree setting.
The main and extension mill grade control system can also be set up to operate the two rear axle cylinders 81 , providing the reference for full, main frame grade control (as discussed earlier). In this case fully extending the hydraulic cylinders 116 raises the left and right grade control station's frames 114 , thereby hydraulically locking the mills to the mainframe's grade. Adjusting the height adjustments screws 119 can individually control adjustments to the mills depth of cut.
FIGS. 22 and 23 show the heated, insulated and covered asphalt surge bin/vertical elevator 17 . The vertical elevator 140 , consists of frame 141 , lower idler shaft 142 , inner chain guide 143 , middle chain guide 144 , outer chain guide 145 , drive shaft 146 , slatted chain 147 , motor coupling 148 , and hydraulic drive motor 149 . Hydraulic cylinders 150 raise and lower the surge bin/elevator 17 into the windrow 151 when the machine moves along path of travel indicated by arrow 152 . The on-board computer monitors a pressure transducer, used to record the head end hydraulic pressure (load carrying pressure) in the hydraulic cylinders 150 . At a set pressure increase (bin full of asphalt) the hydraulic drive motor 149 is stopped, stopping the pickup of recycled asphalt from windrow 151 . As asphalt is released out of the bin the cylinder's hydraulic pressure decreases. The hydraulic motor 149 is re-started when a preset minimum pressure is reached, again allowing asphalt to be picked up from the windrow. This allows for the automatic filling of the bin. The vertical elevator 140 can also run in manual mode, controlled by the ground operator. Asphalt is lifted, vertically up the front face of the conveyor frame 152 , by slatted chain 147 , operating between two vertical wear plates 144 and 145 . The wear plates are the full width of the slated chain, preventing the asphalt from falling back and segregating. The surge bin 17 is constructed with insulation attached to the outer walls and provides heat retention for the stored asphalt. Propane (vapor from top of the propane tank) is supplied to the burner 155 , which is mounted in a horizontal, double walled tube 156 , spanning the complete width of the bin's sides 157 . The double wall tube prevents direct flame contact with the outer tube (in contact with asphalt), preventing the asphalt from being overheated. Two vertical tubes 158 are used to exhaust the horizontal burner tube to the top of the bin, for safety. The tubes are angled using bends and are attached to vertical baffle plates 159 Controlled heat, transmitted over a large effective area by 156 , 157 , 158 and 159 , increases the heat transfer to the stored asphalt and reduces oxidation. Burner control is automatic and is controlled by an adjustable bin thermostat 160 . The surge bin's rotary discharge valves (left and right side) 161 are mounted in four replaceable bearings 162 and are opened/closed by two independently controlled, hydraulic cylinders 163 attached to arms 164 . The arms 164 are used to turn the rotary discharge valves 161 allowing the stored (heated) asphalt to fall into the left and right auger screws (located in front of the screed assembly). Attached to the front of the vertical elevator is the hopper/diverter valve assembly 165 . The hopper receives new asphalt from the front asphalt hopper (an option attached to the front of the Recycling Machine) via the optional central conveyor (both described in detail later). Rotary valve 166 is attached by arm 167 to the hydraulic cylinder 168 . In the position shown, the valve would be directing the asphalt delivered by the conveyor into the vertical elevator for delivery into the bin for storage.
FIG. 24 shows a close up side view of the hopper/diverter valve with the rotary valve 166 in the closed position.
FIG. 25 shows the hopper/diverter valve in the three operating modes traveling in the direction shown by arrow 152 . FIG. 25A shows the conveyor discharging new asphalt into the hopper. In this mode the rotary valve 166 is closed and the vertical elevator 141 is running. New asphalt is carried up the front of the vertical elevator and fills the surge bin. This operation is used when the surge bin must be initially filled with new asphalt (no windrow has been established). Due to the off-center boom location, the bin may be top loaded manually as well. FIG. 25B shows the conveyor discharging new asphalt into the hopper for a Remix operation. In this mode the rotary valve is closed and the vertical elevator is running and also picking up 100% recycled asphalt from the windrow 151 left by the pug mill. New asphalt is being blended with the recycled asphalt in the vertical elevator and is being carried up the vertical elevator, filling the surge bin. FIG. 25C shows the conveyor discharging new asphalt into the hopper. In this mode the rotary valve is open and the vertical elevator is not running. The amount of 100%, recycled asphalt contained in the windrow 151 , left by the pug mill, is not sufficient to maintain a constant head of asphalt in front of the screed assembly. New asphalt passes through the rotary valve (bypassing the vertical elevator) directly on to the windrow or the milled asphalt's surface. The on-board computer determines when the Recycling Machine's front hopper and conveyor supplies new asphalt by monitoring the volume of asphalt flowing through the pug mill's volume sensing ski. Both the “B” and “C” modes can be used when the “Remix Method” (new asphalt is proportionally mixed with 100% recycled asphalt) is required. The “B” and “C” also allow the Recycling Machine to process asphalt surfaces requiring more asphalt than is available, such as increasing the structural strength of the original asphalt, grade changes and shoulder widening.
FIGS. 26-29 shows the asphalt auger/divider/strike-off blade assembly 18 . The auger/divider/strike-off blade assembly 18 distributes material evenly to left and right side of the screed assembly 19 . The screed assembly 19 is an industry standard unit with all major adjustments being electric/electronic over hydraulic. The screed may be equipped with left and right side extensions. The auger/divider/strike-off blade assembly 18 consists of a left 171 and right 172 auger (looking from the front of the machine) rotated by individual sprocket/chain drives 173 and hydraulic motors 174 . The auger's speed is infinitely variable in both directions, allowing asphalt contained in the windrow 151 to be moved in all directions across the front face of the screed assembly. The windrow divider 175 splits the asphalt windrow 151 and assists the left and right augers 171 and 172 in the distribution of the asphalt windrow 151 , especially on cross slopes and during conditions requiring high volumes of continuous material to either side of the screed assembly. Two hydraulic cylinders 173 are attached between the Recycling Machine's mainframe 3 and the augers mainframe 183 , allowing the auger/divider/strike-off blade assembly 18 to be raised and lowered for varying depths of asphalt laid by the screed assembly. The windrow divider 175 is positioned (turned) by the hydraulic cylinder 176 and arm 177 and is controlled manually or, automatically by the on-board computer. Two electronic sensors (not shown) are located at the end of the screed's extensions and determine the level of the asphalt in front of the screed and screed extensions. As the level of asphalt in front of the screed assembly drops, the electronic sensor(s) automatically speed up the appropriate auger 171 or 172 , delivering more asphalt across the front face of the screed 178 . The angle of the divider 175 is controlled proportional to the speed of each individual auger. An electronic feedback LVDT 179 compares the divider's rotational position to each individual auger's speed. The divider is fitted with replaceable and adjustable blades 180 allowing the height of the divider to be set in relation to the auger's height. For major height adjustments, adding or removing spacers to the rotational shaft 181 moves the divider up and down.
FIG. 29 shows the asphalt auger/divider/strike-off blade assembly with the divider 175 in the straight-ahead position “A”. Both augers are being controlled to the same speed by the electronic sensors mounted on the screed's extensions. The windrow 151 is being split equally to both augers and the asphalt head in front of the screed assembly is even. “B” shows the position of the divider at its maximum rotational angle (in one direction, deflecting a greater proportion of asphalt into the faster auger). The right-hand auger's speed has increased as a result of the right-hand side of the screed and screed extension running low on asphalt. The right-hand sensor has sped up the right-hand auger 172 in an effort to maintain sufficient supply of asphalt at the section of the screed laying the greatest volume of asphalt. The on-board computer has proportionally increased the rotational angle of the divider to match the increased speed of the right-hand auger. The divider angle can be programmed to degrees/per auger RPM, allowing the gain (sensitivity) of the system to be varied for varying applications and asphalt types. To meet additional demands for material, the surge bin rotary valves 161 will open allowing stored asphalt to be dumped into the augers. The manually adjustable strike-off blades 182 are attached to the auger's mainframe 183 and are used to control the flow of asphalt to the left and right augers, preventing excessive asphalt build-up in the augers and in front of the screed assembly, which would cause the screed to rise, due to the increased pressure. The strike off-blades (left and right side) are slotted, allowing for adjustment in height and taper. The height of blade becomes greater towards the end of the augers, allowing more asphalt to flow under the blades towards the end of the augers.
FIG. 30 shows a detailed side view the Recycling Machine 1 with the attached clip-on, front asphalt hopper/5 th wheel pin assembly 190 and the central conveyor assembly 191 , which runs down the center of the machine to feed new asphalt to the hopper/diverter valve assembly 165 . As explained previously, the hopper and central conveyor are used to provide new asphalt when using the “Remix Method” or when extra asphalt is required, such as for shoulder widening.
FIG. 31 shows a simplified view of the Recycling Machine 1 with the major sub-assemblies removed for clarity. Shown are the mainframe 3 , clip-on, front asphalt hopper/5 th wheel-pin assembly 190 , central conveyor assembly 191 , hopper/diverter valve 165 and asphalt surge bin/vertical elevator 17 .
FIG. 32 shows the clip-on, front asphalt hopper/5 th wheel pin assembly 190 in its raised position and FIG. 33 shows the clip-on, front asphalt hopper/5 th wheel pin assembly 190 in its lowered position. The clip-on frame 192 is attached to the Recycling Machine's mainframe 3 top and bottom tubes 193 .
FIG. 34 shows the frame 192 with its safety locks 194 in the open and closed position. The two safety locks 194 (one on either side of the frame 192 ) are mechanically pinned into position by safety pins 195 . Pivot pins 196 allow the safety locks to be opened when the safety pins are removed. The safety locks can only by opened when the clip-on, front asphalt hopper/5 th wheel pin assembly 190 is in the lowered position as the top section of the frame assembly 197 is tapered at point 198 and only allows clearance in this position. This design feature provides a fail-safe attachment mechanism for transportation (raised position) as the frame assembly 197 physically prevents the safety lock from opening, even if the safety pins were not installed. The hydraulic cylinders 199 are attached between frame 192 and frame 197 . Extending the hydraulic cylinders 199 raises the front asphalt hopper/5 th wheel pin assembly 190 . An electronic pressure transducer is used to measure the pressure in the hydraulic cylinders 199 . The on-board computer monitors the amount of asphalt in the front hopper using the pressure in the cylinders as a reference. The pressure is checked at the beginning of the work day by the on-board computer to determine a base line for the assembly weight of the front asphalt hopper/5 th wheel pin assembly, as it will change with accumulated asphalt deposits. The on-board computer gives the operator a graphical display of the weight of asphalt in the front hopper. The on-board computer may also signal the dump truck drivers when to discharge more asphalt into the front hopper. The signal may be audio, electronic or the use of a red and green light, located on the front of the Recycling Machine. Both lights are visible in the truck's side mirror. The systems may also use a live bottom (moving floor) trailer with electronic wireless control of the hydraulically driven, variable speed, live bottom floor, which is generally a belt or slat conveyor. The Recycling Machine will automatically control the discharge rate of asphalt into the front hopper. The front asphalt hopper/5 th wheel pin assembly can be raised and lowered while asphalt is being discharged on to the conveyor assembly 191 , however the height is limited by electronically monitoring the position of frame assembly 197 . Two arms 200 (one on either side of the frame assembly) are attached to frame assembly 197 and contact the conveyor assembly 191 , allowing the front section of the conveyor to follow the movement (raise and lower) of the front asphalt hopper/5 th wheel pin assembly. The central conveyor assembly 191 is attached to a Recycling Machine's mainframe 3 at point 201 , reference of the front axle. This allows the front section of the belt conveyor to pivot. Any change in the conveyer's tension during this movement is taken up by an automatic tensioning system. New asphalt is dumped into the front hopper 202 by dump truck and is conveyed by drag chain 203 to conveyor assembly 191 . A fixed strike-off blade (not shown) controls the height of the asphalt being picked up by the drag chain. The hydraulic motor(s) 204 provide an infinite speed, drive for the drag chain 203 that is controlled by the on-board computer. The asphalt's discharge rate is controlled by electronically monitoring (electrical encoder attached to the rear drive shaft of the conveyor assembly 191 and the front idler shaft 205 of the drag chain 203 ) the conveyor's speed. The ratio in drag chain speed to conveyor speed is programmed into the on-board computer and determines the depth of material deposited on to the conveyor. The amount of asphalt to be delivered by the conveyor is determined by the on-board computer.
FIG. 35 shows the central conveyor assembly 191 passing through the front axle and rear axles 83 . Because the conveyor is located through the passages in the axles, it can be attached to the bottom of the mainframe 3 or supported by the bottom of the mainframe 3 . The conveyor delivers new asphalt to the hopper/diverter valve 165 or to the optional secondary auger/screed assemblies (not shown) and the primary auger/divider/strike off blade and screed assembles used in 100% HIR with Integral Overlay. For the Remix method, the hydraulic drive motor's 207 speed is adjusted proportionally to pug mill material discharge rate. The ratio of new material that can be added to the 100% recycled asphalt exiting the pug mill is set between 0 to 50%, with 10 to 15% being the norm.
For the Integral Overlay method, the speed of the drive motor 207 is matched to the asphalt requirements of secondary auger/screed assemblies and also the primary auger/divider/strike off blade and screed assembles. A shuttle conveyor 23 is used to deliver asphalt from the central conveyor assembly 191 to either the secondary auger/screed assemblies or to the primary auger/divider/strike-off blade assemblies (as discussed in detail later). A proportional, electronic level sensor, mounted in the feed chute to the secondary auger assembly, electronically monitors the asphalt's level. As the material level drops, (more asphalt required by the secondary screed assembly) the drive motor's speed increases (proportional control). As the asphalt's level increases in the feed chute (less asphalt required by the secondary screed assembly) the drive motor's speed is decreased and will eventually stop.
In another embodiment, a conveyor belt is used. The conveyor belt 208 is manufactured from a high temperature material and is carried by troughing idlers 209 and return idlers 210 . The idlers (except the front pivoting section that passes through the front axle) are mounted directly to the Recycling Machine's mainframe for most of the span to reduce weight. Troughing idler 211 is a single point belt scale and is used to measure the weight of asphalt on the belt. By measuring the volume of asphalt exiting the pug mill's discharge (volume sensing ski) and knowing the design weight of the asphalt being 100% recycled, the on-board computer can calculate the correct speed of the conveyor belt, based upon the weight of asphalt passing the scale. A belt scale may be used when the Remix method is required. For greater accuracy the conveyor assembly is designed for the addition of a second belt scale troughing idler. When new asphalt is being supplied to the rear end of the Recycling Machine (100% HIR method) when there is occasionally a deficit of 100% recycled asphalt, the asphalt in the conveying system tends to loss heat at a greater rate than the asphalt stored in bulk in the front hopper. An infrared sensor 212 monitors the temperature of the asphalt on the belt. The on-board computer will automatically, slowly discharge the belt when the temperature drops to a minimum level. The front asphalt hopper's drag chain will remain shut down, keeping the asphalt in the front asphalt hopper in bulk form, which helps retain the asphalt's temperature. When using the Remix or Integral Overlay method, heat loss is minimal as asphalt is being continuously supplied. The front asphalt hopper is also equipped with temperature sensors and will automatically discharge, as discussed previously. The belt conveyor is the preferred conveyor of asphalt, rather than a steel drag conveyor, as the rubber belt better retains the asphalt's temperature, requires less drive torque, reduces segregation, produces less noise, wears less and is lighter in construction. The belt is driven at the rear end of the Recycling Machine by reduction gearbox 206 by hydraulic motor 207 and a crowned and lagged pulley 213 .
FIG. 36 shows the automatic, hydraulic belt tension assembly. The drive pulley 213 and drive shaft 214 is supported by two adjustable bearings 215 , mounted to the pivoting bracket 216 . The hydraulic motor 207 is attached to the reduction gearbox 206 , which is supported by the drive shaft 214 (the driveshaft goes through the reduction gearbox). The torque link 217 attaches the reduction gearbox to the pivoting bracket 216 . The pivoting bracket is attached to the Recycling Machine's mainframe 3 by pivot bearings 218 (one on either side of the mainframe). The hydraulic cylinders 219 (one on either side of the main frame) are attached between the main frame 3 and pivoting bracket 216 . The hydraulic pressure in the head end of the two cylinders is fully adjustable, allowing the belt to be continuously tensioned while the belt is in operation. The hydraulic cylinders extend and turn the pivoting bracket 216 on the pivot bearings 218 , thereby pulling on the belt. The on-board computer only tensions the belt to full tension when the belt is going to be used. When the belt is not in use, the belt is relaxed to a low state of tension, thereby reducing the stress on the belt. The hydraulic control system allows the automatic belt tension assembly to float, under pressure, allowing the front of the conveyor to pivot (raise and lower) while retaining the correct belt tension.
As discussed earlier, utility structures and other obstructions found in asphalt pavement have, until now, presented one of the greatest challenges to the HIR of asphalt, especially in city work.
FIG. 37 shows the details of the rake/blade scarification/collection system 11 , 12 and 13 fitted to the Recycling Machine, and the Preheater located ahead of the Recycling Machine. This assembly consists of a mainframe 220 , mounted to the Recycling Machine and Preheater's mainframe 3 . The mainframe 220 receives a continuous flow of air from the Recycling Machine and Preheater's mainframe 3 providing cooling for the hydraulic cylinders 221 and 222 . The extension rakes 11 may be extended hydraulically, allowing the processing width to be changed (operator control) while the machine is working. Hydraulic tilt cylinders 223 and parallel links 224 are attached to the mainframe 220 and the vertical legs 225 . The pivoting frames 226 are attached to the vertical legs 225 by pivot pins 227 allowing the four main rake/blade pivoting frames 226 to pivot and follow the asphalt's surface and also ride up and over iron utility structures. Hydraulic cylinders 228 are attached to the mainframe 220 and the bottom parallel links 224 allowing the vertical legs 225 , pivoting frames 226 , flat springs 229 , carbide cutter assemblies 230 and blade assemblies 231 to be raised and lowered. The flat springs and carbide teeth assemblies are attached to the front face of the pivoting frames 226 . The hydraulic pressure in cylinders 228 are adjustable, thereby increasing or decreasing the penetration force of the carbide teeth into the heated, softened asphalt. The carbide teeth are set back 15 degrees from vertical when at rest. Working forces bend the springs further back, increasing the set back angle, thereby reducing aggregate fracture and allowing the teeth to ride up and over undulating surface and/or iron utility structures. The on-board computer automatically raises all of the rakes when reverse drive direction is selected, preventing damage to the flat spring 229 . The hydraulic circuit for cylinders 228 allows oil to be forced out of the cylinder (float up) by the upward force developed by the carbide cutter assemblies. Hydraulic oil re-enters the cylinder, under controlled (adjustable) pressure, forcing the carbide cutter assemblies back into the heated asphalt. Other recycling machines that are only fitted with milling units (no scarification teeth) are limited to how close to obstructions they can mill. The milling units must be lifted to prevent damage to the milling unit's carbide teeth and iron utility structures. Scarified asphalt should be removed (scraped away) from any part of the asphalt surface that cannot be milled and collected by the main mill to facilitate proper mixing and the later placement of 100% recycled asphalt. Attached to the rear face of the four pivoting frames 226 are flat springs 229 fitted with a plurality of blades 231 . Blades 231 are mechanically adjustable in height, allowing adjustment for blade and carbide cutter wear.
FIG. 38 shows the operation with a blade 231 in a raised position and FIG. 39 the operation of a blade 231 in a lowered position. In the “blade raised” position (normal scarification) the tilt cylinder 223 remains collapsed (not hydraulically extended). Cylinder 223 , together with parallel link 224 form a parallelogram linkage, keeping the carbide cutters 230 at the correct angle of attack as they raise and lower (float) due to changes in the asphalt pavement's profile. As shown in FIG. 39, when the blades 231 are required to scrape and collect the scarified asphalt (main mill raised by the operator to clear obstruction), tilt cylinder 223 extends causing the vertical leg 225 to pivot around the rear pivot pin 232 attached to parallel link 224 and cylinder 228 . The carbide cutters 230 continue to scarify the heated asphalt independent of the blade position.
The blades may be broken down into sections 231 A- 231 D as shown in FIG. 40 . When an obstacle is encountered 233 in the heated asphalt's surface, the operator may raise any section desired by activating a lifting mechanism such as a hydraulic cylinder associated with each blade section. Section 231 B's blade would remain raised to clear the utility structure 233 while sections 231 A, 231 C and 231 D's blades would be lowered to collect asphalt. While the blade 231 is shown as being linked to the rake by frame 226 , the blade and rake do not need to be linked together. The blade assemblies may be configured to work independently of the rakes. Cylinder 223 bottoms out (fully extends) holding the blades in the lowered position. Cylinder 228 still provides hydraulic down pressure (force) on the carbide cutters 230 and blades 231 . When encountering an obstruction while scraping, cylinder 228 together with carbide cutter springs and blade springs 229 allow the complete assembly to hydraulically float up and over the obstruction, as before. In the event of blade 231 being overloaded by excessive asphalt or an obstruction, cylinder 223 will collapse, allowing the blade 231 to automatically raise. The hydraulic pressure setting (relief valve) of the head end oil supply to the hydraulic cylinder 223 adjusts the amount of load required to collapse the cylinder. The operation of the blades can be fully controlled by the on-board computer when the optional metal detection assemblies are fitted, as described in detail later on.
Cylinders 221 , FIG. 37 attached to the mainframe 220 and the extension frames 234 allow the extension rakes 11 to hydraulically extend and retract, varying the scarification width on the fly. The extension frames (left and right side) 234 slide in and out of the mainframe 220 . The extension's pivoting frame 235 is fitted with the same flat springs 229 and carbide cutter assemblies 230 as the main rake assemblies. Pivoting frame 235 is raised/lowered by pivot arm 236 and hydraulic cylinder 222 . The cylinder's hydraulic pressure is variable (same as cylinder 228 , explained above), increasing or decreasing the penetration force of the carbide cutter assemblies 230 into the heated, softened asphalt. Extending or retracting the extension rakes automatically raises the pivot arm 236 , preventing the carbide cutter assemblies 230 from jamming sideways into the heated asphalt. The extension rakes may include blade assemblies but are not generally required since clean up around obstructions can be performed by the extension mills (sliding in and out) and/or hand shoveling. Shoveling is possible on either side of the Recycling Machine with material returned to the extension or main mill for processing.
FIG. 41 shows the flow of heated asphalt through the extension mills 14 , offset discharging main mill 15 , and offset pug mill 16 . The carbide cutting teeth are not shown on the extension and main mill for clarity. The extension and main mills are directly behind the Recycling Machine's rake scarification and blade collection system and are responsible for profiling and collecting the heated and loosened asphalt surface. As mentioned previously the mills also release further moisture in the form of steam. The main mill and the pug mill are also responsible for the mixing of liquid additives into the recycled asphalt. The pug mill provides the final mixing of all products into a homogeneous, 100% recycled asphalt windrow 151 .
FIG. 42 shows the extension mills 14 (looking from the rear of the Recycling Machine). They are attached to the Recycling Machine's mainframe 3 by R.H. sliders 240 , L.H. slider 241 and wobble link 242 . Sliders 240 and 241 slide through adjustable wear plates (not shown) attached to the Recycling Machine's mainframe 3 , preventing wear to the mainframe. The cross frame 243 is raised, lowered and tilted by two hydraulic cylinders 245 , mounted inside the sliders 240 and 241 . The wobble link 242 prevents the sliders from binding when the cross frame 243 is fully tilted. Pins 246 are the pivots for the cross frame 243 and the left and right crown frames 247 . The hydraulic cylinders 248 are attached to the cross frame 243 and the crown frames 247 allowing positive and negative, left and right crowning (tilt) of the crown frames 247 , independently of the cross frame 243 . The extension frames 248 are slide in and out (varying the extension mill's width of cut) on the crown frames 247 by hydraulic cylinders 249 attached between the crown frames and the extension frames. Being able to independently raise, lower, tilt, crown, and extend the mills provides complete control over the extension mills when working with adverse conditions, such as, changes to grade and/or slope, working around iron utility structures in the asphalt surface, processing driveways, intersections, varying pavement width and damaged curbs
FIGS. 43 and 44 show side views of the extension mills. The two, extension mill rotors 250 feature shallow flighting 251 , tooth holder 252 and replaceable carbide teeth 253 and rotate in a down-cut direction (teeth impinge down on to the heated surface). The rotors 250 are driven by a direct drive, hydraulic motor 254 , through coupling 255 . End plates 256 incorporate the rotor support/thrust bearing 257 used to support the non-driven end of the rotors. The rotors 250 are quickly removed for servicing by removing the end plates 256 , allowing the rotor's couplings 255 to slide off the splined shafts of hydraulic motors 254 . The rotors float free on the hydraulic motor's splined drive shafts, while bearings 257 absorb all end-thrust. Asphalt flow is towards the drive end of the rotors (center of machine) with the asphalt being discharged through openings in the blade bodies 258 into the main mill's rotor. The rotors mill the heated and loosened asphalt in a down-cut direction to reduce the conveying efficiency, thereby causing the asphalt to build up in front of the rotors. The build up of asphalt increases the mixing/steam release time and provides a degree of surge capacity when milling through high areas, allowing the feed of milled asphalt into the main mill's rotor to remain fairly consistent. The down-cut feature of the rotors also prevents damage to the mill rotor's carbide teeth and iron utility structures located in the asphalt. The hydraulic system (initiated by the ground operator) may be used to reduce the hydraulic cylinder's 245 downward pressure (force), while rotor speed and cutting torque are also reduced to allow the rotors to float and freewheel over obstructions. An on-board computer may control this operation. Attached to the blade bodies 258 are adjustable blades 259 . The flat springs 260 , force bodies 258 and blades 259 on to the milled surface, scraping and collecting the fine asphalt, for processing. Current equipment generally leave a layer or patches of fine asphalt and/or rejuvenator fluid behind the mills (rotary scarifiers), resulting in varying quality of the reworked (recycled) asphalt and eventual bleeding of the finished, compacted surface (mat).
FIG. 43 shows a blade body 258 in the relaxed position. FIG. 44 shows the blade body in the maximum up position having pivoted around pin 261 and bending the flat spring 260 . The adjustable blade 259 is set below grade (grade is established by the mill rotor's carbide teeth 253 when milling) to pre-load the flat spring 260 thereby keeping a constant force on the blade 259 and forcing it into contact with the milled surface. The flat spring 260 is anchored (bolted) to the extension frame 248 by attachment plate 262 and permits the up and down movement of the blade while maintaining a constant force on the blade. The flat spring's fulcrum point is the underside of the blade bodies pivot boss, pivoting around pin 261 .
FIGS. 45, 46 and 47 show the main mill assembly 15 attached to the Recycling Machine's mainframe 3 by the R.H. slider 270 , L.H. slider 271 and wobble link 272 . The sliders 270 and 271 slide through adjustable wear plates (not shown) attached to the mainframe 3 preventing wear to the mainframe. The rotor assembly 273 is driven and supported at either end by two direct-drive, hydraulic motors 274 . The motors are attached to removable end plates 275 , allowing the rotor to be quickly removed for servicing by removing one of the end plates. The rotor assembly 273 is spring loaded by spring 276 (in one direction) and floats on the hydraulic motor's 274 splined drive shafts. The hydraulic motors provide main support and one takes the thrust generated by the rotor assembly 273 . The couplings 277 allow for rotor misalignment, deflection and thermal expansion. Asphalt flow is towards one end of the rotor with asphalt discharge through the blade body 278 into the offset pug mill's front rotor. The shallow rotor flighting 279 , together with closely spaced carbide teeth 280 and holders 280 A milling in a down-cut direction, reduce asphalt conveying efficiency, thereby causing the heated asphalt to build up in front of the rotor. The build up of milled asphalt increases mixing/steam release time and provides a degree of surge capacity when milling through high areas, allowing the flow of milled asphalt into the pug mill's front rotor to remain fairly consistent. The down-cut feature of the rotor also prevents damage to the mill rotor's carbide teeth and iron utility structures located in the asphalt. The blade bodies 278 are forced down by flat springs 260 . The blades 281 pivot around pin 282 and operate in the same manner as shown in FIGS. 43 and 44. A venturi (not shown) in the air extraction system creates a negative air pressure at vent tubes 283 and in the boxed in mainframe 284 . The mainframe 284 has cut outs 285 located directly above the rotor assembly 273 allowing rejuvenator fluid to be sprayed directly on to the spinning rotor assembly by spray bar 286 . Rejuvenator fluid is thereby, prevented from direct contact with the milled surface while the spinning rotor assembly spreads the fluid, providing maximum coverage to the milled asphalt. Steam released from the hot, tumbling asphalt also rises through cutouts 285 , mainframe 284 and vent tubes 283 . The air extraction system vacuums or draws off and vents the released steam and other fumes to the top of the Recycling Machine. Other types of vacuum and extraction devices known to those of skill in the art may be used as well. An emission control system for removing fumes and other hazardous materials may also be coupled to vent tubes 283 . An emission control system for removing fumes and other hazardous materials may also be on the extension mills.
The mainframe 284 is raised, lowered and tilted by hydraulic cylinders 287 mounted inside the sliders 270 and 271 . Control of the hydraulic cylinders is manual or by automatic grade controls as discussed before.
FIG. 48 shows the hydraulic schematic for the Recycling Machine's fluid application system. Current machines use positive displacement pumps (gear, vane and roller) fitted with variable speed drive systems to pump and meter only rejuvenator fluid. The application rate of the rejuvenator fluid is generally controlled by operator input (distribution rate, liters/sq. m.) and by monitoring the Recycling Machine's processing speed (distance traveled). Distance traveled, by itself, provides inaccurate and inconsistent results as the volume of asphalt being processed changes constantly as density, depth of cut, pavement profile and width of cut vary. The rejuvenator pump/motor RPM (monitored by electronic pickup) and/or an electronic flow meter measure and control (microprocessor) the rejuvenator fluid application rate. Both systems (either measuring RPM or flow) can produce inaccurate results and are limited to a narrow viscosity range. Both systems also suffer from contamination, as most rejuvenator fluids are unfiltered or not filtered to the level required by positive displacement hydraulic pumps and flow meters containing moving parts. Placing full flow filters into the system reduces contamination, however, constant monitoring of the filter's condition is required, as are frequent filter changes. The more accurate of the two systems is the variable speed, positive displacement pump with an in-line flow meter to monitor/control system flow (microprocessor). Flow meters are available without moving parts, however, they are very expensive and their maximum temperature range is limited at present. Systems using only a variable speed, positive displacement pump with electronic monitoring and control are inaccurate. The pump flow rate changes as internal wear increases, rejuvenator fluid temperature changes (viscosity change) and pressure differential across the pump (delta P) caused by filter restriction increases. Both systems are limited to the lighter types of rejuvenator fluids that do not require heating.
FIG. 48 shows a system used to accurately meter and dose light (unheated), heavy (heated) rejuvenator fluids and polymer liquids. An on-board computer may be used to control and monitor all of the functions of the application system. FIG. 49 shows the liquid spray bar 286 mounted above the front rotor assembly 273 on the main mill and liquid spray bars 289 and 290 mounted above the front rotor assembly 291 of the pug mill 16 . Spraying fluid directly on to the rotating rotor assemblies distributes the fluid over a greater area and reduces the possibility of the fluid coming into direct contact with the milled, base surface. Air is also used to aerate the liquids (described in detail later) exiting the spray bars, providing even greater coverage. The rejuvenator fluid is stored in a heated, insulated and pressurized tank (0.1-0.5 psi) 292 on-board the Recycling Machine. An automated, propane fired burner 293 heats the tank (only required for viscous fluids). The tank is also fitted with heat exchanger tubes 294 (mounted in the tank bottom). When the rejuvenator fluid temperature (monitored by the on-board computer) is below a preset temperature the returning high temperature hydraulic oil from the Extension mills, main mill and pug mill motors, case drain (internal leakage), is diverted through the heat exchanger tubes 294 , thereby heating the rejuvenator fluid. An on-board computer may be used to prevent reverse heat transfer (rejuvenator fluid heating the hydraulic oil when the propane heater is used) by diverting hydraulic oil flow around the in-tank heat exchanger 294 . As shown in FIG. 50, the on-board computer processes information received from the pug mill's variable area discharge, windrow forming ski 343 (asphalt volume measurement), rejuvenator tank temperature (correction factor), operator input (distribution rate, liters/ton) and the Recycling Machine's distance traveled (m/min.) which may be obtained by a rotary-encoder located on one of the wheels. An air operated, positive displacement, diaphragm pump 295 (electronically pulsed by the on-board computer) pumps and meters the fluid stored in the rejuvenator tank 292 delivering it to a hydraulically operated two-way valve 296 . Valve 296 allows fluid to be directed either to the main mill and/or the pug mill spray bars or returned to the tank through two-way valve 297 . Viscous rejuvenator fluids require constant heating to prevent fluid setup. The diaphragm pump 295 runs (pulsed) continuously, returning the rejuvenator fluid back to the tank (when not required by the process), keeping the diaphragm pump, lines, pipes and valves hot. The on-board computer calculates and stores (in memory) the quantity of fluid used when the rejuvenator fluid exits the main mill and/or pug mill spray bars. Normally closed shut off valve 298 (on-board computer controlled) opens when sufficient milled asphalt is flowing through the pug mill's front rotor. Adjustable flow control valve 299 alters the ratio of rejuvenator fluid delivered to the main mill and/or pug mill spray bars 289 and 290 when shut off valve 298 is open. At startup (no asphalt flowing through the pug mill) shut off valve 298 is closed allowing all of the rejuvenator fluid (low flow) to flow from the main mill's spray bar 286 . As the volume of asphalt flowing through the pug mill increases, the on-board computer opens shut off valve 298 . The sprayed rejuvenator fluid (staged) follows the flow of asphalt through the main mill 15 and the pug mill 16 , allowing accurate and complete mixing of the rejuvenator fluid, added aggregate additives and milled asphalt. The spray bars 286 , 289 and 290 (as shown in FIG. 49) are small-bore, varying diameter steel tubes with drilled orifices of varying sizes and spacing. As the rejuvenator fluid flow rate increases (greater volume of milled asphalt), pressure in the spray bars increases, forcing the fluid further along the bars. The main mill's spray bar is supplied fluid at one end (above the offset, asphalt discharge to the inlet of the pug mill's front offset rotor) and is equipped with spray orifices of decreasing size and increased spacing as the fluid travels along the spray bar. As the fluid flow increases, pressure in the spray bar increases, forcing the fluid further along the spray bar towards the center of the main mill. This feature makes sure that fluid is sprayed into the greatest concentration (volume) of milled asphalt, preventing fluid contact with the milled surface. The spray bar should not extend past the coverage area of the pug mill as shown in FIG. 49 . Located between the pug mill's spray bars 289 and 290 is an adjustable flow control valve 300 used to balance the liquid's rate of flow between the front rotor's spiral paddle section (asphalt inlet to pug mill from main mill's offset discharge)) and the alternating paddle section located in the pug mill's mixing chamber. Generally, the flow control valve 300 only comes into play when the rejuvenator flow rates are in the higher range or when polymer additives are being added, as described later. Spray bar tube size and hydraulic supply hoses are small in diameter to reduce the volume of liquid to a minimum, thereby reducing the chance of spray bar drip. Viscous rejuvenator fluids require purging from the diaphragm pump, lines, pipes and valves during periods of inactivity or after use (end of shift) to prevent setup. The use of compressed air, followed by diesel fuel to dilute and clean, prevents fluid setup. While purging, fluid flow to the spray bars is shut off by the two-way valve 296 . Rejuvenator fluid is diverted too the two-way valve 297 and then back to the storage tank 292 . The on-board computer controls the complete purging and cleaning cycle. The fluid supply to the positive displacement pump 295 is shut-off by the N.C. shut off valve 301 (pump stopped). Metered compressed air flows through the N.C. shut-off valve 302 into the inlet line of the diaphragm pump, lines, pipes and two-way valves 296 and 297 , forcing the fluid back to the rejuvenator storage tank 292 . The top of the tank is fitted with a low-pressure relief valve (0.1-0.5 psi) 303 , which allows the compressed air to escape. Adjustable, air flow control valve 304 limits the maximum amount of air flow and the one way check valve 305 prevents rejuvenator fluid from entering the air supply system. After air purging, the fluid return line to the tank (through the two-way valve 297 ) is closed, preventing rejuvenator fluid from flowing back (reverse flow) through the system. The two-way valve 297 now connects, through a hose to a removable fluid catch container 307 . Metered diesel fuel flows through the N.C. shut-off valve 306 into the diaphragm pump's, inlet line. Diesel (along with the air already purging the system) flows into the diaphragm pump, lines, pipes and two-way valves 296 and 297 , diluting any remaining rejuvenator fluid and flushing it into the catch container 307 for disposal. Adjustable diesel flow control valve 308 limits the maximum amount of diesel flow and the one way check valve 309 prevents rejuvenator fluid from entering the diesel supply system. During flushing and cleaning the diaphragm pump is intermittently cycled during the diesel injection stage to help clean the two diaphragms and ball check valves. After flushing, valves 297 , 302 and 306 are automatically closed. For safety and servicing the rejuvenator tank outlet and return connections are fitted with manually operated ball type shut off valves 310 . Tank air pressure automatically bleeds down when the Recycling Machine is not in use.
The positive displacement, diaphragm pump 295 delivers rejuvenator fluid accurately, as each stroke delivers an absolute volume. The pump should be stainless steel with high temperature diaphragms. Air pressure (0.1-0.5 psi) in the storage tank 292 applies a pressure to the inlet of the diaphragm pump, reducing the possibility of cavitation. The pump can accurately pump fluid with particle sizes up to ⅛″ in diameter, however, an in-tank wire mesh strainer 311 limits particle size to less than 50 mesh. As mentioned earlier, spraying the rejuvenator fluid directly on to the main mill's rotor and pug mill's front rotor provides maximum coverage and mixing with the heated, milled asphalt. Also, by reducing direct fluid contact with the milled base surface, bleeding of the finished asphalt surface is eliminated. The rejuvenator fluid also lubricates the main mill's milling teeth and holders, preventing the teeth from sticking (not turning) in their holders, thereby reducing uneven wear. Positive shut down of the rejuvenator fluid flow (at the spray bars) by the two-way valve 296 almost eliminates fluid dripping by preventing the rejuvenator system components from leaking down. The N.C. shut-off valve 312 supplies air to the main mill spray bar 186 to be mixed (depending on the type of fluid) with the rejuvenator fluid (at the outlet of two-way valve 296 ), causing it to aerate. Aerating some rejuvenator fluids provides better coverage (reduced droplet size) of the liquid to the milled asphalt. The air continues to flow (if previously being mixed with the rejuvenator fluid) after the two-way valve 296 is closed (fluid flow shut off) thereby blowing (purging) the remaining fluid out of the spray bars. The N.C. shut-off valve 313 supplies air to the pug mill spray bar 289 and 290 to be mixed (depending on the type of fluid) with the polymer liquid, causing it to aerate. The N.C. shut-off valve 312 and 313 remain on after the liquid supply is stopped, providing additional air as the Recycling Machine slows to a stop. This allows the complete purging of the spray bars of fluid by the time the Recycling Machine has stopped. The air supply is automatically shut-off after an adjustable time delay. The N.C. shut off valves 312 and 313 also supplies air blasts while the purging and cleaning cycle is underway. Adjustable air flow control valves 314 limits the maximum amount of air flow (fluid aeration) and the one way check valves 315 prevents rejuvenator fluid and polymer liquid from entering the air supply system. The on-board computer monitors the volume of asphalt being processed through the pug mill and together with the programmable rejuvenator flow rate (determined by pre-engineering of the asphalt to be recycled), produce consistent and accurate metering of the rejuvenator fluid. Proper mixing and application of rejuvenator fluid is critical to the process. Excess fluid will prevent the recycled asphalt from setting up when compacted by the rolling equipment. Too little fluid will not rejuvenate the recycled asphalt to pre-engineered specifications.
Polymer liquid (used in Superpave applications) is applied to the recycled asphalt by the addition (optional) of the supplemental liquid application system. Polymer liquid is stored in a non-heated, pressurized tank 316 mounted to the front, clip-on frame or the mainframe 3 of the Recycling Machine. An air operated, positive displacement, diaphragm pump 317 (electronically pulsed by the on-board computer) pumps and meters the fluid stored in the supplemental tank 316 delivering it to a hydraulically operated two-way valve 319 . N.C shut-off valve 320 shuts off the supply flow to pump 317 automatically during system shut down and air flushing. The positive displacement, diaphragm pump 317 delivers liquid accurately, as each stroke delivers an absolute volume. Air pressure (0.1-0.5 psi) is applied to the storage tank 316 to reduce the possibility of cavitation of the diaphragm pump 317 . The pump can accurately pump fluid with particle sizes up to ⅛″ in diameter, however, an in-tank wire mesh strainer 321 limits particle size to less than 50 mesh. Hydraulically operated two-way valve 319 allows liquid to be directed either to the pug mill's spray bars 289 and 290 or returned to the tank 316 . Check valve 322 prevents rejuvenator fluid and purge air from reverse flow. In normal operation the pug mill's spray bars 289 and 290 receive rejuvenator fluid from the pump 295 and polymer liquid from pump 317 with or without aeration (using compressed air). The two-way valve 323 allows air purging of pump 317 , valve 319 , check-valve 322 and the pug mill's spray bars 289 and 290 . Purging air is supplied through N.C. shut-off air valve 302 , flow control valve 304 , one way check valve 305 and hydraulically operated two-way valve 323 . Hydraulically operated two-way valve 319 is cycled while air purging, allowing air to first force liquid back to the tank 316 and secondly purge the pug mill's spray bars 289 and 290 . The top of the storage tank 316 is fitted with a low-pressure relief valve (0.1-0.5 psi) 303 , which allows the compressed air to escape A one way check valve 324 prevents purging air and polymer liquids from reaching the main mill's spray bar 186 . The one way check valve 324 also prevents polymer liquid from reaching the main mill's spray bar 186 when only polymer liquid is being sprayed in the pug mill. The tank discharge and return lines are fitted with shut-off valves 310 for system servicing and positive shut off. The supplemental application system is controlled and monitored by the on-board computer and is programmed to execute and apply a predetermined formula. Menus provide operator input for the varying rejuvenator fluids and polymer liquids being applied, application rates and flushing cycles. Electronic readouts (screen) provide information on application rates, accumulated totals, tons of recycled asphalt processed, distance traveled, asphalt temperature, tank temperature and system status.
FIGS. 50, 51 , 52 and 53 shows the offset pug mill 16 used for the final mixing, moisture removal (steam) and volume measurement of the milled (recycled) asphalt. The main housing 330 , is attached to the Recycling Machine's mainframe 3 draft tube by plates 331 and 332 . The bottom links (two) 333 , features plain replaceable steel bushings and threaded joints, allowing the links to twist and turn. The bottom links 333 prevent pug mill side movement, but allow for raising/lowering and tilting. The top links (two) 334 , feature spherical bearing at both ends, allowing movement in all directions, and are adjustable in length, allowing the pug mill to be set flat to the milled, asphalt surface. The hydraulic cylinders (two) 335 , attached to plates 332 and main housing 330 , raise and lower the pug mill. The cylinders 335 provide adjustable (hydraulic) down pressure allowing the pug mill to float but preventing it from riding up when full of asphalt. Three skids 336 attach to the main housing 330 and are responsible for maintaining the front rotor assembly 292 and the rear rotor assembly 337 paddle's 338 distance to the milled surface. Skid wear is low as the hydraulic down pressure is balanced against the lifting action of pug mill, while mixing. Attached to the offset front rotor assembly 292 and the rear rotor assembly 337 are paddle assemblies 338 fitted with replaceable carbide wear pads. The paddle layout of the offset, front rotor assembly 292 has two distinct areas. Area FIG. 52 “A” consists of paddles ( 2 paddles per arm), forming a double spiral with spaces, resulting in an inefficient conveying and mixing auger. Area “B” consists of left and right facing paddles (two and four paddles per arm) used for mixing and tumbling the asphalt and additives. The rear rotor assembly 337 faces area “B” of the offset front rotor assembly 292 . The rear rotor assembly diameter is larger than the front rotor assembly and provides improved mixing and greater material throughput than previous, equally sized rotors. Hydraulic motors 339 (attached to housing 330 ) and drive couplings 340 directly rotate rotor assemblies 292 and 337 in a down-ward direction, thereby reducing damage to the paddles and iron utility structures (compared to up-ward rotating rotors) located in the asphalt pavement to be recycled. The rotor assemblies end thrust and end support is by bearings 341 , attached to the end plates 342 . The end plates 342 allow for the quick and easy removal of the rotors assemblies for servicing. Rotor speed is variable and independent of the Recycling Machine's ground speed, or optionally, tied to ground speed. The non-intermeshing rotors do not require timing, as in the case of intermeshing rotors used in conventional pug mills, allowing rotational speeds to be set individually, promoting better mixing and greater moisture removal (steam).
The windrow forming ski 343 , located between the windrow forming plates 344 , causes resistance to asphalt flow through the pug mill's discharge, allowing the pug mill chamber to become loaded with asphalt. The rotors assemblies 292 and 337 tumble the asphalt and additives from the alternating left and right hand paddles, providing complete mixing and steam release. Resistance to asphalt flow through the pug mill also causes resistance to flow through the main mill, thereby increasing contact time between the asphalt, additives and mechanical mixing elements (mill carbide teeth and pug mill paddles). Close operating distances between the extension mills, main mill and the pug mill reduce the asphalt's heat loss and result in lower emissions. The main housing 330 incorporates a plenum chamber 345 and a steam pipe 346 . The production of negative air pressure at the pipe 346 is by a venturi (not shown), using the heater box blower, air supply. The tumbling and restricted asphalt enclosed in the pug mill's mixing chamber maintains the asphalt's temperature and together with the negative pressure, air extraction system, reduces the level of moisture in the asphalt. Blade 347 operates in the identical manner to main mill and extension mill's blade assemblies, its function being, to scrape the previously milled surface (main mill) and collect the fine asphalt for complete mixing.
Located between the two rotor assemblies 292 and 337 and scraping the complete width of the milled surface covered by the pug mill mixing chamber is the trip blade 348 . The trip blade scrapes the milled surface, picking up the asphalt missed by the pug mill's front rotor paddles. Rejuvenator fluid and polymer liquid inlets 349 and 350 are located directly above the front rotor assembly (spray bars are not shown).
FIGS. 54, 55 and 56 show the windrow forming ski 343 , bottom link 360 , top link 361 , link pins 362 , top pivot pin 363 , electronic sensor 364 , counterbalance hydraulic cylinder 365 and door 366 . The links 360 and 361 form a parallelogram linkage, keeping the windrow-forming ski 343 parallel to the milled asphalt's grade. The on-board computer adjusts the hydraulic pressure in the cylinder 365 electronically by measuring the pressure required to hydraulically drive the pug mill's rear rotor assembly 337 . It is also possible to electronically measure the front rotor assemblies 292 drive pressure to adjust the hydraulic pressure in cylinder 365 . Hydraulic drive pressure increases as the volume of asphalt in the pug mill's mixing chamber increases. Hydraulic pressure in cylinder 365 increases proportionally to the rear rotor's drive pressure and tries to pivot the top link 361 around the top pivot pin 363 , reducing the effective down force of the windrow-forming ski 343 . The pressure in the hydraulic cylinder never reaches a high enough value to physically lift the windrow-forming ski. Less down force on the windrow-forming ski reduces the resistance to the recycled asphalt's flow under the windrow-forming ski, allowing a greater volume of recycled asphalt to by forced out of the mixing chamber by the rear rotor assembly 337 . A reduction of hydraulic drive pressure in the rear rotor assembly causes the hydraulic pressure in cylinder 365 to be reduced, increasing the resistance to flow of recycled asphalt under the windrow-forming ski. The windrow-forming ski maintains a balance between the volume of recycled asphalt in the mixing chamber and the hydraulic pressure driving the rear rotor assembly. The rear rotor's hydraulic drive pressure remains fairly consistent once the mixing chamber has initially filled. The windrow-forming ski forms a slightly compacted, asphalt windrow with a flat top section, resulting in the accurate volume measurement of the recycled asphalt, reduced emissions, maintained heat and reduced segregation by preventing the larger aggregate (stone) from rolling down the windrow's sides.
Thus, the system described above prevents the pug mill's rotors from stalling to ensure proper mixing and retention of asphalt mix. In other words, when not enough material is in the pug mill, the system will sense a decrease in resistance in the rotors causing the windrow-forming ski to move downward to restrict the flow of material exiting the pug mill so as to retain the material in the pug mill for improved mixing as well as steam and fume extraction. When too much material is in the pug mill, the system will sense an increase in drive pressure. This will cause the pressure being exerted by the windrow-forming ski on the material exiting the mill to decrease.
Another way to accomplish this is to raise and lower the ski in response to the rotor pressure. When the rotor pressure is high, the ski is raised. When the rotor pressure is low, the ski is lowered.
The varying asphalt volume passing under windrow-forming ski 343 raises and lowers the windrow-forming ski, rotating the top pivot pin 363 , attached to the top link 361 . Electronic sensor 364 measures the rotation of the top pivot pin 363 , producing an electronic signal used by the on-board computer for processing the amount of rejuvenator fluid and/or polymer liquid to be added to the old asphalt and added aggregate. The electronic signal is proportional to the height of the windrow-forming ski 343 . The pug mill's discharge width is constant and together with the varying windrow-forming ski's height, calculates the volume of asphalt being processed. Door 366 is pushed back by the asphalt flow against the windrow-forming ski 343 , preventing the asphalt from flowing up and past the windrow-forming ski.
FIGS. 57, 58 and 59 show the pug mill's trip blade assembly 348 in its working and tripped position and also in an exploded view. The trip blade assembly 348 is located between the pug mill's front rotor assembly 292 and the rear rotor assembly 337 . The trip blade is the full width of the mixing chamber 370 . The trip blade scrapes the heated, milled, base surface, lifting any asphalt and additives missed by the front rotor paddles (the rotor paddles do not make contact with the milled base). As paddle tip wear increases the amount of asphalt missed would increase, reducing the mixing efficiency of the pug mill. Without the trip blade assembly 348 rejuvenator fluid and polymer liquid could not be sprayed into the pug mill as the fluid would come into direct contact with the milled base surface in the mixing chamber and would not be collected and mixed by the rotor's paddles 338 which would cause bleeding of the finished mat. The trip blade improves mixing and allows rejuvenator fluid and polymer liquid to be sprayed directly into the pug mill's front rotor 292 .
The trip blade body 371 is attached to arm 372 . Hydraulic cylinder 373 is attached between arm 372 and adjuster link 374 . Adjuster link 374 is attached to adjuster screw 375 by threaded pivot 376 and stationary bracket 377 . Adjuster screw 375 is located by stationary bracket 377 attacked to main housing 330 . The trip blade body 371 is adjusted for height by turning adjuster screw 375 while raising or lowering adjuster link 374 and hydraulic cylinder 373 . Hydraulic cylinder 373 is continuously pressurized (head end only) with hydraulic oil, thereby forcing the cylinder rod out to its maximum travel (bottomed out). Adjuster screw 375 can be adjusted while the pug mill is in operation, allowing fine adjustment of the blade's height. Normally the blade is set to just contact the milled surface. The trip blade is fitted with a replaceable, bolt on, carbide-faced blade 377 . When the screw adjustment is at its limit the blade 377 can be lowered (blade has slots for the clamping bolts) allowing the adjuster screw 375 to be returned to the beginning of its adjustment. In the tripped position (FIG. 58 ), the trip blade assembly 348 has rotated sufficiently allowing the blade to ride up and over the utility structure 378 . The trip blade assembly 348 is mounted and rotates in steel bushings 379 located in the left and center, wear shoes 380 . Hitting a utility structure rotates the trip blade assembly and arm 372 , forcing the hydraulic cylinder's rod into the cylinder 373 . The cylinder's head end hydraulic oil is displaced, allowing the trip blade to rotate, changing the blade's angle-of-attack into a ramp, causing the blade to ride up and over the utility structure. Hydraulic oil re-enters the head end of the hydraulic cylinder, automatically returning the trip blade to its working position (after the utility structure is cleared). Hydraulic pressure in the head end of the hydraulic cylinder is adjustable and is used to change the amount of force required to rotate the trip blade. In normal operation, the ground operator is responsible for manually raising and lowering the working sub assemblies, thereby preventing damage to utility structures. The Recycling Machine's rakes, mills and pug mill are all designed to withstand the abuse of hitting a utility structure. The pug mill's front rotor assembly 292 rotates in a down wards direction and is the first part to contact the utility structure. If the ground operator does not raise the pug mill, the front rotor will force the pug mill up with little or no damage to the front rotor's carbide paddles. Manually raising the pug mill cuts off the pug mill's rejuvenator fluid flow (main mill continues to receive rejuvenator fluid) and the windrow-forming ski's electrical sensor 364 signal, used by the on-board computer in calculating the volume of asphalt flowing through the pug mill. The on-board computer locks to the ski's sensor signal value (before manually raising the pug mill) whenever the pug mill is raised. Polymer liquid application to the pug mill is generally not stopped if the pug mill is raised for a brief period, however if the period exceeds a preset number of seconds, flow will be stopped. Lowering the pug mill restores the pug mill's rejuvenator flow and the ski's electrical sensor signal. An electrical limit switch (not shown) monitors the trip blade's position. Tripping the blade (contacting a utility structure) automatically allows the pug mill to raise by reducing the head end, hydraulic pressure (controlled by the on-board computer) in cylinders 335 . The force generated by the pug mill's front and rear rotor assemblies allows the pug mill to be forced up (away from the milled surface), thereby reducing the force of the trip blade assembly upon the utility structure.
It can be seen that iron utility structures located in the asphalt's surface are cause for concern, especially when working in city applications. Normally the Preheater operator will mark the asphalt's surface with a paint marker (spray can) indicating to the Recycling Machine operators where the structures are located. This works well, however some structures have been found to be below the asphalt's surface. To overcome the problem of dealing with iron utility structures the GPS's metal detection readings (described earlier) are used by the final Preheater (unit ahead of the Recycling Machine) and the Recycling Machine's GPS and on-board computers to automatically raise and lower the rake/blades, extension mills, main mill and the pug mill, preventing damage to the sub-assemblies and iron utility structures. For machines not equipped with the optional GPS system a metal detection boom is fitted to the front end of the Recycling Machine's mainframe 3 , or attached to the front asphalt hopper assembly 190 , (when fitted). The metal detection boom assembly is also fitted to the front end of final Preheater mainframe 3 (Preheater ahead of the Recycling Machine) when the rake/blade scarification system 11 , 12 and 13 is fitted. The metal detection boom is hydraulically adjustable in width to allow for varying processing widths.
FIG. 60 shows the main metal detection boom assembly 400 and the extension metal detection boom assemblies 401 , which are hydraulically extended from hopper frame 190 . The booms are located at the front end of the machines where heat and moisture are at the lowest levels. FIG. 61 shows a plan view of the boom assemblies 400 and 401 fitted with a series of metal detector heads 402 . The distance between the booms to the machines sub-assemblies is mechanically fixed. In the example shown the rake/blade assemblies 11 and 12 are at a set distance to the boom assemblies as are the main mill, extension mills and the pug mill. The main boom 400 is about to detect an iron utility structure 233 located in the heated asphalt's surface. Sensors 402 , A, B, and C detect the structure and the electronic input is stored into the on-board computer's memory. The position (location on the mainframe 3 ) of the rakes/blades, extension mills, main mill and pug mill is known. The position of the sensors on the main boom 400 and extension booms 401 is fixed and known. The position of the extension booms is electronically monitored as they are hydraulically moved in and out to adjust for the varying processing width. The on-board computer calculates the distance traveled (by monitoring the Recycling Machine's drive wheel rotary encoder) and the width location of the iron structure(s) by monitoring the individual sensors 402 and the two extension boom's location and sequentially raises and lowers the appropriate rakes/blades, extension mills, main mill and pug mill, preventing damage to the structure and sub-assemblies. The same system is used for Preheater's fitted the rake/blade assemblies 11 , 12 and 13 , however the booms are mounted directly to the front of the Preheater's mainframe 3 .
FIGS. 62, 63 , 64 and 65 show the Preheater's pin-on aggregate bin 21 used to spread aggregate on to the heated asphalt's surface, ahead of the Recycling Machine. The aggregate bin (hopper) 410 typically receives aggregate from a wheel loader. The rotor assembly 411 is mounted and driven (direct drive) at both ends by two, high torque, hydraulic motors 412 . The rotor assembly discharges aggregate as it rotates and it's speed is infinitely variable. The rotor assembly is fitted with equally spaced flutes 413 (bars) running the complete length of the rotor. The adjustable, rotating strike-off blades 414 controls the aggregate's depth on the flutes 413 as the rotor assembly turns. The adjustable, rotating strike-off blades can be adjusted to suit aggregates ranging from washed sand to Superpave sized stone. The flutes 413 provide a positive grip on the aggregate and prevent unwanted aggregate flow around the rotor assembly. Multiple rotating, strike-off blades are mounted across the full width of bin inline with the rotor assembly and are attached to the bin by hinges 415 . Flat springs 416 force the blades into the working (normal) position. An obstruction caught between the rotor's flutes 413 causes the blade to rotate around hinge 415 , allowing the obstruction to pass without damaging (rotor or blade) or stalling the rotor. Recycling continues uninterrupted. Aggregate is dropped on to the heated asphalt's surface in lines (caused by the flutes) allowing the operator and inspector to visually monitor the quantity and distribution pattern. The Recycling Machine's heater box skirts (front and rear) drag the heated aggregate and smooth (flatten) out the lines as the aggregate passes under the heater box 4 , providing complete aggregate drying and surface coverage. The rotor assembly 411 and flutes 413 are manufactured using stainless steel, thus preventing rusting and sticking when using small, damp aggregate. The discharge rate is computer monitored and controlled by measuring the Preheater's groundspeed, width of pass and asphalt surface profile (depth change). The rotor's discharge rate is measured and calibrated (lbs./cu. ft./1 RPM of the rotor assembly) by placing measuring pans on the asphalt's surface to catch the aggregate. The Preheater is used to heat and dry out the aggregate prior to electronic weighing. The dry weight is calculated and entered into the on-board computer as a reference. The operator selects the application rate (lbs./cu. ft.) as determined by prior laboratory testing of the asphalt and the depth of processing to be performed by the Recycling machine (inches). The rotor assemblies width is fixed, therefore the application rate can not be determined only by the distance traveled but must use distance traveled, processing width and asphalt profile (depth change) in the calculation. The wider the Recycling Machine's processing width or the greater the asphalt's processing depth, the faster the rotor assembly 411 must rotate to maintain the correct application rate and visa versa. High sections (greater volume of asphalt to be processed) will require more aggregate, while low sections will require less. One method to input the width of the road being encountered is to outfit the rake assemblies 11 and 12 with linear variable differential transducers (LVDT) to calculate the overall width of the rake assembly, which should match the width of the road. For width measurement with a Preheater that is not fitted with the rake scarification and blade collection system the operator uses two hydraulically operated weighted markers 417 attached to ABS (plastic) extendable arms or pipes 418 , sliders 419 and hydraulic cylinders 420 . The replaceable ABS arms 418 prevent damage to the sliders 419 if contact with solid objects, such as trees, poles etc., occur. As processing width varies the Preheater operator simply moves the weighted markers 417 in and out by supplying hydraulic oil to either hydraulic cylinder 420 attached to the sliders 419 . The right marker normally would hang above the edge of curb (gutter) and left marker, the center of the road. Individually monitored (electronically) sliders 419 provide processing width information to the on-board computer. The electronic sensor 421 , measures the actual rotor assembly speed in relation to the stored (calculated) reference speed (closed loop), insuring that the rotor assemblies speed remains correct, even under varying load conditions. This measuring system insures accurate width measurement, without the operator ever having to get off the Preheater and physically measure (with a tape measure) and manually enter the width into the onboard computer. Of course, other mechanical devices known to those of skill in the art may be used to measure the width of the road as well. For Preheaters fitted with the optional rake scarification and blade collection system the width measuring system's weighted markers, pipes, sliders and hydraulic cylinders are not required. Instead, the position of the extension rakes 11 is electronically monitored. The extension rakes are hydraulically extended or retracted by the operator as the width of processing (scarification) varies. If the rake scarification system is not required the operator uses the rake extensions as markers (rake teeth not lowered).
When the aggregate bin is attached to the front of the Recycling Machine the width and profile measuring system can be used as described below. It is also possible to use the pug mill's material measuring system as the reference for the volume of aggregate to be deposited. The Recycling Machine's on board computer is programmed for the amount of aggregate required (percentage of recycled asphalt being processed). As the volume of processed asphalt increases so does the discharge rate of the aggregate bin. A decrease in the volume of processed asphalt causes a reduction in aggregate being discharded. This system is not as accurate as the profile and width measuring system (described below) as the pug mill's measuring system is some distance behind the discharge of the aggregate bin's discharge. However on highway type work with good grade accuracy will remain high.
FIG. 66 shows the surface profile measuring system attached to the aggregate distribution bin 21 . Two averaging beams 430 (one on either side at the rear of the Preheater) are fitted with three sonic (beam) sensors targeting the heated (scarified or non-scarified) asphalt surface. Each beam has two base height sensors 431 , (one at the front and rear of the beam) and one grade height sensor 432 located in the center of the beam. The grade height sensor 432 is located under the centerline of the aggregate bin's discharge rotor assembly 411 . The on-board computer processes and stores the individual height readings of the front and rear base height sensors 431 (the actual height is not important) in relation to distance traveled (electronic pickup on Preheater drive wheel). The grade height sensor's 432 height is compared to the base height of the front sensor 431 . The rear sensor 431 provides a correction factor to the system, i.e. if the operator lifted the front of the Preheater to its upper limit while processing. Beams 430 would be tilted back resulting in the rear sensor height being less than the front sensors and also the grade height sensor 432 . The front base height sensor 431 provides cleaner target distance information than the rear sensor, due to the fact that the rear sensor is also measuring the lines of deposited aggregate. The programming code recognizes the varying height of the lines of aggregate and the base surface and provides in a consistent (filtered) reference. The difference between the base height and grade height is referred to as reference height. The two reference heights (left and right averaging beams) are then averaged and used by the on-board computer to correct for grade changes such as bumps and depressions. The accuracy of the system does not change when the operator raises or lowers the Preheater while working. The profile measuring system improves the accuracy of the aggregate distribution system when working with poor surface grades. For greater accuracy the number of averaging beams can be increased across the width of the asphalt being processed. The profile measuring system duplicates the grade profile to be milled by the Recycling Machine when operating on automatic grade and slope controls. For instance, a depression 3 feet wide by 2 inches deep across the width of the asphalt being processed would cause the volume of aggregate applied at the depression to be reduce as the amount of material to be milled to grade when reaching the depression will also be reduced. Without the profile measuring systems correction factor the distribution rate for aggregate would be based purely on the processing width and operator input for depth and would have resulted in excessive aggregate at the depressed area. A bump would have the reverse effect by providing too little aggregate for the amount of asphalt being milled to grade. Of course, other mechanical based systems may be used in place of the sensors.
Other systems and equipment spread aggregate (as noted before) by only measuring the distance traveled and therefore are not accurate. Systems that do not add aggregate are not capable of 100% Hot In-place Recycling of asphalt pavement while meeting pre-engineered specifications. The Remix method (mixing a percentage of new asphalt with the old asphalt) has become popular as the accurate control of rejuvenator fluid, addition of aggregate and the complete mixing of additives and asphalt are not required to the same degree as with 100% HIR.
FIG. 67 shows the Recycling Machine configured for 100% HIR with an integral overlay. The sub-component numbers from 1 to 16 are the same as described in the above. For the Integral Overlay method, of the sub-assemblies which may be used are the primary auger/divider/strike-off blade 23 , primary screed/tow arms 24 , secondary auger/strike-off blade 25 and secondary screed and tow arms 26 . The clip-on front asphalt hopper 190 and the central conveyor 191 and shuttle conveyor 29 are required to bring new asphalt to the secondary auger/strike-off blade 25 and secondary screed assembly 26 . The Recycling Machine's mainframe 3 is designed to incorporate the additional sub-assemblies, without having to be modified.
FIGS. 68 and 69 show a close up view of the rear end of the Recycling Machine set up for the Integral Overlay method. The primary auger/divider/strike-off blade 23 incorporates the shuttle conveyor 29 that directs new asphalt from the central conveyor 191 to the secondary auger 25 and screed assembly 26 or to the primary auger/divider/strike off blade 23 and screed assembly 24 . The position of the shuttle conveyor can be manually, or, automatically controlled (hydraulically moved towards the back end of the machine) by the on-board computer allowing new asphalt (delivered by the central conveyor) to spill off the front end of the shuttle conveyor into the primary auger/divider/strike off blade assembly when insufficient recycled asphalt is available to maintain the correct head of asphalt in front of the primary screed assembly. The design of the shuttle conveyor allows new asphalt to be delivered to both the primary and secondary auger and screed assemblies at the same time as the on-board computer monitors the asphalt requirements for both the primary and secondary operations and will increase the central conveyors delivery rate to match the increase demand. New asphalt can spill off the front of the shuttle conveyor while it is also conveying asphalt to the secondary operations.
Four hydraulic cylinders 450 and 451 attach the primary and the secondary screed to the Recycling Machine's mainframe 3 . The primary auger/divider/strike-off blade 23 is identical in construction and operation as described. The secondary auger/strike-off blade assembly is identical in construction, except that the divider is not attached. Electronic asphalt level sensors are fitted to the secondary auger/strike-off blade assembly 23 and move the new asphalt away from the chute 452 . As mentioned before, an electronic, proportional sensor monitors the level of asphalt in the chute 452 and the on-board computer controls the flow of new asphalt from the front asphalt hopper assembly 190 , central conveyor assembly 191 and the shuttle conveyor 29 into the chute 452 . The shuttle conveyor 29 is driven by hydraulic motor 453 and is electronically matched in speed to the central conveyor's speed. The primary and secondary screeds are attached to the primary and secondary tow arms 454 and 455 . Both of the tow arms are attached to the same pickup point 456 , which is part of the fulcrum arm 457 . Attached between the fulcrum arm 457 and the secondary screed tow arm 454 is the hydraulic cylinder 458 (one on both sides of the machine). The primary screed tow arm 455 does not require a hydraulic cylinder. The hydraulic cylinder is modified with a third port, allowing the rod's piston to float against a small flow (0.5 to 1 GPM) of high-pressure oil entering at a specific point in the cylinder barrel. The Recycling Machine pulls along the screed assemblies that are attached to the machine's mainframe 3 by housing 459 , horizontal fulcrum 460 , fulcrum-arm 457 and the screed's tow arms 454 and 455 . The horizontal fulcrum 460 can be pinned to the housing 459 if automatic grade controls are not required. The hydraulic cylinder 462 is attached between the horizontal fulcrum 460 and the housing 459 and receives hydraulic oil from the automatic grade control system (described in detail before). The horizontal fulcrum 460 is raised and lowered (by pivoting around point 461 ) by hydraulic cylinder 462 , which in turn raises and lowers the horizontal fulcrum's pivot point 456 . The screed tow arms are attached to pivot 456 .
FIG. 70 shows a cross section of hydraulic cylinder 458 . Hydraulic oil enters the cylinder barrel at port “A” at a controlled flow rate of 0.5 to 1 GPM. The maximum pressure is limited to 3000 psi. The oil flow entering port “A” is allowed to exit port “B”. Port “C” is connected to tank (low pressure). As the rod 463 is pushed into the cylinder the attached piston 464 begins to block off the oil passage at port “B”. The force pushing on rod 194 determines the hydraulic pressure at port “A”, which changes with the load on the screeds. Hydraulic pressure balances the load (pull). Two electronic pressure transducers monitor the pressures in each the two hydraulic cylinders (one on the left and right side, secondary tow arms). This pressure is graphically shown on the machine and the screed operator's terminal as a bar graph and is used in balancing the load on the screeds. This can be accomplished by the offset of the Recycling Machine and the screed's extension position. For example, if the left extension is extended to two feet and the right extension is not extended, the pull on the left side of the screeds will be greater. This causes the machine to be pulled to the side with the greatest load, resulting in constant steering corrections at the rear steering axle. The solution is to move the machine over to the left and extend the right extension and retract the left extension. The on-board computer also uses the transducer information to make small adjustments to the tow arm position by raising or lowering the tow arm pivot point 456 by controlling the operation of the hydraulic cylinder 462 . An electronic sensor measures the position of the horizontal fulcrum 460 . This feature is generally only used when the Recycling Machine is operating with the one screed assembly and with no automatic grade controls (city streets). With the single screed configuration the on-board computer makes small changes to the position of the tow arm pivot point to compensate for the varying load on the screed assembly. If the pressure increases in one or both of the cylinders 458 the horizontal fulcrum 460 will lower the tow arm pivot point. The ratio of pressure increase in the hydraulic cylinder 458 and the amount of movement of the horizontal fulcrum 460 are programmed into the on-board computer, and can be simply changed. The other function of hydraulic cylinder 458 is to prevent unwanted feedback into the screed assemblies. This can happen when a truck driver backs the dump truck too fast into the front asphalt hopper causing the Recycling Machine to be pushed back. When this happens the cylinder's rod 463 and piston 464 , are pulled out of the cylinders until the pistons hit the end of the cylinders. This gives plenty of travel and prevents the screed(s) from being pushed backwards. A make-up valve, located in the hydraulic manifold takes care of oil cavitation at port “A”. As soon as the Recycling Machine moves forward again the rod and piston is forced back into the “B” port position.
FIG. 69 shows the primary 24 and secondary 26 screed assemblies. The secondary screed 26 is allowed to float and features the same weight transfer system, as described earlier. The primary screed 24 requires no grade or slope controls and is also allowed to float, but not to the same degree as the secondary screed. The primary screed 24 senses the position of the secondary screed 26 through two proportional, hydraulic or electronic sensors 465 (electronic sensor are shown). The sensors are attached to the left and right side of the secondary screed tow arms 454 and sense the position of the left and right side of the primary screed tow arms 455 . The height of the sensor plates 466 can be adjusted by adjuster screw 467 to set the height differential between the primary and the secondary screed assemblies, which is generally ½″ to 1½″. The two screed sensors send information to the on-board computer, which in turn operates two hydraulic, 4-way, proportional, directional control valves. The secondary screed is the master while the primary is the slave and tries to match every move made by the secondary screed (master). The secondary screed is the master since it is the screed, which sets the final grade of the finished surface. To accomplish this the primary screed is attached to the Recycling Machine's mainframe 3 by two hydraulic cylinders 450 and the secondary screed by cylinders 451 . The four hydraulic cylinders prime function is to raise and lower both of the screeds. The secondary screed cylinders are allowed to float (move up and down freely) as all of the cylinder's hydraulic ports are connected to tank (return hydraulic oil) when laying asphalt. The primary screed's cylinders are also allowed to float; however the hydraulic cylinder's ports are connected to tank through flow control valves. The sensors that are attached to the left and right side of the secondary screed's tow arms 454 , sense the position of the left and right side, sensor plates 466 , that are attached to the primary screed's tow arms. The varying height differential is used by the on-board computer to controls the proportional valves (variable flow depending on the sensor output) which send a varying flow of hydraulic oil to the rod or head end of the hydraulic cylinders 450 . Oil is also flowing through the flow control valves. The greater the flow of hydraulic oil, the greater the pressure differentials across the flow control valves. The varying pressure differential influences the position of the primary screed assembly. The screed sensors will eventually turn off the proportional valves when the primary screed reaches the set point (differential height). The crank handles 467 on the primary screed can be adjusted to manually set the depth of asphalt being laid in relation to the secondary screed 26 if the system is being run in the manual mode. The crank handles must also be initially, manually adjusted in the automatic mode to make sure that the screed plates are operating at the correct angle, otherwise excessive screed plate wear will occur. To assist in the correct adjustment of the crank handles 467 , LED's (light emitting diodes) located on the control panels (on either side of the machine); monitor the operation of the two proportional valves. When the cranks are set properly and the primary screed is laying the correct differential of asphalt, no LED's will be on. The primary screed is setting its own height (grade). An example; the LED indicating that hydraulic oil is being supplied to the rod end, of the left side cylinder is on (the screed is low on that side), indicating to the operator that the crank handle for that side of the screed must be turned to raise the screed. The flow control valves allow the primary screed's cylinders to float in the same manner as the secondary screed's cylinders. The flow of oil through the flow control valves is approximately 1 to 2 GPM. This low rate is sufficient to allow the screed to float and find its own level, while at the same time, allowing the oil flow from the proportional valves to build up pressure in the appropriate cylinder.
One of the major problems associated with this type of recycling equipment has been the transportation to and from sites and the removal of equipment from major highways at the end of the day. Both the Recycling Machine and Preheaters are designed to be self-transportable (do not require a trailer) using a highway tractor to tow the machines.
FIG. 71 shows the invention in the transportation mode.
Attached to the mainframe of either the Recycling Machine or Preheater (Recycling Machine shown with all sub-assemblies removed for clarity, except the screed assembly 473 ), is the clip-on, stinger assembly 20 , shown extended and attached to the highway tractor 470 . Attached to an opposite end of the mainframe 3 is the clip-on, rear transportation frame assembly 471 shown with three air-ride axle assemblies 472 . The sub-assemblies of the invention are raised for the transportation position. Sub-assemblies such as screed 473 may be removed when weight and length restrictions prevent the device from being shipped as a complete unit, as shown in the lower view.
FIGS. 72, 73 74 and 75 show the clip-on stinger assembly 20 in the normal working mode “A” in the transportation mode “B” and an exploded view “C” and “D”. The stinger has a clip-on support frame 474 , which is attached to the mainframe's 3 two bottom cross tubes or attachment points 475 . The support frame 474 , which is attached without the stinger boom 476 or hydraulic cylinder 477 being in position. The support frame 474 is designed with left and right side hook plates 478 , allowing the frame to hang on the cross tubes 475 . Two safety latches 479 (one on either side) are used to secure the support frame 474 to the mainframe 3 . FIG. 75 shows the safety latch in the closed position (top) and in the open position (bottom). The safety latch is pinned into position by two safety pins through holes 480 . The safety latches must be in the closed position before the stinger boom 476 can be fitted. This design feature provides a failsafe locking arrangement as the support frame 474 cannot be removed without first removing the stinger boom 476 . In the unlikely event of both safety pins being removed or falling out, the safety latches 479 are still secured by the top surface of the stinger boom 476 . The hydraulic cylinder 477 is attached between the mainframe 3 and the stinger boom 476 and is used to extend or retract the stinger boom. The stinger boom is held in the extended (transportation) position by the hydraulic cylinder 476 and also pinned to the support frame 309 by two safety pins (one on either side), which are fitted into safety pin holes 480 . Attached to the stinger boom is the 5 th wheel pin 481 that attaches to the highway tractor's 5 th wheel plate.
FIGS. 76, 77 and 78 show close up views of the clip-on rear transportation frame assembly 471 . The air-ride axle assemblies 491 are attached to the sliding frame 492 . Holes 493 are located along the sliding frame at spaced intervals and line up with equally spaced holes 494 in clip-on support frame 495 . Four pins (not shown) attach the sliding frame 492 to the clip-on support frame 495 . FIG. 76 shows the position of the sliding frame and clip-on support frame in a configuration for use when all of the machine's sub-assemblies are attached for transportation. FIG. 77 shows the position of the sliding frame and clip-on support frame when sub-assemblies have been removed. In some states, weight restrictions prevent heavy axle loads from being used, necessitating the removal of sub-assemblies. As mentioned earlier, the three axle, sliding frame can be replaced with a four axle, sliding frame, without having to change the clip-on support frame. Also the sliding frame is fitting with four pin bosses 496 at the rear end allowing a pin-on attachment axle assembly to be fitted. This is generally required in northern climates when half load seasons are used. The clip-on support frame is attached to the Recycling Machine or Preheater's mainframes 3 by lowering the mainframe's 3 rear cross tubes FIG. 2, 22 into the top and bottom saddles (four) 497 . Two safety latches 498 are used to secure the clip-on support frame 495 to the machine's mainframe 3 . Two locking pins (not shown) are installed and secured through holes 499 , preventing the safety latches from moving. The design is such that the weight of the machines is sufficient to keep the clip-on support frame attached to the machine's mainframe. The safety latches provides a failsafe attachment system. FIG. 78 shows the clip-on support frame 495 with the safety latches 498 in the open position, allowing the machine's mainframe to be lowered into the saddles 497 . The ability to position frame 492 with respect to frame 495 allows for flexibility in positioning and weight loads over the axles.
FIG. 79 shows the Recycling Machine 3 (all major sub-assemblies removed for clarity) fitted with the clip-on, front asphalt hopper/5 th wheel pin 190 and the central conveyor 191 , both described in detail before. When 190 and 191 are attached to the Recycling Machine the clip-on stinger assembly 20 is not required as the clip-on, front asphalt hopper is fitted with a 5 th wheel pin attachment allowing the tractor 470 to reverse and lock into the 5 th wheel pin 500 for transportation when said hopper is in a raised position. For normal paving operations, the bin will be in a lowered position as shown in the drawings. A rear clip-on transportation frame 471 transports the rear end of the Recycling Machine or the Preheater, when the clip-on aggregate bin 21 is not attached. Generally only one Preheater is fitted with the aggregate bin 21 . For transportation, the bin may be removed and the clip-on rear transportation frame assembly 471 attached, or a fixed frame, clip-on transportation frame 501 (as shown in FIG. 80) may be attached to the aggregate bin, cross tubes FIG. 3, 22 . The aggregate bin remains attached to the Preheater's mainframe tubes 22 . The Recycling Machine and Preheaters hydraulic system is used to retract all of the attached sub-assemblies (including the front and rear axle assemblies 8 ) once the transportation frames and tractors have been attached, providing the necessary ground clearance for highway transportation.
Changes may be made to various components and the interconnecting thereof as described in the disclosure or the preferred embodiment, without departing from the spirit and scope of the present invention. | A method for providing hot-in-place recycling and repaving of an existing asphalt-based pavement, in which the pavement is first heated. The heated pavement surface is then sacrified, and new aggregate is dispensed onto it, to form a recycled, preheated asphalt and aggregate mixture. This mixture is again heated and scarified to premix it, and a new pavement surface is now milled to grade and width by applying this mixture using a plurality of extension mills having a main frame. The pavement surface is then remilled to grade using a main mill. Rejuvenator fluid is introduced in the main mill, and mixed with the recycled asphalt and aggregate mixture. Rejuvenator fluid is also introduced into a pug mill and again mixed with the recycled asphalt and aggregate mixture. The rejuvenator-enriched, recycled asphalt and aggregate windrow thus formed is then laid to grade using one or more screeds. | 4 |
BACKGROUND OF THE INVENTION
[0001] 1. Technical Field
[0002] The present invention relates to a phenol resin composition and a phenol resin copper-clad laminate using the same.
[0003] 2. Description of the Related Art
[0004] With recent miniaturization and multifunctionalization of electronic devices, printed wiring boards are also being densified and miniaturized. In such electronic devices, paper-based phenol resin copper-clad laminates are widely used as substrates for printed wiring boards of household electronic devices, because the laminates are excellent in stamping properties as well as drilling properties and they are also inexpensive.
[0005] The paper-based phenol resin laminate is produced by reacting a phenol and an aldehyde in the presence of an alkali catalyst to obtain a phenol resol resin, dissolving the resin in a solvent, impregnating paper-based sheets with the resultant solution, drying them to obtain prepregs, superimposing the several prepregs on each other, and then heating and pressing them. Usually, the prepregs are combined with a copper foil to form a copper-clad laminate, and the copper foil is then etched to form a circuit, thereby preparing a printed wiring board.
[0006] Moreover, owing to environmental protection, set makers have investigated or employed materials using no halogen flame retardant (halogen-free materials) and lead-free solder using no lead which is a harmful substance. For example, these materials are disclosed in Japanese Patent Laid-open No. 2001-181474. However, the lead-free solder has a higher melting temperature as compared with a conventional lead-containing solder (Sn—Pb). Therefore, a set temperature in a reflow step tends to be high. Thus, in recent years, there is required the improvement of heat resistance of the printed wiring boards, particularly the improvement of heat resistance in the reflow step.
[0007] The paper-based phenol resin copper-clad laminates are inexpensive, and therefore they are widely used. However, their heat-resistant levels are lower as compared with glass-based epoxy resin copper-clad laminates, and hence the temperature in the reflow step is also set at a low level. In consequence, when the set temperature is high, defects such as blister may occur. On the other hand, since the melting temperature of the lead-free solder is higher than that of the conventional solder (Sn—Pb), the temperature in the reflow step is set at a high temperature. Therefore, the printed wiring boards using the paper-based phenol resin copper-clad laminates containing lead-free solder tend to have defects such as blister.
[0008] As the phenol resin used in the paper-based phenol resin copper-clad laminate, a dry oil-modified phenol resol resin is mainly used in order to impart good stamping properties. However, the phenol resol resin forms water at a curing reaction during lamination and the water remains in the laminate. It is the main reason for decreased heat resistance. Moreover, when the dry oil is used, the ratio of combustible materials in the resin increases. In particular, in the case that the phenol resin is halogen-free, a sufficient flame resistance cannot be obtained unless a large amount of a phosphorus or nitrogen flame retardant is blended as described in Japanese Patent Laid-open No. 2001-181474. However, when a phosphorus flame retardant is used in a certain amount or more, the number of fine cracks at the time of stamping increases and water absorbability and heat resistance decrease. Furthermore, when a melamine-modified phenol resin is used in a certain amount or more as a nitrogen flame retardant, it is known that exfoliation increases at low-temperature stamping.
[0009] Hitherto, there is required a phenol resin composition having good flame resistance and stamping properties with no occurrence of defects such as blister in a reflow step when lead-free solder is used for printed wiring board, and also a phenol resin copper-clad laminate (halogen-free paper-based phenol resin copper-clad laminate) using the same.
SUMMARY OF THE INVENTION
[0010] Embodiments of the present invention are as follows:
[0011] (1) A phenol resin composition comprising: a melamine-modified phenol novolak resin; a phosphate ester; an epoxy resin; and a dry oil-modified phenol resin. (2) The phenol resin composition described in (1), which comprises 80 to 150 parts by weight of the phosphate ester 5 to 30 parts by weight of the epoxy resin and 65 to 100 parts by weight of the dry oil-modified phenol resin with respect to 100 parts by weight of the melamine-modified phenol novolak resin.
[0012] (3) A phenol resin copper-clad laminate which is obtainable by impregnating paper-based sheets with the phenol resin composition described in (1) or (2), drying them to prepare prepregs, superimposing the prepregs on each other, and then laminating a copper foil on the outermost layer of the prepregs.
[0013] According to the embodiments of the present invention, there are provided a halogen-free phenol resin composition which does not bring about defects such as blister in a reflow step when a lead-free solder is used for printed wiring boards, and which is excellent in stamping properties, and also a paper-based phenol resin copper-clad laminate in which the above composition is used.
[0014] The present disclosure relates to subject matter contained in Japanese Patent Application No.2003-195660, filed on Jul. 11, 2003, the disclosure of which is expressly incorporated herein by reference in its entirety.
DETAILED DESCRIPTION OF THE INVENTION
[0015] A melamine-modified phenol novolak resin for use in the present invention preferably contains 3 to 15% by weight of nitrogen. When nitrogen is less than 3% by weight, a sufficient flame resistance cannot be obtained in some cases, and when it exceeds 15% by weight, heat resistance and stamping properties are poor in some cases. An example of the melamine-modified phenol novolak resin includes, but not limited to, a melamine-modified phenol novolak resin (trade name: PR-6000 manufactured by Hitachi Chemical Co., Ltd.).
[0016] Examples of a phosphate ester for use in the present invention includes, but are not limited to, triethyl phosphate, tributyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, resorcyl diphenyl phosphate, and triisopropyl phenyl phosphate. They may be used singly or in combination of two or more of them. In particular, triphenyl phosphate is preferable because of being inexpensive.
[0017] The phosphate ester is preferably blended in an amount of 80 to 150 parts by weight with respect to 100 parts by weight of the melamine-modified phenol novolak resin. The phosphate ester functions as a flame retardant and a plasticizer. Therefore, when the amount of the blended phosphate ester is insuffcient, the laminate is poor in flame resistance and tends to occur exfoliation at the time of stamping. On the contrary, when it exceeds 150 parts by weight, white-eye (Mejiro; fine cracks on the resin around the hole) is remarkable at the time of the stamping, and water absorbability and heat resistance decrease in some cases.
[0018] An epoxy resin for use in the present invention preferably has an epoxy equivalent of 100 to 1000 and a weight-average molecular weight of 5000 or less and has two or more epoxy groups in a molecule. Examples of the epoxy resin include, but are not limited to, bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, alicyclic epoxy resins, phenol novolak epoxy resins, cresol novolak epoxy resins, bisphenol A novolak epoxy resins, diglycidyl-etherified products of polyfunctional phenols, and diglycidyl-etherified products of polyfunctional alcohols. They may be used singly or in combination of two or more. Among them, a liquid epoxy resin having an epoxy equivalent of 150 to 230 is preferable because of good workability.
[0019] The epoxy resin is preferably blended in an amount of 5 to 30 parts by weight with respect to 100 parts by weight of the melamine-modified phenol novolak resin. The epoxy resin is easily reacted with the melamine-modified phenol novolak resin to form a tough resin. However, when more than 30% parts by weight of the epoxy resin is blended, the reaction proceeds in a stage of a varnish or prepregs to shorten a pot life in some cases. On the contrary, when the amount of the epoxy resin is less than 5 parts by weight, the toughness of the resin becomes insufficient, and heat resistance and stamping properties deteriorate in some cases.
[0020] A dry oil-modified phenol resin for use in the present invention is preferably a dry oil-modified phenol resol resin. The dry oil-modified phenol resol resin is obtained by reacting a phenol with a dry oil in the presence of an acid catalyst, followed by the reaction with an aldehyde in the presence of an alkali catalyst.
[0021] Examples of the usable dry oil include, but are not limited to, tung oil, linseed oil, dehydrated castor oil, and oiticica oil. Examples of the usable phenol include, but not llimited to, phenol, m-cresol, p-cresol, o-cresol, isopropylphenol, and nonylphenol. A modification rate of the dry oil is preferably from 10 to 40% by weight. When the modification rate is less than 10% by weight, stamping properties are poor in some cases. On the contrary, when it exceeds 40% by weight, flame resistance deteriorates in some cases.
[0022] Examples of the usable aldehyde include, but are not particularly limited to, formaldehyde, paraformaldehyde, acetaldehyde, paraacetaldehyde, butylaldehyde, octylaldehyde, and benzaldehyde. Among them, formaldehyde and paraformaldehyde are preferable. An example of the acid catalyst is p-toluenesulfonic acid, and examples of the alkali catalyst include amine catalysts such as ammonia, trimethylamine, and triethylamine.
[0023] The dry oil-modified phenol resol resin is preferably blended in an amount of 65 to 100 parts by weight with respect to 100 parts by weight of the melamine-modified phenol novolak resin. The dry oil-modified phenol resol resin is preferably dispersed homogeneously in the phenol resin composition to impart plasticity. When the blended amount is less than 65 parts by weight, stamping properties decrease in some cases. Moreover, when the resin is blended in an amount exceeding 100 parts by weight, heat resistance decreases in some cases owing to the oil component contained.
[0024] The phenol resin composition of the present invention is dissolved or dispersed in a solvent to regulate the composition, and the thus regulated composition is then used as a varnish to impregnate paper-based sheets therewith. An example of the solvent is methanol. The varnish may be blended with a flame retardant other than the phosphate ester, for example, an inorganic filler-based flame retardant such as aluminum hydroxide, boric acid, zinc borate or magnesium hydroxide in such a manner that the amount of the flame retardant may be not more than 30 parts by weight of 100 parts by weight of the total composition. When the flame retardant other than the phosphate ester is blended, flame resistance can be enhanced by synergistic action and hence the case is preferable. When the blended amount of these flame retardants other than the phosphate ester exceeds 30 parts by weight, stamping properties and heat resistance tend to deteriorate.
[0025] Form the viewpoint of stamping properties, the base material to be used is preferably paper-based sheets. As the paper-based sheets, there can be used kraft papers, cotton linter papers, mixed papers of linter and kraft pulp, mixed papers of glass fibers and paper fibers, and the like.
[0026] It is preferable that the paper-based sheets are beforehand impregnated with a water-soluble phenol resin and then dried prior to the use of them.
[0027] Furthermore, the resulting paper-based sheets are impregnated with the varnish containing the above phenol resin composition and then dried to form prepregs. At this time, it is preferable to use a water-soluble phenol resin mixed with a solution containing an alkoxysilane derivative or its condensate, whereby heat resistance is further improved. The predetermined number of the thus obtained prepregs are superimposed on each other, and a copper foil is then laminated on the outermost layer of the prepregs, followed by heating and pressing to prepare a paper-based phenol resin copper-clad laminate. Lamination conditions are preferably a temperature of 150 to 180° C., a pressure of 9 to 20 MPa, and a period of 30 to 120 minutes.
[0028] The following will specifically describe the present invention with reference to examples, but the invention is not limited thereto.
[heading-0029] (Synthesis of Dry Oil-Modified Phenol Resol Resin)
[0030] Into a reaction vessel were placed 150 parts by weight of tung oil, 280 parts by weight of phenol, and 0.2 part by weight of p-toluenesulfonic acid, followed by 1 hour of a reaction. Then, 200 parts by weight of paraformaldehyde and 30 parts by weight of 28% by weight ammonia water were added thereto and the mixture was reacted at 75° C. for 2 hours to obtain a tung oil-modified phenol resol resin having a tung oil-modification rate of 35% by weight.
[heading-0031] (Blending and Preparation of Phenol Resin for Overcoat)
[0032] With 100 parts by weight of a melamine-modified phenol novolak resin (trade name: PR-6000 manufactured by Hitachi Chemical Co., Ltd.) were blended triphenylphosphate, the tung oil-modified phenol resol resin, and an epoxy resin (EPICLON 840-S manufactured by Dainippon Ink & Chemicals, Incorporated) in amounts shown in Table 1, and the whole was dissolved in methanol to prepare a phenol resin composition varnish having a solid content of 50% by weight.
[heading-0033] (Synthesis of Water-Soluble Phenol Resin for Undercoat)
[0034] One molar amount of phenol, 1.2 molar amount, in terms of formaldehyde, of 37% by weight formalin, and 0.4 molar amount, in terms of triethylamine, of a triethylamine aqueous solution (concentration: 30% by weight) were reacted at 70° C. for 6 hours to obtain a water-soluble phenol resin. The resulting water-soluble phenol resin is diluted with a mixed solvent of water/methanol of 1/1 by weight to obtain a water-soluble phenol resin for undercoat having a solid content of 12% by weight.
EXAMPLES 1 AND 2
[0035] A kraft paper having a thickness of 0.2 mm and a basis weight (weight of one sheet of paper per 1 m 2 ) of 125 g/m 2 was impregnated with the water-soluble phenol resin varnish for undercoat so that its attached amount after drying was 18% by weight, followed by drying. Then, the impregnated paper was further impregnated with the phenol resin varnish for overcoat so that total resin-attached amount was 50% by weight and dried to obtain a prepreg. Eight sheets of the resulting prepregs were superimposed on each other, and copper foils with an adhesive having a foil thickness of 35 μm were superimposed at the both sides so that the adhesive layers are toward the prepreg side. It was heated and pressurized at 170° C. under 15 MPa for 90 minutes to obtain a double-sided phenol resin copper-clad laminate having a thickness of 1.6 mm.
COMPARATIVE EXAMPLES 1 TO 3
[heading-0036] (Blending and Preparation of Phenol Resin for Overcoat)
[0037] With a melamine-modified phenol novolak resin (trade name: PR-6000 manufactured by Hitachi Chemical Co., Ltd.) were blended triphenyl phosphate and the tung oil-modified phenol resol resin having a tung oil-modification rate of 35% by weight in amounts shown in Table 1, and the whole was dissolved in methanol to prepare a phenol resin varnish having a solid content of 50% by weight. Except for the above, a double-sided phenol resin copper-clad laminate having a thickness of 1.6 mm was obtained in the same manner as in Examples 1 and 2.
[0038] With regard to the double-sided phenol resin copper-clad laminate obtained in the above, reflow heat resistance, flame resistance and stamping properties were evaluated. The results are shown in Table 1. Test methods are as follows.
[heading-0039] (Reflow Heat Resistance Test)
[0040] The copper foils of the resulting phenol resin copper-clad laminate were etched to prepare a printed wiring board having a remaining copper rate of 70%. In a reflow apparatus, the printed wiring board was flowed and presence of blister was visually observed. The temperature of the reflow apparatus was set so that maximum temperature of base material surface of the printed wiring board was 240, 250, or 260° C., and measurement was carried out. In Table 1, absence of blister was indicated by ◯, while presence of blister was indicated by X.
[heading-0041] (Flame Resistance Test)
[0042] The copper foils of the resulting phenol resin copper-clad laminate were etched over a whole area and then a test piece of 127×13 mm was cut off. The test piece was held so that the long edge was in a perpendicular position. The test piece was brought into contact with flame from the bottom for 10 seconds by a burner and this operation was repeated twice. A period required for quenching flame was measured. The flame resistance test was carried out on five test pieces and evaluation was conducted in accordance with the UL method.
[heading-0043] (Stamping Properties Test)
[0044] Stamping was conducted using a 24-hole test mold having a punch diameter of 1.0 to 1.2 mm, a pitch between holes of 2.54 mm while surface temperature of the test piece was changed. The periphery of holes of the punched test piece were visually observed and the state was indicated by symbols (◯: no exfoliation and no white-eye, Δ: slight exfoliation and white-eye, X: presence of exfoliation and white-eye). “White-eye” herein means a whitening phenomenon caused by occurrence of a number of fine cracks on the resin at the periphery of the hole surface when the test piece was punched.
TABLE 1 Example Comparative Example 1 2 1 2 3 Melamine-modified phenol 100 100 100 100 150 novolak resin* Tung oil-modified phenol 70 70 — 70 100 resol resin* Triphenyl phosphate* 40 80 40 40 40 Epoxy resin 15 15 — — — Reflow heat 240° C. ◯ ◯ ◯ ◯ ◯ resistance (maximum 250° C. ◯ ◯ ◯ ◯ X surface 260° C. ◯ ◯ X X X temperature) Flame resistance (UL method) 94 V-1 94 V-0 94 V-0 94 V-0 94 V-0 Stamping properties 40° C. Δ ◯ X X ◯ (surface 50° C. ◯ ◯ X ◯-Δ ◯ temperature) 60° C. ◯ ◯-Δ Δ Δ ◯-Δ *parts by weight
[0045] As shown in Examples 1 and 2, in the phenol resin compositions of the present invention, good reflow heat resistance and stamping properties were observed. Moreover, as shown in Example 2, the amount of triphenyl phosphate was increased to 80 parts by weight, flame resistance became better than that in Example 1 and thus requirements of UL94V-0 were satisfied.
[0046] On the other hand, in Comparative Examples, blister, exfoliation, and white-eye occurred. Therefore, it is apparent that reflow heat resistance and stamping properties are poor.
[0047] It should be understood that the foregoing relates to only a preferred embodiment of the invention, and it is intended to cover all changes and modifications of the examples of the invention herein chosen for the purposes of the disclosure, which do not constitute departures from the sprit and scope of the invention. | The present invention provides a phenol resin composition which does not cause any defect such as blister in a reflow step and which are excellent in flame resistance and stamping properties, and a phenol resin copper-clad laminate in which the above composition is used. The invention relates to a phenol resin composition which is obtainable by blending a melamine-modified phenol novolak resin with a phosphate ester, an epoxy resin and a dry oil-modified phenol resin, and also relates to a phenol resin copper-clad laminate which is obtainable by impregnating paper-based sheets with the above phenol resin composition, drying them to obtain prepregs, superimposing the prepregs on each other, and then a laminating copper foil on the outermost layer of the prepregs. | 2 |
CROSS REFERENCE
This application claims priority from U.S. provisional application Ser. No. 61/111,499 filed Nov. 5, 2008, herein incorporated by reference.
BACKGROUND OF THE INVENTION
The task of epigenomic mapping is inherently more complex than genome sequencing since the epigenome is much more variable than the genome. While an individual only has one genome, one's epigenome varies in time and space with age, tissue type, exposure to environmental factors, and shows aberrations in diseases especially in cancer. With methylated CpG's only accounting for ˜2-6% of the genome (18), large scale shotgun sequencing efforts will require some form of purification of short CpG methylated sequences. Many current enrichment technologies fall short of the dynamic range necessary to capture minute changes in CpG methylation that can have large repercussions in gene expression.
In the mammalian genome, 60-80% of relatively infrequent (1 per 100 bp on average) CpG dinucleotides are methylated at the carbon 5 position (1). In contrast, dense clusters of unmethylated CpG sequences (˜1 per 10 bp) are found at the transcription start sites of genes (2). In certain circumstances, these CpG islands are heavily methylated with the concomitant silencing of the promoter and the silencing of gene activity (3). These modifications are considered to be important for development (4), genomic imprinting (5), and X chromosome inactivation through gene silencing (6, 7). Aberrant DNA methylation of CpG islands has been frequently observed in cancer cells (8).
Many techniques exist for the enrichment of heavily methylated CpG islands from genomic DNA. One protocol relies on methylation-sensitive restriction endonucleases such as HpaII (CCGG) and HhaI (GCGC) followed by PCR identification, Southern Blot analysis or microarray profiling (9). Another approach utilizes the ability of an immobilized methyl-CpG-binding domain (MBD) of the MeCP2 protein to selectively bind to methylated double-stranded DNA sequences. Restriction endonuclease-digested genomic DNA is loaded onto the affinity column and methylated-CpG island-enriched fractions are eluted by a linear gradient of sodium chloride. PCR, microarray, DNA sequencing and Southern hybridization techniques are used to detect specific sequences in these fractions (10). These techniques are limited due to the specific cleavage moiety of the restriction enzyme and therefore will not completely reflect all combinations of bases flanking the methylated CpG dinucleotide.
There are several additional methods for analysis of methylation patterns. In the bisulfite method, single-stranded DNA (ssDNA) is exposed to a deamination reagent (bisulfite) that converts unmethylated cytosines to uracils while methylated cytosines remain relatively intact (11). After cleanup, the resultant treated DNA of interest must be PCR amplified (converting the uracils to thymines) and analyzed by a myriad of techniques that can distinguish between methylated and unmethylated DNA. If the PCR products are cloned and sequenced, alignment analysis of the untreated and treated nucleotide sequences can reveal the in vivo methylation status of the amplified region. The PCR products can also be analyzed by combined bisulfite-restriction analysis (COBRA assay) and methylation-specific PCR (MSP) (12, 13).
Recently, direct shotgun ultra-high-throughput sequencing of bisulfite-converted DNA using the Illumina 1G Genome Analyzer and Solexa sequencing technology have yielded insights of the methylation state of the small (˜120 Mbp) genome of the mustard plant Arabidopsis (14). This new technology allowed the exact identification and quantification of 5-methylcytosines at the single-nucleotide level in genes. Although highly specific and reasonably sensitive, it required at least 20-fold coverage to theoretically cover all potential methylated cytosines. Currently, no method exists to enrich bisulfite-converted CpG methylated DNA, which by the nature of the deamination reaction, is single-stranded, from total genomic DNA.
SUMMARY
Methods and compositions are described herein that include the embodiments listed below.
In one embodiment, an isolated first polypeptide is provided that includes an amino acid sequence having at least 90% homology or identity with SEQ ID NO:3 and is capable of binding single-stranded methylated polynucleotides. The first polypeptide may be fused to a second polypeptide and may be immobilized on a solid substrate by means of the second polypeptide if the second polypeptide is a substrate-binding domain such as maltose-binding domain (MBP). A property of the isolated first polypeptide may include an ability to bind a methylated CpG in a single-stranded polynucleotide.
Examples of the first polypeptide are human UHRFI, and mouse NP95 SRA. Either of these polypeptides may be used in series or in parallel with a methyl-binding domain (MBD), which binds double-stranded methylated DNA and thus recovery of methylated DNA may be enhanced. For example, the sample may be applied to a MBD column, eluted, denatured and then applied to an SRA column. Additionally, one aliquot of a sample may be applied to an MBD column and one aliquot of sample applied to an SRA column.
The above-described polypeptides either alone or as a fusion protein, either in solution or immobilized on a substrate, may be used for differentially binding a single-stranded methylated polynucleotide to a solid substrate, for example at a CpG site in a low salt solution.
In an embodiment of the invention, a method is provided for enriching for CpG methylated single-stranded polynucleotides from a mixture containing methylated and unmethylated polynucleotides. This method includes: binding the mixture to the first polypeptide described above; eluting the unmethylated polynucleotide from the isolated polypeptide in a solution containing a low concentration of a salt; and eluting the methylated polynucleotide from the isolated polypeptide in a solution containing a high concentration of a salt. The eluted methylated polynucleotide can then be sequenced and the methylation site analyzed.
In embodiments of the invention, a low concentration of the salt is less than 0.4 M salt and a high concentration of the salt is 0.4 M-0.6 M salt. The salt may be, for example, sodium chloride.
In an embodiment of the invention, a method is provided which can be applied to determining the existence of pre-cancerous cells. The method includes: (a) comparing the methylation pattern for selected polynucleotide sequences in both pre-identified transformed eukaryotic cells and non-transformed eukaryotic cells by differential binding of methylated polynucleotides to the first polypeptide of claim 1 ; (b) determining the presence of abnormal methylation patterns associated with alteration of tumor suppressor function; and (c) utilizing the abnormal methylation patterns as a diagnostic tool for determining whether any eukaryotic cells in a sample are transformed. (In this context “transformed” is intended to mean converted to a pre-cancerous state where the cell is immortalized.)
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1A-1C show a GST-SRA-domain resin with bound and eluted methylated, and unmethylated dsDNA at low NaCl; and eluted methylated ssDNA at high NaCl.
FIG. 1A is a chromatogram profile at A280 of human chromatin DNA spiked with a small amount of FAM-labeled methylated (M) and unmethylated (U) CpG-containing oligonucleotides. Both the unmethylated and methylated oligos co-eluted with the bulk of the chromatin DNA between 0.2 M and 0.3 M NaCl.
FIG. 1B shows a gel containing individual column fractions in each lane. At higher NaCl, a faint band (*) on the gel was observed corresponding to single-stranded methylated DNA.
FIG. 1C shows a side-by-side comparison of the methylated and unmethylated oligos confirming that the band (*) corresponded to methylated CpG-containing ssDNA.
FIGS. 2A-2B show a DNA preparation with significantly altered elution characteristics of the GST-SRA-domain column.
FIG. 2A is a comparison of chromatogram profiles at A280 of 100 μg of MseI-digested HeLa DNA spiked with 3 μg of MseI digested M.SssI-labeled 3 H-Adomet HeLa DNA. The DNA composition was heated to 98° C. for one minute and quickly chilled prior to loading onto the column. A large portion of the 3 H-labeled DNA eluted off the column at 0.15 M NaCl, however, three distinct peaks that eluted at 0.3 M, 0.35 M and 0.4 M NaCl were observed with a small peak of 3 H-labeled DNA co-eluted with the 0.4 M NaCl peak. The gel shows the content of each fraction.
FIG. 2B shows the same DNA load preparation, which was sonicated for 1 minute followed by heating of the sample to 98° C. for 1 minute, chilled, and loaded onto the column. Three peaks were observed at 0.35 M, 0.4 M and 0.45 M NaCl with the bulk of the 3 H-labeled DNA co-eluted with the 0.4 M and 0.45 M peaks, respectively. The gel shows the content of each fraction.
FIG. 3 shows a flowchart of the procedures used to enrich single-stranded methylated CpG-containing DNA. Total genomic DNA was sonicated to 50-150 base fragments. The sample was heated to 98° C., chilled and loaded onto the GST-SRA-domain column (or magnetic beads), or bisulfite-converted (which made the sample single-stranded and converted all non-methyl cytosines to uracils) prior to loading. The column/beads were washed with buffer containing 0.3 M NaCl, which eluted the active gene fraction. Methylated CpG-containing DNA remained on the column matrix and can be eluted with 0.5 M NaCl or alternatively equilibrated with low NaCl buffer prior to the addition of the “fourN” cloning/sequencing primer (SEQ ID NO:1). The sample was heated to 98° C., chilled to 4° C., and then slowly raised to 37° C. Sequenase was introduced into the reaction, allowed to extend the ssDNA fragments, heated and chilled, with more Sequenase added to label the other end of the DNA fragment. The defined-ends DNA was further amplified by a complementary PCR primer without the random nucleotides, purified and digested with BamH1, purified and cloned into a sequencing vector.
FIGS. 4A-4D show a simplified step salt gradient of GST-SRA-domain column yielded reproducible elution profiles.
FIGS. 4A-4B show a comparison of two chromatogram profiles at A280 of 100 μg of sonicated, heated HeLa genomic DNA FIG. 4A or 200 μg initial concentration of sonicated, bisulfite-converted genomic DNA FIG. 4B . The 0.3 M and 0.5 M fractions were characterized by qRT-PCR or cloned and sequenced.
FIG. 4C shows the bisulfite-converted fractions which were labeled and extended with a random “fourN” oligonucleotide, and PCR amplified. Ethidium-stained 20% TBE polyacrylamide gel analysis of the PCR products before (−) and after (+) BamH1 treatment showed the size distribution of fragments from the two peaks.
FIG. 4D shows GST-SRA-domain coupled magnetic beads only retained methylated (M) ssDNA lambda DNA after extensive washing with 0.3M NaCl as assayed on an ethidium-stained 20% TBE polyacrylamide gel.
FIG. 5 shows active and inactive gene enrichment from GST-SRA-domain column. Active genes showed at least a 2-fold enrichment over input DNA in the 0.3 M peak. Single copy inactive genes showed a direct correlation of the fold enrichment and CpG occupancy in the 0.5 M peak. As the copy number increased, satellite and line elements showed an inverse correlation between CpG occupancy and enrichment.
FIG. 6 shows a cartoon of the UHRFI gene illustrating the location of the different domains in the protein. The inset shows an amino acid alignment of the SRA domains from mouse and human (SEQ ID NOS:2 and 3, respectively), revealing that the sequences are 90% identical.
FIG. 7 shows the DNA sequences of mouse and human (SEQ ID NOS:4 and 5, respectively).
FIG. 8 shows how SRA domain can be used in sequencing platforms (e.g. Helicos sequence platform) to detect methylated CpG DNA. 1. Methylated ssDNA (SEQ ID NO:6) annealed to polyT on a slide. 2. Methylated cytosine detected by fluorescence labeled NP95 SRA domain and 3. SRA is washed off. DNA is sequenced. Within the flow cells, billions of single molecules of ssDNA are captured on a solid surface. These captured strands serve as templates for the sequencing-by-synthesis process. Prior to the addition of polymerase and one fluorescently labeled nucleotide (C, G, A or T), the cell is flooded with MBP-SRA domain protein, which binds specifically to methylated CpG sequences. The cell is washed with a 100 mM NaCl wash buffer, and fluorescently labeled Anti-MBP antibody couples to the MBP-NP95 SRA domain/methylated CpG DNA complexes. After a wash step, which removes free Anti-MBP antibody, the cell is imaged and the positions of the methylated CpG-containing DNA strands are recorded. A high wash step (500 mM NaCl) removes the Antibody-MBP-NP95 SRA domain and the sequencing process continues with a polymerase catalyzing the sequence-specific incorporation of fluorescent nucleotides into nascent complementary strands on all the templates. Multiple cycles result in complementary strands greater than 25 bases in length synthesized on billions of templates, providing a sequence read on the methylated CpG templates.
FIG. 9 shows a flowchart of the procedure used to compare a commercially available methylated CpG DNA enrichment system (e.g. Invitrogen) with MBP-NP95 SRA domain. Total HeLa genomic DNA was sonicated to 50-150 base fragments. Half of the sample was heated to 95° C. for 5 minutes and chilled on ice. The other half of the sample was not heated. To 1 μg of unheated sample, 1 μg of biotinylated (bt) MBD and buffer were added. Similarly, to 1 μg of heated DNA, 1 μg of MBP-NP95 SRA domain and buffer were added. Both samples were incubated at room temperature for 20 minutes. To the bt-MBD sample 100 μl (1 mg) of Streptavidin Magnetic Beads was added. To the MBP-NP95 SRA domain sample 100 μl (1 mg) of Anti-MBP Magnetic Beads was added. The samples were then incubated overnight at 4° C. with rotation. The bound complexes were then washed 3× with 100 mM NaCl, 1% Triton, 0.1% Tween buffer, with magnetic separation and aspiration of buffer and 1× with TE buffer containing 0.1% Tween. Finally, a small quantity of water was added to the aspirated samples, and the enriched methylated DNA complexes were eluted from the magnetic beads by heat. The complexes were then assayed by qPCR using primer sets to known active and inactive genes in HeLa DNA.
FIG. 10 shows the number of fold enrichment values of known methylated (inactive) and unmethylated (active) genes comparing a commercially available methyl CpG enrichment system (e.g. Invitrogen) with MBP-NP95 SRA domain protein. Both techniques resulted in similar enrichment of the inactive genes rDNA and MYOD, with no enrichment of the active gene RPL30.
DETAILED DESCRIPTION OF EMBODIMENTS
UHRFI is a ubiquitin-like protein that improves fidelity of maintenance of methylation and has a histone methyltransferase function. It contains multiple domains (see FIG. 6 ). Two adjacent domains in the protein are named SET and RING and together are called the SRA domain. The SRA domain has a sequence shown in FIG. 7 . The SRA domain is capable of binding methylated CpG in a salt-dependent manner. In an embodiment of the invention, the SRA is immobilized on a matrix and can be used to bind methylated and unmethylated ssDNA or bisulfite-converted genomic DNA at low salt conditions (for example 0.15 M NaCl). The unmethylated DNA can be eluted from the SRA protein in conditions of increased salt concentration such as 0.3 M NaCl while methylated DNA can be eluted at 0.5 M NaCl.
Human UHRFI is an example of a family of DNA-binding proteins that are associated with regulating gene expression via methylation. Other example include DNMTI and mouse NP95 SRA. This family of related proteins are shown here to be effective in differentiating methylated from unmethylated DNA.
These proteins can be produced in high yield and are relatively stable, which makes them suitable for attaching to solid substrates such as agarose resin or carbohydrate-coated beads or magnetic beads (NEB) without loss of binding activity. The immobilized protein can easily be integrated in a high-throughput bisufite sequencing setup. With just one wash step, mild elution characteristics, sensitivity and accuracy are enhanced. Thus, the reusable matrix provides valuable information on the methylome, providing insights into aging and disease.
There are a variety of approaches by which the SRA-like proteins can be immobilized on a matrix. The matrix may include beads, 96 well plastic dishes, columns or any other support material. Where beads are selected, these can be magnetic, colored and/or coated with a carbohydrate or other ligand suitable for binding the SRA. To facilitate binding of the SRA-like proteins to a matrix, the SRA-like protein can be synthesized as a fusion protein by standard molecular biology techniques in prokaryotic or eukaryotic host cells. For example, the SRA-like proteins may be synthesized as SRA-chitin-binding domain for binding chitin or SRA-MBP for binding to amylose. Examples of suitable fusion proteins are provided for example in U.S. Pat. No. 5,643,758.
Other examples of fusion proteins include SRA-AGT or SRA-ACT proteins (using the SNAP-tag™ or CLIP-tag™ technology provided commercially by New England Biolabs). These fusion proteins can be labeled as required for detection of purification of polynucleotides for example by using fluorescent labels after covalent binding of the ACT/AGT in the fusion protein to labeled substrates such as benzyl guanine or benzyl cytosine, leaving available the SRA to bind methylated DNA in vitro or in vivo.
The SRA may also be bound to a matrix or solid substrate such as beads, columns, glass, plastic or polymer surfaces, etc. Binding can be achieved by any ligand/ligand-binding molecule system including antibody/antigens or biotin/strepavidin, chitin-binding domain, maltose-binding domain, etc. SRA-like proteins may be synthesized as intein fusions to facilitate certain separation methods (U.S. Pat. Nos. 5,496,714 and 5,834,247).
In an embodiment of the invention, a binding preference for methylated single-stranded polynucleotides by SRA-like proteins was demonstrated. This property can be exploited for detection, purification and analysis of the polynucleotides using immobilized SRA bound to the matrix. The methylated polynucleotides can then be sequenced to identify the location of the methylated CpG. In another embodiment, a double stranded polynucleotide can be bound to SRA where methylation if present can be detected on one strand or the other.
Mammalian UHRF1 SRA domains (such as human UHRF1 or murine NP95) can be used to augment high-throughput sequencing methodologies, for example, True Single Molecule Sequencing (tSMS)™ technology (Helicos Biosciences) by binding and identifying single-stranded methylated CpG-containing DNA prior to a series of nucleotide additions and detection cycles that will then determine the sequence of each fragment ( FIG. 8 ). By integrating the UHFR1-SRA domain into this instrumentation setup, additional epigenetic information can be layered on top of rapid and inexpensive resequencing of genomes to facilitate the understanding of methylation states in complex organisms.
The mammalian UHRF1 SRA domains can be displaced from the polynucleotide by adding cations that neutralize the charge on the DNA and thereby release the electrovalently bound protein. In embodiments of the invention, the protein binding to the polynucleotide is disrupted using NaCl. However, the use of this salt is not intended to be limiting. Moreover, it was found that protein binds to polynucleotide at methylated CpGs more tightly so that a high salt concentration was required to release CpG methylated polynucleotides and a low salt concentration was required to release CpG unmethylated polynucleotides. In an embodiment of the invention, the low salt concentration was 0.3 M NaCl whereas the high salt concentration was 0.5 M NaCl. Table 1 provides the results of a two-step salt gradient.
Table 1 shows a sequence analysis of the two NaCl peaks from the GST-SRA-domain column. Greater than 10-fold enrichment of methylated CpG-containing DNA was observed. 19/30 reads with an average size of 63 bases in the high (0.5 M) NaCl fraction contained at least one methylated CpG. 44/1900 bases were methylated CpG or 2.32% of the total. 3/22 reads with an average size of 105 bases in the low salt 0.3M peak contained methylated CpG. 5/2327 bisulfite-converted bases were identified as methylated CpG or 0.215% of the total.
EXAMPLES
Example 1
SRA-Domain Protein Purification and the Covalent Coupling of the Protein to Solid-State Matrixes
The SRA domain (386-618) was amplified from full-length human UHRF1 cDNA synthesized using total RNA from HeLa cells. The product was cloned into pENTR-TEV (GST Tag Invitrogen) and recombined into pDEST15 (Invitrogen, Carlsbad, Calif.) to create the GST fusion. The construct was propagated in T7 Express E. coli (NEB) to an OD 590 of 0.5 at 37° C. and induced with 0.1 mM IPTG overnight at 16° C. Cells were spun, broken open by French press, spun again and the supernatant layered over a 10 ml Glutathione Separose High Performance column (GE Healthcare). After a 10-column wash, the protein was eluted with a 10 mM L-Glutathione (Sigma) solution. The yield was 12 mg total of purified SRA-domain from 8 liters shake flasks.
GST-SRA Column
9 μls of 1.2 mg/ml (10.8 mg total) of previously purified and dialyzed GST-SRA-domain protein in 10 mM Tris pH. 7.5, 1 mM EDTA and 0.2 M NaCl was layered onto a 4.5 ml Glutathione Sepharose matrix equilibrated with the above buffer. Of the 10.8 mg load, 7.83 mg remained bound to the column. The resin was washed with 10 column volumes of the above buffer, then cycled twice with the above buffer supplemented with 1 M NaCl before final equilibration at 0.05 M NaCl. Sequences of the methylated oligonucleotides were FAM-GTAGG5GGTGCTACA5GGTTCCTGAAGTG top strand (SEQ ID NO:7), FAM-CACTTCAGGAAC5GTGTAGCAC5GCCTAC bottom strand with 5=5 methyl cytosine. Sequences of the unmethylated oligonucleotides were GTCACTGAAGCGGGAAGGGACTGGCTGCTCCCGGGCGAAGTGCCGGGG CAGGATCT-FAM top strand (SEQ ID NO:8), AGATCCTGCCCCGGCACTTCGCCCGGGAGCAGCCAGTCCCTTCCCGCTT CAGTGAC-FAM bottom strand.
qPCR Analysis of NaCl Fractions From GST-SRA-Column
DNA from the high and low salt fractions were characterized by real-time PCR on a Bio-Rad MyiQ iCycler using Bio-Rad iQ SYBR Green Supermix and the following primer sets: hsALDOA TCCTGGCAAGATAAGGAGTTGAC forward (SEQ ID NO:9), ACACACGATAGCCCTAGCAGTTC reverse (SEQ ID NO:10), hsSERPINA GGCTCAAGCTGGCATTCCT forward (SEQ ID NO:11), GGCTTAATCACGCACTGAGCTTA reverse (SEQ ID NO:12), hsRPL30 CAAGGCAAAGCGAAATTGGT forward (SEQ ID NO:13), GCCCGTTCAGTCTCTTCGATT reverse (SEQ ID NO:14), hsRASSF1 TCATCTGGGGCGTCGTG forward (SEQ ID NO:15), CGTTCGTGTCCCGCTCC reverse (SEQ ID NO:16), hsMYO-D CCGCCTGAGCAAAGTAAATGA forward (SEQ ID NO:17), GGCAACCGCTGGTTTGG reverse (SEQ ID NO:18), hsMYT1 TGAAACCTTGGGTGTCGTTGGGAA forward (SEQ ID NO:19), TTGCGGGCCATTGTTCCATGATGA reverse (SEQ ID NO:20), rDNA CGTACTTTATCGGGGAAATAGGAGAAGTACG forward (SEQ ID NO:21), GTGCTTAGAGAGGCCGAGAGGA reverse (SEQ ID NO:22), hsSAT ATCGAATGGAAATGAAAGGAGTCA forward (SEQ ID NO:23), GACCATTGGATGATTGCAGTCA reverse (SEQ ID NO:24), LINE CGGAGGCCGAATAGGAACAGCTCCG forward (SEQ ID NO:25), GAAATGCAGAAATCACCCGTCTT reverse (SEQ ID NO:26). Cycle program was as follows: cycle 1: (1×) 95° C., 5 minutes, cycle 2 (40×) step 1: 95° C. 10 seconds, step 2: 61° C. 30 seconds, step 3 72° C. 30 seconds.
Cloning and Sequencing of NaCl DNA Fragments from GST-SRA-Column
Eluted and de-salted DNA fragments were cloned into BamH1 cut and alkaline phosphatase (CIP) treated LITMUS 28i cloning vector using the “fourN” procedure (17) with the exception of the sequence of the oligonucleotide: GTTTCCCAGTCAGGATCCNNNN (SEQ ID NO:1) and PCR primer GTTTCCCAGTCAGGATCC (SEQ ID NO:27). PCR products were purified using Qiagen columns cut with BamH1, purified again, ligated to the vector and cloned as stated.
Results
GST-SRA-Domain of Human UHFR1 Coupled to a Solid Matrix Enriched Single-Stranded Methylated CPG-Containing DNA
To determine the preference of the SRA-domain for unmethylated, fully methylated or hemi-methylated double-stranded or ssDNA in a solid state matrix, the following experiment was performed. 7.83 milligrams of purified GST-SRA domain was bound to a 4.5 ml GST column. 1.68 milligrams of MNase digested chromatin (˜150-1000 bp) from human Jurkat cells spiked with 1 μg each of fluorescein (FAM)-labeled double-stranded methylated CpG oligonucleotide and unmethylated CpG oligonucleotide of different sizes were layered onto the column in buffer A (10 mM Tris pH. 7.5, 1 mM EDTA, 0.05 M NaCl). After a 10 volume column wash with buffer A, the column was developed with a 100 ml NaCl gradient to 1 M and the fractions were assayed by gel electrophoresis ( FIGS. 1A-1C ). Both the methylated and unmethylated DNA oligos co-eluted with the bulk of the chromatin DNA between 0.2 M and 0.3 M NaCl. Interestingly, a faint fluorescent band that was smaller than the two annealed oligos was eluted off the column at ˜0.4 M NaCl. It was speculated that this band might contain unannealed methylated ssDNA.
To further investigate the binding preferences of the SRA-domain resin for ssDNA, 100 μg of MseI-digested HeLa DNA spiked with 3 μg of MseI-digested M.SssI-labeled 3 H-Adomet HeLa DNA was applied to the above equilibrated GST-SRA domain column. After column wash in buffer A, a 30 ml step gradient from 0.1 M to 0.6 M NaCl was initiated and fractions collected. The double stranded DNA and the 3 H-labeled fully methylated double-stranded DNA eluted off the column in the first two fractions at 0.15 M NaCl. Next, another DNA preparation of the same composition was heated to 98° C. for 1 minute and quickly chilled on ice for 5 minutes prior to loading on the equilibrated column. The above step gradient was used to elute the DNA and the fractions were analyzed as before. A large portion of the 3 H-labeled DNA eluted off the column at 0.15 M NaCl; however, three distinct peaks that eluted at 0.3 M, 0.35 M and 0.4 M NaCl were observed with a small peak of 3 H-labeled DNA co-eluted with the 0.4 M NaCl peak. Finally, a third DNA load preparation was sonicated for 1 minute followed by heating of the sample to 98° C. for 1 minute, chilled, and loaded onto the column. Three peaks were observed at 0.35 M, 0.4 M and 0.45 M NaCl with the bulk of the 3 H-labeled DNA co-eluted with the 0.4 M and 0.45 M peaks, respectively ( FIGS. 2A and 2B ). It was concluded that sonication plus heating of the sample fully fractionated the genomic DNA into a single-stranded form that facilitated binding of the DNA to the resin and greatly improved the resolving power of the matrix to discriminate between unmethylated and fully methylated CpG DNA.
Simplified Elution Profile Enriched Active and Inactive Genes
A new DNA preparation containing 100 μg of sonicated, heated HeLa genomic DNA was layered onto the above equilibrated column in buffer A. To simplify the elution protocol, a 0.15 M wash step and a 0.3 M and 0.5 M elution steps were employed. Fractions containing the 0.3 M and 0.5 M peaks were collected, desalted and concentrated using a Qiagen miniprep column ( FIG. 3 flow chart and FIGS. 4A-4D ). The products from the salt fractions were characterized by qPCR on a BioRad iCycler using primers to known active and inactive genes in HeLa cells ( FIG. 5 ). The actively transcribed genes Aldolase A (ALDOA), serpin peptidase inhibitor (SERPINA) and 60S ribosomal protein L30 (RPL30) showed a consistent two-fold enrichment in the 0.3 M peak over input DNA. The high salt peak, presumably containing the inactive gene fraction, revealed little or no enhancement of these genes.
Six known repressed areas of the HeLa genome were interrogated in a similar fashion. Single-copy genes RAS association domain family protein 1 (RASSF1), myogenic differentiation 1 (MYO-D), and myelin transcription factor 1 (MYT1) as well as tandem repetitive ribosomal DNA (rDNA) showed a direct correlation of fold enrichment and CpG occupancy in the 0.5 M peak. Highly repetitive satellite DNA (hsSAT) showed less enrichment in the high salt peak. In spite of high CpG content, long interspersed nuclear (LINE) elements that are transcribed by RNA polymerase II into mRNA (16) showed little difference between the low and high salt fractions, suggesting that the SRA-domain column may accurately reflect the extent of methylation of these sequences in the genome.
Random Sequencing of Cloned Fragments Derived from NaCl Eluted Fractions
Sodium bisulfite conversion of genomic DNA, while highly degrading as a consequence of the reaction, can yield very high-resolution information about the methylation state of a given segment of DNA. As the SRA-domain resin favored fragmented ssDNA, it was ideally suited to bind and resolve bisulfite-converted DNA. To explore the characteristics of the SRA-domain column when bisulfite DNA is applied, 200 μg of HeLa genomic DNA converted by the Epitect Bisulfite Kit (Qiagen) was applied to the equilibrated column, washed and eluted as before. As in previous runs, two peaks were observed at the 0.3 M and 0.5 M NaCl step elutions. Fractions were collected, concentrated and de-salted by Qiagen columns. Cloning of the fragments was accomplished using a modification of the “fourN” procedure (17) in which a small oligonucleotide containing four random bases followed by a BamHI restriction site were annealed to the fragments at both ends and extended with Sequenase. Primers complementary to known sequences introduced during the random priming reaction were added and a PCR reaction amplified the products. After cleavage with BamHI restriction enzyme, the DNA was cloned into a BamHI linearized Litmus 28i vector and plated on AMP/IPTG/XGAL plates ( FIG. 3 flow chart).
The DNA from 100 white colonies of the 0.5 M peak and 50 colonies of the 0.3 M peak were submitted for sequencing. Of those 100 reads from the 0.5 M peak, 30 were deemed suitable for analysis by the following criteria: 1) Contained viable sequences that could be identified by NCBI BlastN as human; 2) Showed evidence of non-methyl cytosine conversion (C to T or G to A, depending on orientation); and 3) unconverted C that was followed by G or unconverted G followed by C, again depending on forward or reverse sequencing orientation. Out of these 30 reads (Table 1) with an average size of 63 bases, 19 contained at least one methylated CpG. Of the 1900 bases sequenced, 44 were methylated CpG or 2.32% of the total. Amazingly, out of the 19 methylated CpG sequences, 10 mapped to known CpG methylation sites: nuclear receptor subfamily 4 (19), Fanconi anemia (20), von Willebrand factor (21), coagulation factor XIII and transglutaminase (22), chromodomain protein Y-like (23), spectrin repeat (24), HECTD1 (25), zinc finger and BTB domain containing 46 (26), and pumilio (27). Out of 22 reads with an average size of 105 bases in the low salt 0.3M peak, 3 contained methylated CpG. Of these 2327 bisulfite-converted bases, 5 were identified as methylated CpG or 0.215% of the total. Although limited in scope, these data showed a better than 10-fold enrichment of methylated CpG from the high NaCl peak versus the low NaCl peak. Additional sequencing efforts will be required to fully determine the potential fold enrichment by the SRA-domain resin as compared to random sequencing of genomic DNA or to CpG methylated DNA that was augmented by other means such as an MBD column.
GST-SRA-Domain Protein Covalently Coupled to Magnetic Beads Showed Similar Binding and Elution Characteristics
An alternative to column chromatography, GST-SRA-domain protein covalently coupled to a nonporous paramagnetic particle was tested for its suitability as a high-throughput purification matrix for methylated CpG sequences. To compare the binding characteristics of the GST-SRA-domain magnetic beads, 5 μg of sonicated unmethylated lambda DNA or 5 μg of sonicated fully enzymatically methylated (M.SssI) lambda DNA was added to a 50 μl of a 50% slurry of 10 mg/ml SRA-domain magnetic beads in 150 mM NaCl, 0.1% Tween 20, 10 mM Tris pH 7.5, and 1 mM EDTA and allowed to mix end over end for 30 minutes at room temperature. The tubes were placed on a magnetic separation rack and the supernatant was aspirated. The samples were washed and magnetically separated three times by the above buffer supplemented with 150 mM NaCl. The beads were then loaded directly on a 20% native TBE acrylamide gel for analysis. Similarly, sonicated methylated and unmethylated lambda DNA samples were heated to 98° C. and chilled prior to binding on the magnetic beads, followed by washes as stated above. Based on the ethidium stained DNA gel, it was determined that only the methylated heated lambda DNA remained on the beads after the 0.3 M NaCl washes ( FIGS. 4A-4D ). Additional work is needed to characterize the DNA fragments that remain bound to the beads by direct linker addition and DNA sequencing.
Example 2
Common Properties Shared by Sra Domains from Different Sources
MBP-NP95 SRA-domain fusion protein effectively enriched single-stranded methylated CpG DNA using a small amount of input DNA. This was demonstrated as described below.
The SRA domain of mouse NP95, which is 90% identical to human UHRF1, bound and enriched fragmented methylated ssDNA using 1 μg of input DNA. In addition, mouse NP95 SRA domain purified methylated CpG-containing DNA by 20-25 fold from 1 μg of fractionated ssDNA, and was comparable to methyl binding domain in yield and sensitivity.
An alternative to column chromatography, a MBP-NP95 SRA-domain fusion protein in conjunction with Anti-MBP monoclonal antibody coupled to a paramagnetic bead was tested for its suitability as a high-throughput purification matrix for methylated CpG sequences. To compare the binding and elution characteristics of the NP95 SRA-domain with a commercially available methylated CpG enrichment system employing biotinylated MBD (MethylMiner™ Methylated DNA Enrichment Kit from Invitrogen), 1 μg of sonicated, heated HeLa DNA (NP95 SRA) and 1 μg of sonicated HeLa DNA (MBD) was added to 1 μg of MBP-NP95 SRA (15 μl) or 1 μg of biotinylated MBD (2 μl), in a 200 μl total reaction mix containing 20 μl 10× NEBuffer 4 (50 mM potassium acetate, 20 mM Tris-acetate, 10 mM magnesium acetate, 1 mM dithiothreitol pH 7.9) and 2 μl 100 μg/ml BSA was incubated for 30 minutes at room temperature. To the MBP-NP95 SRA reactions, 100 μl (1 mg) of Anti-MBP magnetic beads (NEB) was added. To the MBD reactions, 100 μl (˜1 mg) of streptavidin magnetic beads (Invitrogen) was added. Both reactions were allowed to mix end over end over night at 4° C. The tubes were placed on a magnetic separation rack and the supernatant was aspirated. The samples were washed and magnetically separated 3× by 15 ml of wash buffer (20 mM Tris-HCl pH 7.5, 100 mM NaCl, 1 mM EDTA, 1% Triton X-100, 0.1% Tween 20) followed by a final 15 ml wash in low salt buffer (20 mM Tris-HCL, 1 mM EDTA, 0.1% Tween 20 (see FIG. 9 ). 140 μl of water was added to the bead complexes and the DNA samples were heated to 98° C. to liberate the enriched methylated DNA. The products from this heat step were characterized by qPCR on a BioRad iCycler using primers to known active and inactive genes in HeLa cells. The actively transcribed gene ribosomal protein L30 (RPL30) showed no enrichment in the MPB-NP95 SRA samples or the bt-MBD samples. The methylated genes myogenic differentiation 1 (MYO-D), and tandem repetitive ribosomal DNA (rDNA) showed a 20-25 fold enrichment in MPB-NP95 SRA samples, and is comparable to the enrichment values in the bt-MBD samples ( FIG. 8 ). Additional work is needed to characterize the DNA fragments that remain bound to the beads by direct linker addition and DNA sequencing.
TABLE 1 High Salt 0.5 M (enriched) peak, no CpG 1 1-33 .5 TGTGGGGTTGTTGTTTTGAGAGGGTTTTTTTTTGGG GTTTTTATTAATGATG (SEQ ID NO: 79) 6-33 .5 AAACATTGGGAATATAGTATTTATTTTTGGTGATTA TGTGTTTAGTTAAGTATTAGAGGATATTTTTA (SEQ ID NO: 28) 7-33 .5 AATTTTTGTAGTTTTAGTAGAGATGGAGTTTTATTA TGTTGGTTAGGTTGG (SEQ ID NO: 29) 8-33 .5 GAAACAGGAGAATTTTTTGAATTTGGGTGGTAGAGG (SEQ ID NO: 30) 9-33 .5 AGAAAATATGGTTTGTTAATGAATGATAGGTTAATT TTAGTATGTTGGTTATTTTAATATTTTGTTATTAGT TGGTTTGG (SEQ ID NO: 31) H19-33 .5 CAGGTATAGTGGTAAGAATTTGTAGTTTTAGTTATT TGGGAGGTTGAGTTAGGA (SEQ ID NO :32) H76-33 .5 AAACTTTTGGTTGGGGGTGGTGGTTTATGTTTGTAA TTTTAGTATTTTGGGAGGTCAAGGTGAGTGGAT (SEQ ID NO: 33) H2-33 .5 AGGTAGTTTTATTTTGGGTTTTAGGGAATAGGAGGG AATTAGAAGGA (SEQ ID NO: 34) H5-33 .5 CAGTATTTTGGGAGGTTAAGGTAGGTGGATTATGAG GTTAGGAGATTGAGA (SEQ ID NO: 35) H21-33 .5 GATGGATTGTTTGAGTTTAGGAGTTTGAGATTAG (SEQ ID NO: 36) H24-33 .5 5TGAGTTTAGTTTAAGTTGATTGGGTAGGTAAATGT TTGTTATGAATTTGGAAGTGAGAGA (SEQ ID NO: 37) High Salt 0.5 M (enriched) peak, CPG 3-33 .5 725439 bp at 3′ side: nuclear receptor subfamily 4, group A, member 2 isoform a CAGGTGTTGAGTGGTGAGGGATGTGTAAATAAGTAA GTGTGGGGTTCGGTTATTGCGTATAGTTAGGTATAT TGGTTGTTGTGGGGTGGGGTAGGTAATTTAAGTATT AGTATGGGTATTGGTTTTTTGTGAGGC (SEQ ID NO: 38) 4-33 .5 Fanconi anemia, complementation group M ACAAAAATTAGTTAGGTATAGTGGTATGTATTTGTA GTTTTAGTTAATCGGGATCCTGA (SEQ ID NO: 39) 5-33 .5 GENE ID: 10692 RRH|retinal pigment epithelium-derived rhodopsin homolog GAATGGCAAGTATTGGATTATTTACGGTCGTGGTTG TGGATCGATA (SEQ ID NO :40) 10-33 .5 transglutaminase 2 isoform b AGTTTGTACGGTGAAGTTTAGGTTTTATTGTGGATA CGGTTGAAATAGAAGAGTGATGGG (SEQ ID NO: 41) H6-33 .5 31781 bp at 5′ side: von Willebrand factor preproprotein 46059 bp at 3′ side: CD9 antigen TGAACGCGGGAGGCGGAGTTTGTAGTGAGTTAAGAT CGCGTTATTGTATTTTAG (SEQ ID NO :42) H7-33 .5 ref|NW_001838799.1|Hs2_WGA192_36 GGAAACGAATGAAATTATCGAATGGAATCGAATGGT GTTATCGAACGGA (SEQ ID NO :43) H12-33 .5 coagulation factor XIII A1 subunit precursor CGGATAGGAGGGGTTGTTATGAAG (SEQ ID NO: 44) H15-33 .5 545337 bp at 5′ side: EGF-like repeats and discoidin I-like domains-containing TAGTTAATTATATGTGTTCGTTATTTGTGTATGTGG (SEQ ID NO: 45) H45-33 .5 114563 bp at 5′ side: similar to hCG2036843 ATGAAAGTGTTTTGGGGATGGATGGGGGATATGGTT GTATAATGTGGCGGACG (SEQ ID NO :46) H55-33 .5 B-cell novel protein 1 isoform a AGAATCGTTTGAGTTTAGGAGTTTAAGATTAGTTTG GGTAATATAGTGAGATTTTGTTGTTACGAAAATAAA TAAAAAATTAGTTAGGTGTGGTGGTGTATGTTTGTG GT (SEQ ID NO: 47) H64-33 .5 17408 bp at 5′ side: musashi 2 iso- form b TGTTTGTTGAGTGTACGTNTNNNGTATTTGTGTTGG GTGTATGTGGATGTGTGNGNTGAG (SEQ ID NO: 48) H74-33 .5 Homo sapiens HECT domain containing 1 (HECTD1), mRNA AGTTTGAAGTTTTTATAGAAGAAGGTTATGATTTAT TTTCGGTAGGAAGTTTTGAAGAG (SEQ ID NO: 49) H15a-33 .5 62438 bp at 5′ side: D-amino acid oxidase activator AGGAAAGTTGGAAGGATGAGGATAACGTAGTGTTTT GTTGAAGAAGGAAGAGANNNNGGATTAAATTGAAAT TGATTGGGTTTYTAAAATGGATGGGAT (SEQ ID NO: 50) H27-33 .5 unc-51-like kinase 4 AGTTTGATTTTAGATTGTTGTGTTAGTAATGAGCGA GG (SEQ ID NO: 51) H30-33 .5 spectrin repeat containing, nuclear envelope 2 isoform 1 TTATTTTTATAAAAATAAAAAAATTAGTTGGGTGTA GTGGCGTATGTTTGTNGTTTTAGT (SEQ ID NO: 52) H H31-33 .5 256834 bp at 5′ side: alpha 1 type IV collagen preproprotein AACGATAAAGAAAATAAAAGGAGTGAGGGAGGATAG ATGGG (SEQ ID NO: 53) H35-33 .5 pumilio 1 isoform 1 ATTAGTTAGGCGTGGGGGTGGGTGTTTGTAGTTTTA GTTATTTAGGAGGTTGAGGTAGGA (SEQ ID NO: 54) H7a-33 .5 zinc finger and BTB domain containing 46 AAGGTGGGGGTTGGGGGGNTNGTTTTTTCGGGNTGT TGTCGCGGNGGAGGAGCGTTTTAGAGTTTACGGCGT AGTTTTATTCGTCGGNATTTAGGTGGACGTTGATCG GGGGAGAGAATTGAGTATCGGGATC (SEQ ID NO: 55) H9-33 .5 259088 BP AT 3′ SIDE: CHROMODOMAIN PROTEIN, Y-LIKE 2 AGAGTAGAGAGATGATTAAATTTATGTTAATTTTAT TATTTTGGTTTTGAGGTTGTTGTRYAAGTTTTTTAG AATGTGAGTCGGGTATTGTTTTTGAGGTTAACGTTA TTTGGTTTGCGTTT (SEQ ID NO: 56) Low Salt 0.3 M (control) peak, CPG 13-33 .3 GGGAGGTAGTGATGAGAGTAATAGATAGGGTTTAGG TGTTTGTGTATGATATGTTTG (SEQ ID NO: 57) L9-33 .3 GATGTTATTAAATAATTAGATTATTTGTATTCGAAT TGGGTAAGTAGTATAAAGGANAANGATATTATTAAA TAATTAGACTATTTGTATTCGAATTGGGTAAGTAGT ACAAAGGAGAAGTGGGGNAA (SEQ ID NO: 58) 3-2-33 .3 19744 bp at 3′ side: Myc-binding protein-associated protein TTTGTAGAAGGATGTGAGAGGAGAAGTGAGCGGTTT TATAGGTATGATGTTAGTTATAAGGGGTTGGTGAGT TGATGTGGGAGGATTATTTGGTTTAGGAGTTTAAGG TTGCGGTGAGT (SEQ ID NO: 59) L-17.33 dihydrouridine synthase 3-like TGAGGGTTGGGTTTAGGATAGAGTATAGAGAGGGAG ATTTAGTTAGGAGTTTTTTTAAGGTATATAGTTTTT GATTTTTAGGTAGTTAGAATAGGAACGTGGATATAG TTGGTATTTAATAGACGTATATTAGATGGATAGATT TGTTATTGA (SEQ ID NO: 60) Low Salt 0.3 M (control) peak, no CpG 3-5-33 .3 TAGTAGTATGATGTTAGTTTTTTTTAAATTATAGAT TCAATAANATTCAGTTAAAATTTTATTAGTTTTATT TATTTATTGATTTAGTAGAGATGGATATAGTACTGT (SEQ ID NO: 61) 3-6-33 .3 GTGTTATCGTATTGGGGTTATTTGTGTAATTAATAT GTGTTATTTAGTTTTAGGGTGTATGTTTATTGTTTT AATTATGATGGAGGTGTAGTTTGGAGATTTTGTGTT AGGAGATTAGTAGAGTTTGGGGTTTTAAGGGGATTT TTTGTGGGGGAGAGGGATAGTTGTGTAGTAGAGTGA TAATGAAGGTTTTTGATTTAATGTGTAGTTTTTAGG TTATGTGT (SEQ ID NO: 62) 3-8-33 .3 TTTGGGAGGTTGAGGTGGGTAGATTATGATGTTAAG AGATTGAGATTAT (SEQ ID NO: 63) L1-33 .3 GATGAAAGGTTAAAATTGAGATAGAAGATGTGATTT GGAAGGTTATAAGAGAAGTTGGATAAAGTTAAATAA GGA AAGGAATTTAGAAAAAAGTGTTTAATGTTGTAGAAG G (SEQ ID NO: 64) L1-19 .3 CTATTCTTCCCATTCTCAACATAACTCTAACCTTCC TTCATCCTCACACCCAACAATCATTCACTCATTTAT CTA (SEQ ID NO: 65) L-1.33 GATAAAGTTGTGNGTAGGGATTTTTGGTAGAGGGAA TAGAAAGATGGAGGTGTTGAGGTAGGAGTGATGGGT AGGTTTGAAGAGTAGAGTTTAGTGTAGTGAGGGGGT TATTAGTAAGGG (SEQ ID NO 66) L-11.33 ATATTTTATGGAGGAGTAATTTTTAGAGTATATGAA TTGGTTTTATGGAGGAAGATTGTTATTTATAGGTTG GTGTAAGTGATGGTAGTAGTGGTTTGTC (SEQ ID NO: 67) L-12.33 AGAAGATAAGGAGAAGATAATTATTNTTTTGGTAGA GGTAATTGATTTGATTATTAGGA (SEQ ID NO: 68) L-15.33 ATGTGTATTTAAAGTAAGGTTATGAGATTTTGGATT GTTTTTTGTTTAGGATGATATGTG (SEQ ID NO: 69) L-16.33 AAGTAAAATAATTTTGTTTTTATTTATTTTANAGGA TTGTT (SEQ ID NO: 70) L-18.33 AAAATTTTAAGATTAGGTAAAAATATTGTGTAAAGT GAGAGGGATGTGATGGTTAAAAAGTGATTTAAGATT TTTGTAATTTTTAGTTATAATTTAAGA (SEQ ID NO: 71) L-2.33 GAGATAATAGTGAGTATGATATTTTTTGTTTTTTTT ATTATGTGTTAAGTATTGTTTAGGGATTAAGTGGGG TTGTGTTTATTGTAGATGTTGTAGGTATGGAGTTAG TA (SEQ ID NO: 72) L-20.33 ATGTATTTAGTTGTTTATTGAATATTATTTTAATAT TGTATTATGAATATTGTTATGTTATGGATTTTAGGT TTTATTAGATTGGTATTAGTATCATTTAGGAATATT TTATGATGTGTGTTGATAAATTTTTAAGATAAATGA ATTTGAGATATGTGTGAGTATTTTATAAAATAAATT TTGTTGGA (SEQ ID NO :73) L-23.33 ATGGTTTGTTTGTTTTTGTGGAAAATGGTATGAAGA TTGGGTTTGTATTGAATTTG (SEQ ID NO :74) L-24.33 TGTAGTTTTAGTTATTTAGGAGGTTGAGATATGAGA ATTATTTGAATTTGGGGGGGGAAGGTTGTAGTGA (SEQ ID NO: 75) L-27.33 TGAGAAGGGGGTAGTGGGGATGGTTTTGTGGGTTTA TGTTGTTTTTGATTTTAGAAAATAAAGTTTTTTGTA GGAAGTAGGTGGGAAGTAATTTGTTGATAAGTGTAA AGATTTGGGAATTATATTAAGGGGTAAATGGAGGAN AGGTGTTGGTGTTAANGAGGTAGACNTATGGGAGTT NGGTTTTAGGAANGGNNGTGGNTAGAAAGG ((SEQ ID NO: 76) L-28.33 GGTAGGTAGATTATTTGAGGTTAGGAGTTTAAG (SEQ ID NO: 77) L-4.33 ATATTTTTTTATTGAAGAATGTAGTTTTTTAAAATT AAAATGTATTTTTAAAATTTATTTATTATTTTTT-- GAGATAAGGTTTTGTTTTGTTGTTTAAGTTAGAGTA TAGTATGTGATTATAGTTTATTGTAGTTTTGAATTT TTGGGTTTAAG (SEQ ID NO: 78)
Table 1 above shows the results of sequence analysis of the two NaCl peaks from the SRA-domain column showed a better than 10-fold enrichment of methylated CpG DNA. Out of 30 reads with an average size of 63 bases in the high (0.5 M) NaCl fraction, 19 contained at least one methylated CpG. Of the 1900 bases sequenced, 44 were methylated CpG or 2.32% of the total. Out of 22 reads with an average size of 105 bases in the low salt 0.3M peak, 3 contained methylated CpG. Of these 2327 bisulfate-converted bases, 5 were identified as methylated CpG or 0.215% of the total.
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25. Carrasco D, Tonon G, Huang Y, Zhang Y, Sinha R, Feng B, Stewart J, Zhan F, Khatry D, Protopopova, M. (2003) High-resolution genomic profiles define distinct clinico-pathogenetic subgroups of multiple myeloma patients. Cancer Cell, 9(4): 313-325.
26. Filion G J P, Zhenilo S, Salozhin S, Yamada D, Prokhortchouk E, Pierre-Defossez P A. (2006) A Family of Human Zinc Finger Proteins That Bind Methylated DNA and Repress Transcription Mol Cell Biol. 26(1): 169-181.
27. Li Z X, Ma X, Wang Z H. (2006) A differentially methylated region of the DAZ1 gene in spermatic and somatic cells. Asian Journal of Andrology. 8(1): 61-67. | Compositions and methods are provided for facilitating the enrichment of single-stranded DNA containing methylated CpG in a mixture containing methylated and unmethylated DNA. The compositions relate to methylation-binding protein domains that selectively bind to methylated single strand DNA. In embodiments of the invention, the methylated DNA is eluted in 0.4M-0.6M NaCl while the unmethylated single strand DNA is eluted in less than 0.4M salt. The ability to readily enrich for methylated DNA permits high throughput sequencing of the methylated DNA and identification of abnormal methylation patterns associated with disease. | 6 |
FIELD OF THE INVENTION
This invention is in the field of corn breeding, specifically relating to an inbred corn line designated G06-NP2760. This invention also is in the field of hybrid maize production employing the present inbred.
BACKGROUND OF THE INVENTION
The original maize plant was indigenous to the Western Hemisphere. The plants were weedlike and only through the efforts of early breeders were cultivated crop species developed. The crop cultivated by early breeders, like the crop today, could be wind pollinated. The physical traits of maize are such that wind pollination results in self-pollination or cross-pollination between plants. Each maize plant has a separate male and female flower that contributes to pollination, the tassel and ear, respectively. Natural pollination occurs when wind transfers pollen from tassel to the silks on the corn ears. This type of pollination has contributed to the wide variation of maize varieties present in the Western Hemisphere.
The development of a planned breeding program for maize only occurred in the last century. A large part of the development of the maize product into a profitable agricultural crop was due to the work done by land grant colleges. Originally, maize was an open pollinated variety having heterogeneous genotypes. The maize farmer selected uniform ears from the yield of these genotypes and preserved them for planting the next season. The result was a field of maize plants that were segregating for a variety of traits. This type of maize selection led to, at most, incremental increases in seed yield.
Large increases in seed yield were due to the work done by land grant colleges that resulted in the development of numerous hybrid corn varieties in planned breeding programs. Hybrids were developed from inbreds which were developed by selecting corn lines and selfing these lines for several generations to develop homozygous pure inbred lines. One selected inbred line was emasculated and another selected inbred line pollinated the emasculated inbred to produce hybrid seed F1 on the emasculated inbred line. Emasculation of the inbred usually is done by detasseling the seed parent; however, emasculation can be done in a number of ways. For example an inbred could have a male sterility factor which would eliminate the need to detassel the inbred.
In the early seventies the hybrid corn industry attempted to introduce CMS (cytoplasmic male sterility) into a number of inbred lines. Unfortunately, the CMS inbreds also introduced some very poor agronomic performance traits into the hybrid seed which caused farmers concern causing the maize industry to shy away from CMS material for a couple of decades thereafter.
However, in the last 10-15 years a number of different male sterility systems for maize have been successfully deployed. The most traditionally of these male sterility and/or CMS systems for maize parallel the CMS type systems that have been routinely used in hybrid production in sunflower.
In the standard CMS system there are three different maize lines required to make the hybrid. First, there is a cytoplasmic male-sterile line usually carrying the CMS or some other form of male sterility. This line will be the seed producing parent line. Second, there must be a fertile inbred line that is the same or isogenic with the seed producing inbred parent but lacking the trait of male sterility. This is a maintainer line needed to make new inbred seed of the seed producing male sterile parent. Third there is a different inbred which is fertile, has normal cytoplasm and carries a fertility restoring gene. This line is called the restorer line in the CMS system. The CMS cytoplasm is inherited from the maternal parent (or the seed producing plant), therefore for the hybrid seed produced on such plant to be fertile the pollen used to fertilize this plant must carry the restorer gene. The positive aspect of this is that it allows hybrid seed to be produced without the need for detasseling the seed parent. However, this system does require breeding of all three types of lines: 1) male sterile—to carry the CMS: 2) the maintainer line; and, 3) the line carrying the fertility restorer gene.
In some instances, sterile hybrids are produced and the pollen necessary for the formation of grain on these hybrids is supplied by interplanting of fertile inbreds in the field with the sterile hybrids.
Whether the seed producing plant is emasculated by detasseling or by CMS or by transgenes, the seed produced by crossing two inbreds in this manner is hybrid seed. This hybrid seed is F1 hybrid seed. The grain produced by a plant grown from a F1 hybrid seed is referred to as F2 or grain. Although, all F1 seed and plants, produced by this hybrid seed production system using the same two inbreds should be substantially the same, all F2 grain produced from the F1 plant will be segregating maize material.
The hybrid seed production produces hybrid seed which is heterozygous. The heterozygosis results in hybrid plants, which are robust and vigorous plants. Inbreds on the other hand are mostly homozygous. This homozygosity renders the inbred lines less vigorous. Inbred seed can be difficult to produce since the inbreeding process in corn lines decreases the vigor. However, when two inbred lines are crossed, the hybrid plant evidences greatly increased vigor and seed yield compared to open pollinated, segregating maize plants. An important consequence of the homozygosity and the homogenity of the inbred maize lines is that all hybrid seed produced from any cross of two such elite lines will be the same hybrid seed and make the same hybrid plant. Thus the use of inbreds makes hybrid seed which can be reproduced readily.
The ultimate objective of the commercial maize seed companies is to produce high yielding, agronomically sound plants that perform well in certain regions or areas of the Corn Belt. To produce these types of hybrids, the companies must develop inbreds, which carry needed traits into the hybrid combination. Hybrids are not often uniformly adapted for the entire Corn Belt, but most often are specifically adapted for regions of the Corn Belt. Northern regions of the Corn Belt require shorter season hybrids than do southern regions of the Corn Belt. Hybrids that grow well in Colorado and Nebraska soils may not flourish in richer Illinois and Iowa soil. Thus, a variety of major agronomic traits is important in hybrid combination for the various Corn Belt regions, and has an impact on hybrid performance.
Inbred line development and hybrid testing have been emphasized in the past half-century in commercial maize production as a means to increase hybrid performance. Inbred development is usually done by pedigree selection. Pedigree selection can be selection in an F 2 population produced from a planned cross of two genotypes (often elite inbred lines), or selection of progeny of synthetic varieties, open pollinated, composite, or backcrossed populations. This type of selection is effective for highly inheritable traits, but other traits, for example, yield requires replicated test crosses at a variety of stages for accurate selection.
Maize breeders select for a variety of traits in inbreds that impact hybrid performance along with selecting for acceptable parental traits. Such traits include: yield potential in hybrid combination; dry down; maturity; grain moisture at harvest; greensnap; resistance to root lodging; resistance to stalk lodging; grain quality; disease and insect resistance; ear and plant height. Additionally, Hybrid performance will differ in different soil types such as low levels of organic matter, clay, sand, black, high pH, low pH; or in different environments such as wet environments, drought environments, and no tillage conditions. These traits appear to be governed by a complex genetic system that makes selection and breeding of an inbred line extremely difficult. Even if an inbred in hybrid combination has excellent yield (a desired characteristic), it may not be useful because it fails to have acceptable parental traits such as seed yield, seed size, pollen production, good silks, plant height, etc.
To illustrate the difficulty of breeding and developing inbred lines, the following example is given. Two inbreds compared for similarity of 29 traits differed significantly for 18 traits between the two lines. If 18 simply inherited single gene traits were polymorphic with gene frequencies of 0.5 in the parental lines, and assuming independent segregation (as would essentially be the case if each trait resided on a different chromosome arm), then the specific combination of these traits as embodied in an inbred would only be expected to become fixed at a rate of one in 262,144 possible homozygous genetic combinations. Selection of the specific inbred combination is also influenced by the specific selection environment on many of these 18 traits which makes the probability of obtaining this one inbred even more remote. In addition, most traits in the corn genome are regrettably not single dominant genes but are multi-genetic with additive gene action not dominant gene action. Thus, the general procedure of producing a non segregating F 1 generation and self pollinating to produce a F 2 generation that segregates for traits and selecting progeny with the visual traits desired does not easily lead to a useful inbred. Great care and breeder expertise must be used in selection of breeding material to continue to increase yield and the agronomics of inbreds and resultant commercial hybrids.
Certain regions of the Corn Belt have specific difficulties that other regions may not have. Thus the hybrids developed from the inbreds have to have traits that overcome or at least minimize these regional growing problems. Examples of these problems include in the eastern corn belt Gray Leaf Spot, in the north cool temperatures during seedling emergence, in the Nebraska region CLN (corn Lethal necrosis and in the west soil that has excessively high pH levels. The industry often targets inbreds that address these issues specifically forming niche products. However, the aim of most large seed producers is to provide a number of traits to each inbred so that the corresponding hybrid can useful in a broader regions of the Corn Belt. The new biotechnology techniques such as Microsatellites, RFLPs, RAPDs and the like have provided breeders with additional tools to accomplish these goals.
SUMMARY OF THE INVENTION
The present invention relates to an inbred corn line G06-NP2760. Specifically, this invention relates to plants and seeds of this line. Additionally, this relates to a method of producing from this inbred, hybrid seed corn and hybrid plants with seeds from such hybrid seed. More particularly, this invention relates to the unique combination of traits that combine in corn line G06-NP2760.
Generally then, broadly the present invention includes an inbred corn seed designated G06-NP2760. This seed produces a corn plant.
The invention also includes the tissue culture of regenerable cells of G06-NP2760 wherein the cells of the tissue culture regenerates plants capable of expressing the genotype of G06-NP2760. The tissue culture is selected from the group consisting of leaf, pollen, embryo, root, root tip, guard cell, ovule, seed, anther, silk, flower, kernel, ear, cob, husk and stalk, cell and protoplast thereof. The corn plant regenerated from G06-NP2760 or any part thereof is included in the present invention. The present invention includes regenerated corn plants that are capable of expressing G06-NP2760's genotype, phenotype or mutants or variants thereof.
The invention extends to hybrid seed produced by planting, in pollinating proximity which includes using preserved maize pollen as explained in U.S. Pat. No. 5,596,838 to Greaves, seeds of corn inbred lines G06-NP2760 and another inbred line if preserved pollen is not used; cultivating corn plants resulting from said planting; preventing pollen production by the plants of one of the inbred lines if two are employed; allowing cross pollination to occur between said inbred lines; and harvesting seeds produced on plants of the selected inbred. The hybrid seed produced by hybrid combination of plants of inbred corn seed designated G06-NP2760 and plants of another inbred line are apart of the present invention. This inventions scope covers hybrid plants and the plant parts including the grain and pollen grown from this hybrid seed.
The invention further includes a method of hybrid F1 production. A first generation (F1) hybrid corn plant produced by the process of planting seeds of corn inbred line G06-NP2760; cultivating corn plants resulting from said planting; permitting pollen from another inbred line to cross pollinate inbred line G06-NP2760; harvesting seeds produced on plants of the inbred; and growing a harvested seed are part of the method of this invention.
The present invention also encompasses a method of introducing at least one targeted trait into maize inbred line comprising the steps of: (A) crossing plant grown from the present invention seed which is the recurrent parent, representative seed of is which has been deposited, with the donor plant of another maize line that comprises at least one target trait selected from the group consisting of male sterility, herbicide resistance, insect resistance, disease resistance, amylose starch, and waxy starch to produce F1 plants; (b) selecting from the F1 plants that have at least one of the targeted trait, forming a pool of progeny plants with the targeted trait; (c) crossing the pool of progeny plants with the present invention which is the recurrent parent to produce backcrossed progeny plants with the targeted trait; (d) selecting for backcrossed progeny plants that have at least one of the target trait and physiological and morphological characteristics of maize inbred line of the recurrent parent, listed in Table 1 forming a pool of selected backcrossed progeny plants; and (e) crossing the selected backcrossed progeny plants to the recurrent parent and selecting from the resulting plants for the targeted trait and physiological and morphological characteristics of maize inbred line of the recurrent parent, listed in Table 1 and reselecting from the pool of resulting plants and repeating the crossing to the recurrent parent and selecting step in succession to form a plant that comprise the desired trait and all of the physiological and morphological characteristics of maize inbred line of the recurrent parent if the present invention listed in Table 1 as determined at the 5% significance level when grown in the same environmental conditions.
This method and the following method of introducing traits can be done with less back crossing events if the trait and/or the genotype of the present invention are selected for or identified through the use of markers. SSR, microsatellites, SNP and the like decrease the amount of breeding time required to locate a line with the desired trait or traits and the characteristics of the present invention. Backcrossing in two or even three traits (for example the glyphosate, Europe corn borer, corn rootworm resistant genes) is routinely done with the use of marker assisted breeding techniques. This introduction of transgenes or mutations into a maize line is often called single gene conversion. Although, presently more than one gene particularly transgenes or mutations which are readily tracked with markers can be moved during the same “single gene conversion” process, resulting in a line with the addition of more targeted traits than just the one, but still having the characteristics of the present invention plus those characteristics added by the targeted traits.
The method of introducing a desired trait into maize inbred line comprising: (a) crossing plant grown from the present invention seed, representative seed of which has been deposited the recurrent parent, with plant of another maize line that comprises at least one target trait selected from the group consisting of nucleic acid encoding an enzyme selected from the group consisting of phytase, stearyl-ACP desaturase, fructosyltransferase, levansucrase, amylase, invertase and starch branching enzyme, the donor parent to produce F1 plants; (b) selecting for the targeted trait from the F1 plants, forming a pool of progeny plants; (c) crossing the progeny plants with the recurrent parent to produce backcrossed progeny plants; (d) selecting for backcrossed progeny plants that have at least one of the target trait and physiological and morphological characteristics of maize inbred line of the present invention a listed in Table 1 forming a pool of backcrossed progeny plants; and repeating a step of crossing the new pool with the recurrent parent and selecting for the targeted trait and the recurrent parents characteristics until the selected plant is essentially the recurrent parent with the targeted trait or targeted traits. This selection and crossing may take at least 4 backcrosses if marker assisted breeding is not employed.
The inbred line and seed of the present invention are employed to carry the agronomic package into the hybrid. Additionally, the inbred line is often carrying transgenes that are introduced in to the hybrid seed.
Likewise included is a first generation (F1) hybrid corn plant produced by the process of planting seeds of corn inbred line G06-NP2760; cultivating corn plants resulting from said planting; permitting pollen from inbred line G06-NP2760 to cross pollinate another inbred line; harvesting seeds produced on plants of the inbred; and growing a plant from such a harvested seed.
A number of different techniques exist which are designed to avoid detasseling in maize hybrid production. Some examples are switchable male sterility, lethal genes in the pollen or anther, inducible male sterility, male sterility genes with chemical restorers. There are numerous patented means of improving upon the hybrid production system. Some examples include U.S. Pat. No. 6,025,546, which relates to the use of tapetum-specific promoters and the barnase gene to produce male sterility; U.S. Pat. No. 6,627,799 relates to modifying stamen cells to provide male sterility. Therefore, one aspect of the current invention concerns the present invention comprising one or more gene(s) capable of restoring male fertility to male-sterile maize inbreds or hybrids and/or genes or traits to produce male sterility in maize inbreds or hybrids.
The inbred corn line G06-NP2760 and at least one transgenic gene adapted to give G06-NP2760 additional and/or altered phenotypic traits are within the scope of the invention. Such transgenes are usually associated with regulatory elements (promoters, enhancers, terminators and the like). Presently, transgenes provide the invention with traits such as insect resistance, herbicide resistance, disease resistance increased or deceased starch or sugars or oils, increased or decreased life cycle or other altered trait.
The present invention includes inbred corn line G06-NP2760 and at least one transgenic gene adapted to give G06-NP2760 modified starch traits. Furthermore this invention includes the inbred corn line G06-NP2760 and at least one mutant gene adapted to give modified starch, acid or oil traits, i.e. amylase, waxy, amylose extender or amylose. The present invention includes the inbred corn line G06-NP2760 and at least one transgenic gene: bacillus thuringiensis , the bar or pat gene encoding Phosphinothricin acetyl Transferase, Gdha gene, GOX, VIP, EPSP synthase gene, low phytic acid producing gene, and zein. The inbred corn line G06-NP2760 and at least one transgenic gene useful as a selectable marker or a screenable marker is covered by the present invention.
A tissue culture of the regenerable cells of hybrid plants produced with use of G06-NP2760 genetic material is covered by this invention. A tissue culture of the regenerable cells of the corn plant produced by the method described above is also included.
DEFINITIONS
In the description and examples, which follow, a number of terms are used. In order to provide a clear and consistent understanding of the specifications and claims, including the scope to be given such terms, the following definitions are provided.
PLANT
This term includes the entire plant and its plant cells, plant protoplasts made from its cells, plant cell tissue cultures from which corn plants can be regenerated, plant calli, plant clumps, and plant cells that are intact in plants or parts of plants, such as embryos, pollen, flowers, kernels, ears, cobs, leaves, husks, stalks, roots, root tips, anthers, silk and the like, and this term also includes any mutated gene, transgenic DNA or (RNA) or portion thereof that have been introduced into the plant by whatever method.
HR Highly resistant
MR moderately resistant
S Susceptible
MS moderately susceptible
COGP— cost to produce seed
TWT
The measure of the weight of grain in pounds for a one bushel volume adjusted for percent grain moisture.
% DROPPED EARS (DE) Or PCTDE
The number of plants per plot, which dropped their primary ear, divided by the total number of plants per plot.
% ROOT LODGE (RL) Or PCTRL
Percentage of plants per plot leaning more that 30 degrees from vertical divided by total plants per plot.
YIELD (YLD)
Actual yield of grain at harvest adjusted to 15.5% moisture. Measurements are reported in bushels per acre.
MOISTURE
The average percentage grain moisture of an inbred or hybrid at harvest time.
% STALK LODGE (SL) Or PCTSL
Percentage of plants per plot with the stalk broken below the primary ear node divided by the total plants per plot.
GREEN SNAP (Gsnap): Count the number of plants in yield rows that snapped below the ear due to brittleness associated with high winds. For FET plots, count snapped plants out of 50 from two locations in each hybrid strip, sum, and record the percentage.
STAY-GREEN (Sgreen): This is an assessment of the ability of a grain hybrid to retain green color as maturity approaches (taken near the time of black-layer) and should not be a reflection of hybrid maturity or leaf disease. Record % of green tissue.
STAND: Shall mean the number of plants in the plot that were harvested.
SCLB—Southern Corn leaf blight
% MR—% medium round seed
% MF—% medium flat seed
% SR—% small round seed
% SF—% small flat seed
% LR— % large round seed
% LF—% large flat seed
Color Choices:
1.
light green
10.
pink-orange
19.
white
2.
medium green
11.
pink
20.
white capped
3.
dark green
12.
light red
21.
buff
4.
very dark
13.
cherry red
22.
tan
green
14.
red
23.
brown
5.
green-yellow
15.
red and white
24.
bronze
6.
pale yellow
16.
pale purple
25.
variegated
7.
yellow
(describe)
26.
other (describe)
8.
yellow-orange
17.
purple
9.
salmon
18.
colorless
Form
Input
#
ABR.
Description
Value
A1
EMRGN
Final number of plants per plot
#
A2
REGNN
Region Developed: 1.Northwest 2.Northcentral
#
3.Northeast 4.Southeast 5.Southcentral
6.Southwest 7.Other
A3
CRTYN
Cross type: 1.sc 2.dc 3.3w 4.msc 5.m3w 6.inbred
#
7.rel. line 8.other
A4
KRTPN
Kernel type: 1.sweet 2.dent 3.flint 4.flour 5.pop
#
6.ornamental 7.pipecorn 8.other
A5
EMERN
Days to Emergence EMERN
#Days
B1
ERTLP
% Root lodging: (before anthesis):
#%
B2
GRSNP
% Brittle snapping: (before anthesis):
#%
C1
TBANN
Tassel branch angle of 2nd primary lateral branch
degree
(at anthesis):
C10
HUPSN
Heat units to 50% pollen shed: (from emergence)
#HU
C11
SLKCN
Silk color:
#/Munsell
value
C12
HU5SN
Heat units to 50% silk: (from emergence)
#HU
C13
DSAZN
Days to 50% silk in adapted zone:
#Days
C14
HU9PN
Heat units to 90% pollen shed: (from emergence)
#HU
C15
HU19N
Heat units from 10% to 90% pollen shed:
#HU
C16
DA19N
Days from 10% to 90% pollen shed:
#Days
C2
LSPUR
Leaf sheath pubescence of second leaf above the
#
ear (at anthesis) 1-9 (1 = none):
C3
ANGBN
Angle between stalk and 2nd leaf above the ear
degree
(at anthesis):
C4
CR2LN
Color of 2nd leaf above the ear (at anthesis):
#/Munsell
value
C5
GLCRN
Glume Color:
#/Munsell
value
C6
GLCBN
Glume color bars perpendicular to their veins
#
(glume bands): 1.absent 2.present
C7
ANTCN
Anther color:
#/Munsell
value
C8
PLQUR
Pollen Shed: 1-9 (0 = male sterile)
#
C9
HU1PN
Heat units to 10% pollen shed: (from emergence)
#HU
D1
LAERN
Number of leaves above the top ear node:
#
D10
LTBRN
Number of lateral tassel branches that originate
#
from the central spike:
D11
EARPN
Number of ears per stalk:
D12
APBRR
Anthocyanin pigment of brace roots: 1.absent
#
2.faint 3.moderate 4.dark
D13
TILLN
Number of tillers:
#
D14
HSKCN
Husk color 25 days after 50% silk: (fresh)
#/Munsell
value
D2
MLWVR
Leaf marginal waves: 1-9 (1 = none)
#
D3
LFLCR
Leaf longitudinal creases: 1-9 (1 = none)
#
D4
ERLLN
Length of ear leaf at the top ear node:
#cm
D5
ERLWN
Width of ear leaf at the top ear node at the
#cm
widest point:
D6
PLHTN
Plant height to tassel tip:
#cm
D7
ERHCN
Plant height to the top ear node:
#cm
D8
LTEIN
Length of the internode between the ear node
#cm
and the node above:
D9
LTASN
Length of the tassel from top leaf collar to tassel
#cm
tip:
E1
HSKDN
Husk color 65 days after 50% silk: (dry)
#/Munsell
value
E10
DSGMN
Days from 50% silk to 25% grain moisture in
#Days
adapted zone:
E11
SHLNN
Shank length:
#cm
E12
ERLNN
Ear length:
#cm
E13
ERDIN
Diameter of the ear at the midpoint:
#mm
E14
EWGTN
Weight of a husked ear:
#gm
E15
KRRWR
Kernel rows: 1.indistinct 2.distinct
#
E16
KRNAR
Kernel row alignment: 1.straight 2.slightly curved
#
3.curved
E17
ETAPR
Ear taper: 1.slight 2.average 3.extreme
#
E18
KRRWN
Number of kernel rows:
#
E19
COBCN
Cob color:
#/Munsell
value
E2
HSKTR
Husk tightness 65 days after 50% silk: 1-9
#
(1 = loose)
E20
COBDN
Diameter of the cob at the midpoint:
#mm
E21
YBUAN
Yield:
#kg/ha
E22
KRTEN
Endosperm type: 1.sweet 2.extra sweet 3.normal
3
4.high amylose 5.waxy 6.high protein 7.high
lysine 8.super sweet 9.high oil 10.other
E23
KRCLN
Hard endosperm color:
#/Munsell
value
E24
ALECN
Aleurone color:
#/Munsell
value
E25
ALCPR
Aleurone color pattern: 1.homozygous
#
2.segregating
E26
KRLNN
Kernel length:
#mm
E27
KRWDN
Kernel width:
#mm
E28
KRDPN
Kernel thickness:
#mm
E29
K1KHN
100 kernel weight:
#gm
E3
HSKCR
Husk extension: 1.short (ear exposed) 2.medium
#
(8 cm) 3.long (8-10 cm) 4.very long (>10 cm)
E30
KRPRN
% round kernels on 13/64 slotted screen:
#%
E4
HEPSR
Position of ear 65 days after 50% silk: 1.upright
#
2.horizontal 3.pendent
E5
STGRP
Staygreen 65 days after anthesis: 1-9 (1 = worst)
#
E6
DPOPP
% dropped ears 65 days after anthesis:
%
E7
LRTRP
% root lodging 65 days after anthesis:
%
E8
HU25N
Heat units to 25% grain moisture: (from
#HU
emergence)
E9
HUSGN
Heat units from 50% silk to 25% grain moisture in
#HU
adapted zone:
DETAILED DESCRIPTION OF THE INVENTION
G06-NP2760 is shown in comparison with a number of standard inbreds adapted for the same region as the present invention. The present inbred is in the hybrid, X4618A and as shown in Table 2, the hybrid is a 102 day hybrid with RM of 4.
The inbred provides uniformity and stability within the limits of environmental influence for traits as described in the Variety Description Information (Table 1) that follows.
The inbred has been self-pollinated for a sufficient number of generations to give inbred uniformity. During plant selection in each generation, the uniformity of plant type was selected to ensure homozygosity and phenotypic stability. The line has been increased in isolated farmland environments with data on uniformity and agronomic traits being observed to assure uniformity and stability. No variant traits have been observed or are expected in G06-NP2760.
The best method of producing the invention, G06-NP2760 which is substantially homozygous, is by planting the seed of G06-NP2760 which is substantially homozygous and self-pollinating or sib pollinating the resultant plant in an isolated environment, and harvesting the resultant seed.
TABLE 1 G06-NP2760 VARIETY DESCRIPTION INFORMATION NPCode CommonRust EarRot Eyespot GossWilt GrayLeafSpot SCLB NP2361 HR HR HR HR HR NP2752 MR HR MR G06- MR HR MR NP2760 NP2830 MR HR MR 50POL Heat 50SLK Heat NPCode PlantHeight PlantHeightAdj EarHeight EarHeightAdj Units Units NP2832 72 Tall 26 low 1383 1380 G06-NP2760 72 Tall 35 Medium 1445 1481 NP2752 63 Medium 34 Medium 1565 1573 NP2793 69 Medium 30 Medium 1475 1470 21- 17- 21-23% Large 23% Large 20% Medium 17-20% Medium NPCode #Locs (1,000/acre)FinalStand round Flat Round Flat NP2832 7 32.5 1 0 13 43 G06-NP2760 7 32.8 7 4 29 44 NP2752 7 31.8 10 2 57 23 NP2793 7 32.9 7 12 32 43 15- 15- 16% Small NPCode 16% SmallRound Flat >24<15% Discard OverallSeeds/# 80k/FEacre 80k %SetAvg YldStabili COGP FemaleRating NP2832 6 36 10.3 1999 87 113 Average Low Good G06- 5 11 1.5 1814 78 101 Average Average Acceptable NP2760 NP2752 5 4 1.4 1747 55 72 Average Very high Poor NP2793 2 4 1 1676 100 129 Average Very low Very good NPCode M/F Sterility Anther Glume Silk BraceRootColor CobColor KernelColor NP2832 F yellow other/absent yellow red/purple Red Yellow G06-NP2760 F yellow green yellow other White Yellow NP2752 F yellow other/absent pink red/purple Red Yellow NP2793 F pink other/absent yellow red/purple White Yellow
Heat Units per day were calculated: HU=[MaxTemp(86)−Min Temp(50)]/2−50. Large standard deviations are probable due to environmental factors at the locations of observation. Additionally the present invention has a tall plant phenotype with a medium ear height. The present inbred differs from the comparison inbreds in that it has a white cob and a brace root color that is something other than red/purple.
The data provided above is often a color. The Munsell code is a reference book of color, which is known and used in the industry and by persons with ordinary skill in the art of plant breeding.
Hybrid Performance of G06-NP2760
Table 2 shows the inbred G06-NP2760 in hybrid combination in X4618A in comparison with a number of other hybrid combinations. The other hybrid combinations shown are commercial or experimental hybrids which are adapted for similar region of the Corn Belt. When in this hybrid combination the present inbred G06-NP2760 carries less yield than Hybrids 1-4 but more moisture than all of the hybrids. On the other hand X4618A shows good agronomic performance with little tendency to root lodging, but the hybrids stalk lodging is the second highest of all the compared hybrids. The test weight for the hybrid combination containing the present invention is lighter than all of the other hybrids except hybrid 4.
TABLE 2
PAIRED HYBRID COMPARISON DATA
AbbrCode
Yld
Moist
TWT
PCTSL
PCTRL
PCTDE
Stand
Sgreen
Gsnap
Hybrid 1
216.1
18.1
57.0
3.1
1.7
0.0
64.0
27.0
0.0
Hybrid 2
213.0
18.7
56.2
7.1
5.1
0.0
64.0
34.0
1.5
Hybrid 3
211.9
19.2
56.2
0.6
1.0
0.0
62.9
33.0
0.0
Hybrid 4
210.3
19.5
55.4
0.9
3.4
0.0
63.6
33.3
0.0
X4618A*
206.3
20.1
55.8
6.1
0.2
0.0
64.3
26.0
2.3
Hybrid 5
203.2
19.0
56.2
3.6
0.0
0.0
64.8
39.6
3.8
Hybrid 6
203.2
18.8
56.0
5.3
1.0
0.0
62.3
26.0
0.0
*indicates G06-NP2760 is in the hybrid
This invention also is directed to methods for producing a corn plant by crossing a first parent corn plant with a second parent corn plant wherein the first or second parent corn plant is an inbred corn plant from the line G06-NP2760. Further, both first and second parent corn plants can come from the inbred corn line G06-NP2760 which produces a self of the inbred invention. The present invention can be employed in a variety of breeding methods which can be selected depending on the mode of reproduction, the trait, and the condition of the germplasm. Thus, any breeding methods using the inbred corn line G06-NP2760 are part of this invention: selfing, backcrosses, hybrid production, and crosses to populations, and haploid by such old and known methods of using stock six material that induces haploids and anther culturing and the like.
All plants and plant cells produced using inbred corn line G06-NP2760 are within the scope of this invention. The invention encompasses the inbred corn line used in crosses with other, different, corn inbreds to produce (F1) corn hybrid seeds and hybrid plants and the grain produced on the hybrid plant. This invention includes plant and plant cells, which upon growth and differentiation produce corn plants having the physiological and morphological characteristics of the inbred line G06-NP2760.
Additionally, this maize can, within the scope of the invention, contain: a mutant gene such as, but not limited to, the amylose, amylase, sugary 1 or shrunken 1 or waxy or AE or imazethapyr tolerant (IT or IR™) mutant gene; or transgenic genes such as but not limited to insect resistant genes such as Corn Rootworm gene, Bacillus thuringiensis (Cry genes), or herbicide resistant genes such as Pat gene or Bar gene, EPSP, or disease resistant genes such as the Mosaic virus resistant gene, etc., or trait altering genes such as flowering genes, oil modifying genes, senescence genes and the like. The methods and techniques for inserting, or producing and/or identifying a mutation or a transgene into the present invention through breeding, transformation, or mutating are well known and understood by those of ordinary skill in the art.
A number of different inventions exist which are designed to avoid detasseling in maize hybrid production. Some examples are switchable male sterility, lethal genes in the pollen or anther, inducible male sterility, male sterility genes with chemical restorers, sterility genes linked with parent. U.S. Pat. No. 6,025,546, relates to the use of tapetum-specific promoters and the barnase gene. U.S. Pat. No. 6,627,799 relates to modifying stamen cells to provide male sterility. Therefore, one aspect of the current invention concerns the present invention comprising one or more gene(s) capable of restoring male fertility to male-sterile maize inbreds or hybrids.
Various techniques for breeding and moving or altering genetic material within or into the present invention (whether it is an inbred or in hybrid combination) are also known to those skilled in the art. These techniques to list only a few are anther culturing, haploid production, (stock six is a method that has been in use for thirty years and is well known to those with skill in the art), transformation, irradiation to produce mutations, chemical or biological mutation agents and a host of other methods are within the scope of the invention. All parts of the G06-NP2760 plant including its plant cells produced using the inbred corn line is within the scope of this invention. The term transgenic plant refers to plants having genetic sequences, which are introduced into the genome of a plant by a transformation method and the progeny thereof. Transformation methods are means for integrating new genetic coding sequences into the plant's genome by the incorporation of these sequences into a plant through man's assistance, but not by breeding practices. The transgene once introduced into plant material and integrated stably can be moved into other germplasm by standard breeding practices.
Though there are a large number of known methods to transform plants, certain types of plants are more amenable to transformation than are others. Transformation of dicots is usually achievable for example, tobacco is a readily transformable plant. Monocots can present some transformation challenges, however, the basic steps of transforming plants monocots have been known in the art for about 15 years. The most common method of maize transformation is referred to as gunning or microprojectile bombardment though other methods can be used. The process employs small gold-coated particles coated with DNA which are shot into the transformable material. Detailed techniques for gunning DNA into cells, tissue, callus, embryos, and the like are well known in the prior art. One example of steps that can be involved in monocot transformation are concisely outlined in U.S. Pat. No. 5,484,956 “Fertile Transgenic Zea mays Plants Comprising Heterologous DNA Encoding Bacillus Thuringiensis Endotoxin” issued Jan. 16, 1996 and also in U.S. Pat. No. 5,489,520 “Process of Producing Fertile Zea mays Plants and Progeny Comprising a Gene Encoding Phosphinothricin Acetyl Transferase” issued Feb. 6, 1996.
Plant cells such as maize can be transformed not only by the use of a gunning device but also by a number of different techniques. Some of these techniques include maize pollen transformation (See University of Toledo 1993 U.S. Pat. No. 5,177,010); Whiskers technology (See U.S. Pat. Nos. 5,464,765 and 5,302,523); electroporation; PEG on Maize; Agrobacterium (See 1996 article on transformation of maize cells in Nature Biotechnology , Volume 14, June 1996) along with numerous other methods which may have slightly lower efficiency rates. Some of these methods require specific types of cells and other methods can be practiced on any number of cell types.
The use of pollen, cotyledons, zygotic embryos, meristems and ovum as the target issue can eliminate the need for extensive tissue culture work. Generally, cells derived from meristematic tissue are useful. The method of transformation of meristematic cells of cereal is taught in the PCT application WO96/04392. Any number of various cell lines, tissues, calli and plant parts can and have been transformed by those having knowledge in the art. Methods of preparing callus or protoplasts from various plants are well known in the art and specific methods are detailed in patents and references used by those skilled in the art. Cultures can be initiated from most of the above-identified tissue. The only true requirement of the transforming plant material is that it can form a transformed plant.
The DNA used for transformation of these plants clearly may be circular, linear, and double or single stranded. Usually, the DNA is in the form of a plasmid. The plasmid usually contains regulatory and/or targeting sequences which assists the expression of the gene in the plant. The methods of forming plasmids for transformation are known in the art. Plasmid components can include such items as: leader sequences, transit polypeptides, promoters, terminators, genes, introns, marker genes, etc. The structures of the gene orientations can be sense, antisense, partial antisense, or partial sense: multiple gene copies can be used. The transgenic gene can come from various non-plant genes (such as; bacteria, yeast, animals, and viruses) along with being from plants.
The regulatory promoters employed can be constitutive such as CaMv35S (usually for dicots) and polyubiquitin for monocots or tissue specific promoters such as CAB promoters, MR7 described in U.S. Pat. No. 5,837,848, etc. The prior art promoters, includes but is not limited to, octopine synthase, nopaline synthase, CaMv19S, mannopine synthase. These regulatory sequences can be combined with introns, terminators, enhancers, leader sequences and the like in the material used for transformation.
The isolated DNA is then transformed into the plant. After the transformation of the plant material is complete, the next step is identifying the cells or material, which has been transformed. In some cases, a screenable marker is employed such as the beta-glucuronidase gene of the uidA locus of E. coli . Then, the transformed cells expressing the colored protein are selected. In many cases, a selectable marker identifies the transformed material. The putatively transformed material is exposed to a toxic agent at varying concentrations. The cells not transformed with the selectable marker, which provides resistance to this toxic agent, die. Cells or tissues containing the resistant selectable marker generally proliferate. It has been noted that although selectable markers protect the cells from some of the toxic affects of the herbicide or antibiotic, the cells may still be slightly affected by the toxic agent by having slower growth rates. If the transformed material was cell lines then these lines are regenerated into plants. The cells' lines are treated to induce tissue differentiation. Methods of regeneration of cellular maize material are well known in the art.
A deposit of at least 2500 seeds of this invention will be maintained by Syngenta Seed Inc. Access to this deposit will be available during the pendency of this application to the Commissioner of Patents and Trademarks and persons determined by the Commissioner to be entitled thereto upon request. All restrictions on availability to the public of such material will be removed upon issuance of a granted patent of this application by depositing at least 2500 seeds of this invention at the American Type Culture Collection (ATCC), at 10801 University Boulevard, Manassas, Va. 20110. The date of deposit was Jan. 31, 2008. The ATCC number of the deposit is PTA-8906 and on Feb. 15, 2008 the seeds were tested and found to be viable. The deposit of at least 2500 seeds will be from inbred seed taken from the deposit maintained by Syngenta Seed Inc. The ATCC deposit will be maintained in that depository, which is a public depository, for a period of 30 years, or 5 years after the last request, or for the enforceable life of the patent, whichever is longer, and will be replaced if it becomes nonviable during that period.
Additional public information on patent variety protection may be available from the PVP Office, a division of the US Government.
Accordingly, the present invention has been described with some degree of particularity directed to the preferred embodiment of the present invention. It should be appreciated, though that the present invention is defined by the following claims construed in light of the prior art so that modifications or changes may be made to the preferred embodiment of the present invention without departing from the inventive concepts contained herein. | Basically, this invention provides for an inbred corn line designated G06-NP2760, methods for producing a corn plant by crossing plants of the inbred line G06-NP2760 with plants of another corn plants. The invention relates to the various parts of inbred G06-NP2760 including culturable cells. This invention also relates to methods for introducing transgenic transgenes into inbred corn line G06-NP2760 and plants produced by said methods. | 0 |
FIELD OF THE INVENTION
[0001] This invention relates generally to building foundations, and more particularly to a diverter for directing water away from a building foundation.
BACKGROUND OF THE INVENTION
[0002] Damaged foundations resulting from frost heave or wet basements and crawl spaces are a persistent and widespread problem, especially in geographical regions that are prone to large amounts of rainfall. Building foundations are susceptible to leakage when the soil surrounding the foundation becomes saturated with rainwater. Flooded and wet basements and crawl spaces, as well as wetness beneath slabs, may contribute to property damage. Standing water and humidity resulting from leakage contribute to the growth of harmful microorganisms, such as dust mites and mold, which may produce allergens, toxins, irritants and unwanted odors. Additionally, in post and pier foundation, frost heave is a particular nuisance that may result in cracked and damaged foundations in climates with freezing weather.
[0003] Saturated soil typically results from the direct rainfall on and around a structure, as well as from runoff from surrounding lots and structures which may be uphill from a particular structure. Conventional methods for preventing leakage of water into basements and crawl spaces include the construction of a surface or sub-surface drainage system. With a surface system, the type of soil utilized should be relatively impermeable and graded to a visible slope away from the structure, which typically is at least one-half inch per foot. With a sub-surface system the rainwater typically is drained to a buried pipe, which must remain unclogged and effective whether it drains to a sump pump, municipal storm system or ambient atmosphere.
[0004] However, even under ideal conditions where drainage systems are operating normally, some water can accumulate in the soil surrounding a structure. Thus, in addition to drainage, foundation walls typically are “damproofed” with a coating of bitumen and/or a layer of plastic placed beneath the concrete floor slab to retard movement of water vapor into the building. Furthermore, as a backup, a sump pump often is installed to collect and discharge any water that may accumulate in the soil or gravel beneath the floor slab. Such methods, however, are not effective when the soil surrounding the foundation is saturated.
SUMMARY OF THE INVENTION
[0005] The instant invention is directed to a system of one or more preformed diverters for directing water away from a building foundation having a generally vertical section with a first predetermined width and an angled section having a second predetermined width and being angled downwardly and away from both the vertical section and the building foundation.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] Other features, objects and advantages of the invention will be apparent by reference to the drawings, of which:
[0007] FIG. 1 is a front perspective view of an exemplary house and foundation with a preferred embodiment diverter system of the instant invention;
[0008] FIG. 2 is side perspective view of an outside corner of an exemplary house and foundation with a preferred embodiment outside corner unit and a preferred embodiment generally planar unit of the instant invention;
[0009] FIG. 3 is a side perspective view of a preferred embodiment outside corner unit of the instant invention coupled to a building foundation;
[0010] FIG. 4 is a side elevational view of a preferred embodiment outside corner unit of the instant invention;
[0011] FIG. 5 is a side elevational view of a preferred embodiment inside corner unit of the instant invention;
[0012] FIG. 6 is a side elevational view of a preferred embodiment generally planar unit of the instant invention;
[0013] FIG. 7A is a top elevational view of the sheet of material from which a preferred embodiment outside unit may be formed;
[0014] FIG. 7B is a side elevational view of the assembly of a preferred embodiment outside corner unit;
[0015] FIG. 7C is a top elevational view of the sheet of material from which a preferred embodiment inside corner unit may be formed;
[0016] FIG. 8A is a side perspective view of a preferred embodiment outside corner unit;
[0017] FIG. 8B is a side perspective view of a preferred embodiment inside corner unit of the instant invention;
[0018] FIG. 9A is a front perspective view of a post foundation coupled to a post unit;
[0019] FIG. 9B is a front perspective view of a pier foundation coupled to a plurality of outside corner units; and
[0020] FIG. 10 is a side elevational view of an outside corner unit of an embodiment of the instant invention.
DETAILED DESCRIPTION OF THE INVENTION
[0021] The instant invention is directed to a system that diverts water away from a building foundation that includes one or more preformed diverters that are configured for on-site installation, and which are shaped to at least partially abut the building foundation and divert water away therefrom. Buildings and their foundations are constructed to assume a wide variety of architectural shapes, and accordingly, the system of the instant invention includes preformed diverters that readily accommodate the various corners and planar surfaces included in the structure of a building and its foundation. More specifically, the instant invention includes a plurality of preformed diverters having predetermined shapes that accommodate inside corners and outside corners of a foundation, as well as the generally planar wall surfaces of a foundation. Additionally, the instant invention contemplates that preformed diverters may be provided for a vast array of foundation shapes, including but not limited to radiused foundations, such as round foundations, or polygonal foundations, such as pentagonal, hexagonal, heptagonal, or octagonal foundations, or corners having angles of greater than or less than 90°.
[0022] For purposes of illustration, FIG. 1 illustrates an exemplary house 10 constructed atop a foundation 12 . In addition to generally planar wall surfaces 14 , the illustrated house 10 includes two kinds of corners: outside corners 16 and inside corners 18 . Outside corners 16 are corners are corners where walls meet to form an interior angle, which is an angle facing the interior of the structure, of approximately less than 180°, for example a 90°. Conversely, inside corners 18 are corners where walls meet to an internal angle of greater than 180°, for example 270°. Typically, the foundation 12 underlying the house 10 corresponds to the shape of the house, and will accordingly include corresponding outside corners 16 and inside corners 18 .
[0023] Thus, as illustrated in FIGS. 4, 5 and 6 , the diverter system of the instant invention includes a plurality of preformed diverter units, more specifically an outside corner unit 24 , an inside corner unit 26 , and a generally planar unit 28 . Once dimensions are specified for the diverter units 24 , 26 , 28 , diverter units may be preformed in a customized configuration to accommodate a specified foundational shape and size. Each of the diverter units 24 , 26 , 28 includes a generally vertical section 30 and an angled section 32 that are preferably of unitary construction, but which may optionally be assembled from multiple sub-units and subsequently sealed to prevent leakage. Additionally, the dimensions of the respective vertical sections 30 and angled sections 32 may vary from unit to unit.
[0024] Turning now to FIGS. 2, 3 and 4 , the outside corner unit 24 includes a preferably unitary diverter body generally shaped to fit closely to the outside corners 16 of the building foundation 12 . Accordingly, the generally vertical section 30 of the outside corner unit 24 is generally L-shaped and includes first and second portions 34 , 36 that are disposed at an angle with respect to one another. For purposes of illustration only, the first and second portions 34 , 36 are disposed at a right angle in FIGS. 2, 3 , and 4 . However, as illustrated in FIG. 8A , the first and second portions 34 , 36 may be disposed at other angles as well. The angle of abutment 38 in the instant embodiment, which is the angle defined by the surfaces of the generally vertical section 30 that are configured to abut the foundation 12 , is approximately 90°. However, as illustrated in FIG. 8A , the angle of abutment 39 is approximately 135°.
[0025] The outside corner unit 24 also includes the angled portion 32 . In the outside corner unit 24 , the angled portion 32 extends downwardly and away from both the vertical section 30 and the building foundation 12 . The angled portion 32 is preferably unitary with the vertical section 30 , and extends from the vertical section preferably at a grade of approximately 20%. While the angled portion 32 may assume a variety of configurations, the preferred embodiment includes an angled portion having two planar surfaces 40 , 42 that are angled with respect to one another so that a longitudinal peak 44 is formed on a common side of the planar surfaces. In alternative embodiments, where the two planar surfaces 40 , 42 may be assembled from multiple sub-units, the longitudinal peak 44 may form a junction between sub-units. This configuration eliminates the possibility that water in the surrounding soil could pool within the outside corner unit 24 . Thus, water in the surrounding soil first encounter one of the planar surfaces 40 , 42 and owing to the angle at which the planar surfaces are disposed, will be forced downwardly on either side of the planar surfaces and away from the foundation.
[0026] Both the vertical section 30 and the angled section 32 include predetermined dimensions, with the width of the vertical section preferably being at least slightly smaller than that of the angled section. For example, while dimensions may be varied to suit individual applications, the preferred vertical section 30 of the outside corner unit 24 has a predetermined width of approximately ten inches, a predetermined thickness of approximately 0.045 inches (1 mm), and each of the first and second portions 34 , 36 have a predetermined length of approximately 24 inches. Typically, a ratio of the widths of the vertical section 30 and the angled section 32 are preferably between approximately 1:1 and 1:10.
[0027] Similarly, while the dimensions of the angled section 32 may vary to suit individual applications, the preferred angled section has a length of approximately 30 inches. As illustrated in FIG. 4 , there is a shared boundary between the vertical section 30 and each of the planar surfaces 40 , 42 , and as such, the length of each of the planar surfaces will preferably correspond to that of each of the first and second portions 34 , 36 of the vertical section 30 , which in the preferred embodiment is approximately 24 inches. Also, because the vertical section 30 and the angled section 32 are preferably unitary and constructed from a single sheet of composite material, the thickness is typically uniform throughout both the vertical section and the angled section.
[0028] Turning now to FIG. 5 , the inside corner unit 26 includes a unitary diverter body generally shaped to fit closely to the inside corners 18 of the building foundation 12 . Therefore, the generally vertical section 30 of the inside corner unit 26 is generally L-shaped and includes first and second portions 44 , 46 that are disposed at an angle with respect to one another. For purposes of illustration only, the first and section portions 44 , 46 of the instant embodiment are illustrated at a right angle with respect to one another in FIG. 5 . However, the angle at which the first and second portions 44 , 46 are oriented with respect to one another may vary to suit individual applications, as illustrated in FIG. 8B where the angle of abutment 47 is approximately 225°. The angle of abutment 48 for the vertical section 30 of the inside corner unit 26 is generally the inverse of that of the outside corner unit 24 . As such, the angle of abutment 48 for the inside corner unit 26 illustrated in FIG. 5 is approximately 270°.
[0029] Like the outside corner unit 24 , the inside corner unit 26 also includes the angled portion 32 . In the inside corner unit 26 , the angled portion 32 extends downwardly and away from both the vertical section 30 and the building foundation 12 preferably at a grade of approximately 20%. The angled portion 32 is preferably unitary with the vertical section 30 , and extends at an obtuse angle from the vertical section. While the angled portion 32 may assume a variety of configurations, the preferred embodiment wherein the angle of abutment 48 is approximately 270° includes an angled portion having three generally triangular planar surfaces 50 , 52 , 54 that are generally isosceles in shape, each having a base 56 and two equal sides 58 . The planar surfaces 50 , 52 , 54 are angled with respect to one another so that a pair of longitudinal valleys 60 is formed. In alternative embodiments wherein the planar surfaces 50 , 52 , 54 are assembled from multiple sub-units, the longitudinal valleys 60 may form the junction between the planar surfaces. This configuration reduces the possibility that water in the surrounding soil could pool within the inside corner unit 26 because water in the surrounding soil first encounters one of the planar surfaces 50 , 52 , 54 , and owing to the angle at which the planar surfaces are disposed, will then be forced downwardly into one of the longitudinal valleys 60 and away from the foundation 12 .
[0030] However, as FIG. 8B illustrates, three planar surfaces are not necessary. In the embodiment illustrated in FIG. 8B , where the angle of abutment 47 is approximately 315°, only two planar surfaces 61 a, 61 b are provided.
[0031] Both the vertical section 30 and the angled section 32 include predetermined dimensions, with the width of the vertical section preferably being at least slightly smaller than that of the angled section. Typically, a ratio of the widths of the vertical section 30 and the angled section 32 are preferably between approximately 1:1 and 1:10.
[0032] For example, while dimensions may be varied to suit individual applications, the preferred vertical section 30 of the inside corner unit 26 has a predetermined width of approximately ten inches, a predetermined thickness of approximately 0.045 inches, and each of the first and second portions 44 , 46 have a predetermined length of approximately 44 inches.
[0033] Similarly, while the dimensions of the angled section 32 may vary to suit individual applications, the two outside planar surfaces 50 , 54 of the preferred angled section have a base length of approximately 30 inches. The center planar surface 52 has a base length of approximately 53 inches. As illustrated in FIG. 5 , there is a shared boundary between the vertical section 30 and the two outside planar surfaces 50 , 54 . As such, the length of each of those planar surfaces 50 , 54 will preferably correspond to that of each of the first and second portions 44 , 46 of the vertical section 30 , which in the preferred embodiment is approximately 44 inches. Also, because the vertical section 30 and the angled section 32 are preferably unitary and constructed from a single sheet of composite material, the thickness is typically uniform throughout both the vertical section and the angled section.
[0034] The generally planar unit 28 , illustrated in FIG. 6 , is dimensioned and configured to abut the planar wall surfaces 14 included in the structure of a building and its foundation. The planar unit 28 preferably includes a unitary diverter body generally shaped to fit closely to the planar wall surfaces 14 of the building foundation 12 . However, as with both the inside and outside corner units 24 , 26 , alternative embodiments of the planar unit 28 may include multiple sub-units that are subsequently assembled into a preformed unit. Therefore, the generally vertical section 30 of the planar unit 28 is generally planar and has an angle of abutment 62 of approximately 180°.
[0035] Like both the outside and inside corner units 24 , 26 the planar unit 28 also includes the angled portion 32 . The angled portion 32 similarly extends downwardly and away from both the vertical section 30 and the building foundation 12 . The angled portion 32 is unitary with the vertical section 30 , and extends downwardly preferably at a grade of approximately 20%. However, unlike the other two units 24 , 26 , the angled portion 32 of the preferred embodiment includes a single generally rectangular, generally planar surface 64 . This configuration also eliminates the possibility that water in the surrounding soil could pool within the planar unit 28 because there is no surface on which water could collect. Rather, water will follow the path of least resistance and flow downwardly along the generally planar surface 62 .
[0036] Both the vertical section 30 and the angled section 32 include predetermined dimensions, with the width of the vertical section preferably being at least slightly smaller than that of the angled section. Typically, a ratio of the widths of the vertical section 30 and the angled section 32 are preferably between approximately 1:1 and 1:10.
[0037] For example, while dimensions may be varied to suit individual applications, the preferred vertical section 30 of the planar unit 28 has a predetermined width of approximately ten inches, a predetermined thickness of approximately 0.045 inches, and a predetermined length of approximately 27 inches. When a plurality of planar units 28 are installed, they are installed so that at least a portion of one unit overlaps at least a portion of the adjacent unit, thereby preventing any unprotected surfaces. Thus, in the preferred embodiment, the 27 inch length anticipates that as much as 1½ inches on either side of the vertical section 30 may be obscured by the adjacent unit 28 , leaving only approximately 24 inches exposed.
[0038] However, the predetermined length may optionally be configured to include any predetermined measurement designated by an end user, preferably measured in a discrete unit such as, for example, inches, feet, yards, centimeters and meters. For example, an end user may desire a few larger units rather than many smaller units, and may accordingly specify units measuring from between 3 and 12 feet, or any similar measurement. Alternatively, an end user may, for example, specify two corner units (outside corner units 24 , inside corner units 26 or a combination of both) and a single planar 28 unit having a predetermined length to span the distance between the corner units. Thus, the instant invention contemplates providing a bolt of material having a predetermined length, that is either rolled or folded for delivery to the end user, which is subsequently installed.
[0039] Similarly, while the dimensions of the angled section 32 may vary to suit individual applications, the planar surface 62 of the preferred angled section has a length of approximately 30 inches. There is a shared boundary between the vertical section 30 and the planar surface 62 , whether unitary or composed of multiple sub-units. As such, the width of the planar surface 62 will preferably correspond to that of the vertical section 30 , which in the preferred embodiment is approximately 27 inches. Also, when the vertical section 30 and the angled section 32 are unitary and constructed from a single sheet of composite material, the thickness is typically uniform throughout both the vertical section and the angled section.
[0040] In addition to the outside, inside and planar units 24 , 26 , 28 , the instant invention contemplates providing diverter units for a vast array of foundation shapes, including but not limited to radiused foundations or polygonal shapes. The invention contemplates providing customized units preformed to the specifications of a user, having such custom polygonal or radiused shapes. For example, where pier or post foundations are provided, alternative customized shapes may be desireable. Where the soil in contact with the pier or post is saturated with water, it may freeze during cold weather, resulting in the ice attaching to the surface of the pier. As the water beneath the ice turns to ice, it heaves or lifts the ice above, as well as the pier that is strongly attached thereto. The amount of heave depends on the degree of saturation as well as on the severity of the freeze event.
[0041] Turning now to FIG. 9A , a post unit 66 coupled to a post foundation 68 is illustrated. Preferably, as illustrated in FIG. 9A , the post unit 66 is a single unit preformed to be coupled to a post foundation (not shown). However, it is anticipated that the post unit 66 may optionally include multiple sub-units as well. While the post unit 66 preferably includes a through-cut 68 to permit coupling to an existing post foundation, it is also anticipated that an uninterrupted post unit could be coupled to a post foundation during construction of the foundation. In the preferred embodiment, the through-cut 68 extends downwardly through the vertical portion 70 and angled portion 72 to permit coupling to the post foundation, wherein an angled portion of the post unit 66 includes sufficient surface area to provide for some lapping.
[0042] Turning now to FIG. 9B , the pier unit 74 preferably includes four preformed outside corner units 24 . The pier unit 74 could optionally be preformed to omit through-cuts, and could thus be coupled to a pier foundation (not shown) during construction. Similar to the post unit 66 , the pier unit 74 could also optionally include a single through-cut cut 76 . The pier unit 74 preferably includes multiple through-cuts 76 , such as two through-cuts as illustrated in FIG. 9B , or such as four through-cuts.
[0043] Like the outside, inside, planar and pier units 24 , 26 , 28 , 74 , the post unit 66 may either be of unitary construction or assembled from a rubber such as recycled tire buffings in a polyethylene matrix, EPDM (ethylene propylene diene monomer) or neoprene. The invention contemplates use of other fabrication materials, such as polymeric materials like polyvinyl chloride (PVC), polyethylene, acrylonitrile butadiene styrene (ABS), polypropylene, as well as bitumen materials modified with styrene butadiene styrene (SBS) or atactic polypropylene (APP). Preferably, the post unit 66 may be preformed from the angled portion 72 , which is preferably a generally circular inclined sub-unit, and a generally rectangular vertical panel that may be formed into the generally cylindrical shaped vertical portion 70 . During assembly, the vertical portion 70 and the angled portion 72 interface generally at an outer circumference of the vertical portion 70 that has been formed to have a generally cylindrical shape, and are sealed together with neoprene or other adhesive.
[0044] The pier unit 74 may be preformed in a plurality of ways: as a single unitary unit by using a mold having a predetermined configuration, with multiple sub-units having a generally horizontal joint, or as a plurality of outside corner units 24 .
[0045] Since post foundations 68 and pier foundations 74 do not typically extend to the same depths as a basement, for example, and because the inclemency being protected against is frost heave rather than rainfall or other precipitation, the post and pier units 66 , 74 preferably extend outwardly at a distance that is smaller than an outward extension of the angled portions 32 of the outside corner, inside corner and planar units 24 , 26 , 28 . In one embodiment, for example, the post and pier units 66 , 74 extend outwardly at a distance of about 16 inches with an upward extension of approximately 10 inches.
[0046] In the preferred embodiment, the outside corner unit 24 , inside corner unit 26 and planar unit 28 are preformed from the same composite material, which is preferably a rubber such as recycled tire buffings in a polyethylene matrix, EPDM (ethylene propylene diene monomer) or neoprene. The invention contemplates use of other fabrication materials, such as polymeric materials like polyvinyl chloride (PVC), polyethylene, acrylonitrile butadiene styrene (ABS), polypropylene, as well as bitumen materials modified with styrene butadiene styrene (SBS) or atactic polypropylene (APP).
[0047] Preferably, each of the units 24 , 26 , 28 is preformed from a single piece of composite material. However, the instant invention contemplates embodiments wherein each unit 24 , 26 , 28 may be preformed from multiple sub-units. Ultimately, multiple methods of performing the diverter units 24 , 26 , 28 are contemplated, where once preformed, the diverter units are capable of ready installation. Where the diverter units 24 , 26 , 28 include multiple sub-units, the diverter units may be preformed to assume the same shapes and dimensions as those preformed from a single piece of composite material, with junctions between the sub-units preferably sealed in a manner adequate to prevent or reduce leakage.
[0048] In the preferred embodiment the diverter units 24 , 26 , 28 are preformed from a single piece of composite material, as illustrated in FIGS. 7A and 7B . For example, FIGS. 7A and 7B illustrate a possible configuration for the outside and inside corner units 24 , 26 , where a 54″×54″ sheet of composite material is cut and folded. Cuts 80 are represented by solid lines, whereas folds 82 are represented by dotted lines. Preferably, the folds 82 that divide the vertical section 30 and angled section 32 are oriented with respect to one another at a slightly obtuse angle, such as at 92 degrees with respect to one another. The slightly obtuse angle promotes subsequent folding of the corner units 24 , 26 to have a configuration wherein the angled section 32 and the vertical section 30 are disposed at a grade of approximately 20%. Tile planar unit 28 is also preformed from a single sheet of composite material that is folded but uncut.
[0049] More specifically, as illustrated in FIGS. 7A and 7B , in performing a preferred embodiment of the outside corner unit 24 , two triangular shaped sections, which when combined form a generally square piece of material, are excised from the sheet of material. More specifically, a first generally triangular section is excised, and discarded, leaving a corresponding V-shaped cut-out section 84 . A second triangular section 86 is also excised, either subsequent to or prior to the excision of the first triangular section. As illustrated in FIG. 7B , the second triangular section 86 is folded and coupled to the assembled outside corner unit 24 over an area generally corresponding with the V-shaped cut-out section 84 , preferably with the second triangular section overlapping at least a portion of the first and second portions 34 , 36 . The second triangular section 86 may be secured thereto in a variety of ways, such as with a preferred overlap of approximately 1 inch between the second triangular section and the cut-out 84 created by the excision of the first triangular section, and held together with an adhesive such as contact adhesive.
[0050] Alternatively, an additional strip of rubber 88 , (best shown in FIG. 10 ) preferably uncured neoprene, may be coupled to the outside corner unit 24 and fastened with an adhesive. The strip of rubber 88 optionally includes a release paper having a tacky surface. A sheetgood surface to which the strip of rubber 88 is applied is preferably primed with an adhesive compound, subsequently allowed to “flash” for about 30 seconds, and then the sheetgood surface and the strip of rubber are mated. The resulting adhesive joint is considered in the art to be one of the better joints that include rubber compounds.
[0051] When a strip of rubber 88 is included in the assembled outside corner unit 26 , assembly proceeds as illustrated in FIGS. 7A and 7B . As illustrated in FIG. 10 , a piece of uncured neoprene is cut, preferably in a V-shape, with a thickness of each leg of the V-shape being between approximately 1½ and 2 inches. The second triangular section 86 is cut so that it generally corresponds to the hole created by the excision of the first triangular section 84 . A bottom portion of the V-shape is preferably cut to have a radius of approximately 1 inch, and is manipulated so that it flares outwardly.
[0052] Turning now to the inside corner unit 26 illustrated in FIG. 7C , this unit may be preformed in a variety of ways, such as from a single piece of material, with an overlap generally disposed at a corner joint 90 (best shown in FIG. 5 ) first and second portions 44 , 46 meet. The inside corner unit 26 is preferably assembled by the cutting of sheet material as illustrated in FIG. 7C , and also including an additional strip of rubber (not shown), such as uncured neoprene. The strip of rubber preferably included in the inside corner unit 26 may assume numerous configurations, with one exemplary embodiment having a width of approximately 2 inches and a length of approximately 11 inches. The strip of rubber is preferably shaped to be generally horizontal at a top edge, but a generally semicircular shape at a bottom edge, where the semicircle includes an approximately 1-inch radius. The generally semicircular edge of the strip of rubber is manipulated so that a center of the semicircular edge is enlarged, while the circumference of the same end is preferably unchanged. A primer adhesive compound is subsequently applied to sheetgoods in an approximately 1-inch wide band along a side of each of the first and second portions 44 , 46 . Primer adhesive is also preferably applied at where a bottom point of the corner joint 90 meets the planar surfaces 50 , 52 , 54 , and outwardly at a distance of about 1 inch.
[0053] Once formed, one or more of each of the outside corner, inside corner and planar units 24 , 26 , 28 may be installed around a building foundation 12 . The units 24 , 26 , 28 may be installed atop bare prepared soil or alternatively over thermal insulating materials. FIG. 3 illustrates the outside corner piece 24 installed over thermal insulating materials 92 . Using a thermal insulating material, such as polystyrene or high-density fiberglass, in connection with the diverter units 24 , 26 , 28 of the instant invention confers several additional advantages. First, soil, when excavated and replaced, loses some of its volume. Adding insulation under the diverter unit 24 , 26 , 28 compensates for this lost volume. Use of high-density fiberglass under the vertical section 30 of each unit 24 , 26 , 28 in particular is useful in applications by pest control operators to permit treatment chemicals to be placed beneath the angled portion 32 , ensuring longer service life from the chemicals because they would not be leached out of the soil by slugs of rainwater washing the chemicals downward.
[0054] When applied on bare soil, the soil is preferably prepared by compacting the soil. While multiple methods of compacting the soil are anticipated, the soil is preferably compacted by impacting the soil, either once or multiple times with weighty implements. For example, a length of wood, such as a 4×4 length of wood may be elevated above the soil and released at a predetermined distance above the soil so that an end of the length of wood impacts the soil. Similarly, a steel pipe with a square foot attached may be elevated above the soil and released at a predetermined distance above the soils so that the foot impacts the soil. Also, a motorized plate tamper, such as the Dynapac LT74H Vibratory Jumping Jack Plate Tamper manufactured by Metso Minerals, Ltd. of Helsinki, Finland may also be used for soil compaction.
[0055] Turning now to FIG. 3 , an additional coupling mechanism is preferably provided to maintain placement of the diverter units 24 , 26 , 28 once installed. Accordingly, each diverter unit 24 , 26 , 28 is preferably provided with at least one termination bar 94 that includes a fastening mechanism. The termination bar 94 is generally rectangular in shape, and includes at least one orifice 96 through which a corresponding fastener 98 may be inserted. Each unit 24 , 26 , 28 is preferably provided with a number of termination bars 94 that corresponds to the number of portions included in the respective vertical section 30 .
[0056] More specifically, the outside corner unit 24 , which includes first and second portions 34 , 36 within its vertical section 30 , is preferably provided with two termination bars 94 , one for each of the first and second portions. The inside corner unit 26 , which includes first and second portions 44 , 46 within its vertical section, and is therefore preferably provided with two termination bars 94 . In contrast, the single portion that comprises the vertical section 30 of the planar unit 28 is preferably provided with a single termination bar 94 .
[0057] Each termination bar 94 has a predetermined length that preferably corresponds to the length of the portion of the vertical section 30 to which it will be coupled. Thus, the outside corner unit 24 is provided with two termination bars 94 , each having a predetermined length of approximately 24 inches. The inside corner unit 26 is provided with two termination bars 94 , each having a predetermined length of approximately 44 inches. The planar unit 28 is provided with a single termination bar 94 having a predetermined length of approximately 24 inches. Each termination bar 94 is coupled to an upper edge of the respective vertical portion. The fastener 98 , such as a threaded fastener or a bolt, is then inserted into the respective orifice 96 and coupled to the foundation 12 .
[0058] Alternatively, the termination bar 94 may optionally be provided in fractions of the lengths of the respective vertical section 30 . For example, where the end user has specified that the planar unit 28 measure 8 feet, providing a corresponding length of termination bar 94 may be accomplished by providing several fractions of termination bar that total 8 feet. For example, four two-foot termination bars 94 could be provided with an eight-foot planar unit 28 , which may ease manufacturing, packaging and shipping burdens.
[0059] While various embodiments of the present invention have been shown and described, it should be understood that other modifications, substitutions and alternatives are apparent to one of ordinary skill in the art. Such modifications, substitutions and alternatives can be made without departing from the spirit and scope of the invention, which should be determined from the appended claims. | A method of installing preformed unibody diverter units around building foundations to direct water away from the building foundation including performing the diverter units to have a vertical section and an angled section, preparing the soil surrounding the building foundation, and coupling the vertical section to the building housing. | 4 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a combination drier and washer which washes and dries laundry, and particularly, to a combination drier and washer and an aeration apparatus thereof in which a dry space is closed in a dry processing and exterior air is introduced in a drum when the dry processing is finished.
2. Description of the Background Art
FIG. 1 is a longitudinal sectional view showing a drum-type combination drier and washer in accordance with the conventional art.
The drum-type combination drier and washer in accordance with the conventional art comprises; a tub 21 located in a case 11 for storing washing water; a rotating drum 31 rotatably installed in the tub 21 centering a rotational shaft arranged along a horizontal direction in the tub 21 for washing and drying laundry; and a driving motor 33 located behind the tub 21 for driving the rotating drum 31 .
An opening provided with a door 13 is formed in front of the case 11 to put in and take out laundry. The tub 21 is formed as a cylindrical shape to be connected to the opening of the case 11 .
A spring member 23 and a damper 25 are respectively installed at upper and lower portions of the tub 21 for supporting the tub 21 in the case 11 . A detergent container 30 is provided at an upper portion of the tub 21 to supply detergent. The detergent container 30 is connected to a supplying tube 38 for supplying washing water.
A drain tube 27 is engaged in a lower portion of the tub 21 for draining washing water, and provided with a drain pump 29 .
The drum-type combination drier and washer is provided with a drying unit for drying laundry. The drying unit includes; an air circulation duct 32 connected from a rear bottom portion to a frontal portion of the tub 21 ; a blower 41 and a heater 43 arranged on the air circulation duct 32 for forcibly circulating air and for heating air, respectively; and a condensing water supply tube 37 connected to an entrance of the air circulation duct 32 for supplying condensing water so as to condense water in the air discharged from the tub 21 .
The air circulation duct 32 consists of a condensing tube 35 and an air tube 39 . The condensing tube 35 has one end connected to a lower portion of the tub 21 and the other end prolonged upwardly in the case 11 and connected to the blower 41 . The air tube 39 has one end connected to the blower 41 and the other end connected to a frontal portion of the tub 21 .
Herein, the condensing water supply tube 37 is connected to an upper portion of the condensing tube 35 .
In the drum-type combination drier and washer in accordance with the conventional art, when a washing process is finished and a drying process starts, the blower 41 is driven, and air in the rotating drum 31 and the tub 21 flows towards the blower 41 through the condensing tube 35 .
At this time, if condensing water is supplied in the condensing tube 35 through the condensing water supply tube 37 , whereas water in the air is condensed to be introduced at a lower portion of the tub 21 , dehumidified air passes the blower 41 , flows along the air tube 39 and is heated by the heater 43 , thereby circulating in the tub 21 and the rotating drum 31 .
Dry air of high temperature introduced in the tub 21 and the rotating drum 31 dries laundry, flows along the condensing tube 35 and the air tube 39 from the tub 21 , and repeats the condensing and drying processes, thereby drying laundry.
However, in the drum-type combination drier and washer in accordance with the conventional art, the tub 21 and the air circulation duct 32 have the closed structures so as to prevent air of high temperature from being leaked outward. Accordingly, when a child or a pet is confined in the rotating drum, a suffocation accident can be caused.
Also, in case of that the inside of the tub 21 is communicated with the outside of the case 11 , dry air in the tub 21 is exhausted to degrade drying efficiency, and heated air of high temperature is leaked outward to cause accidents such as a burning.
SUMMARY OF THE INVENTION
Therefore, an object of the present invention is to provide a combination drier and washer, and an aeration apparatus thereof, wherein air of high temperature is prevented from being leaked by closing the inside from outside in a drying process, and inside and outside are communicated to aerate when the drying process is finished, thereby not degrading a drying process and reducing accidents.
To achieve these and other advantages and in accordance with the purpose of the present invention, as embodied and broadly described herein, there is provided a combination drier and washer, and an aeration apparatus thereof comprising an air circulation duct connected from one portion of a tub to the other portion for circulating air in the tub; and an aeration means provided in the middle of the air circulation duct for preventing exterior air being introduced in the tub in a drying process, and for aerating exterior air in the tub in an opened state when the drying process is not performed.
The aeration means includes; an aeration tube connected from the air circulation duct to outside of a case for introducing exterior air; and an opening/closing means provided at a spot where the air circulation duct and the aeration tube meet for opening and closing the aeration tube.
The air circulation duct is connected to a condensing water supply tube for supplying condensing water so as to condense water in the air. The opening/closing means is constructed to open and close the aeration tube by condensing water supplied by the condensing water supply tube.
The opening/closing means located at the spot where the aeration tube and the condensing water supply tube meet makes a constant amount of condensing water stay at the time of supplying condensing water. The opening/closing means includes a condensing water stay container for introducing the stayed condensing water into the aeration tube and for closing the aeration tube.
According to one preferred embodiment of the present invention, the condensing water stay container is provided with a bulkhead for containing a constant amount of condensing water and supplying condensing water by way of flowing over the bulkhead. Also, a drain hole is formed at a lower portion of the bulkhead so as to drain the remained condensing water.
The drain hole is formed to drain less amount than that of condensing water supplied by the condensing water supply tube.
According to another preferred embodiment of the present invention, the condensing water stay container includes; a condensing water supply passage at a height where some amount of condensing water stays for supplying the condensing water into the air circulation duct; and a drain hole at a lower portion for draining remained condensing water when condensing water is not supplied.
A lower portion of the aeration tube is arranged at a lower position than the condensing water supply passage.
The drain hole is formed to drain less amount than that of condensing water supplied by the condensing water supply tube.
To achieve these and other advantages and in accordance with the purpose of the present invention, as embodied and broadly described herein, there is provided an aeration apparatus for a combination drier and washer comprising; an air circulation duct provided to circulate and heat air in a tub and dry laundry, and connected from one portion of the tube to the other portion for circulating air in the tub; a condensing water supply tube connected at an upper portion of the air circulation duct for condensing water in circulated air; a condensing water stay container connected between the air circulation duct and the condensing water supply tube for making a constant amount of condensing water stay when condensing water is supplied in the air circulation duct; and an aeration tube connected to the condensing water stay container towards outside of the case and closed by the condensing water in the condensing water stay container for preventing exterior air from being introduced in the tub.
To achieve these and other advantages and in accordance with the purpose of the present invention, as embodied and broadly described herein, there is provided a combination drier and washer that includes an aeration apparatus comprising; a tub located in a case for storing washing water therein; a drum located in the tub for washing and drying laundry; an air circulation duct connected from one portion of the tub to the other portion of the tub for circulating air in the drum; a blower provided in the air circulation duct; a heater provided in the air circulation duct for heating circulating air; and an aeration means provided at the air circulation duct for opening and closing the air circulation duct for preventing exterior air from being introduced into the tub in a drying process, and for aerating exterior air in the tub in an opened state when the drying process is not performed.
The air circulation duct includes; a condensing tube having one end connected to a lower portion of the tub and the other end upwardly prolonged to an upper portion of the tub, thereby being connected to the blower; and an air tube having one end connected to the blower and the other end connected to a frontal portion of the tub and provided with a heater for heating the circulating air.
A condensing water supply tube is formed to condense water in the circulating air at an upper portion of the condensing tube, and the aeration means is opened and closed by condensing water supplied through the condensing water supply tube.
The foregoing and other objects, features, aspects and advantages of the present invention will become more apparent from the following detailed description of the present invention when taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention.
In the drawings:
FIG. 1 is a longitudinal sectional view showing a drum-type combination washer and dried in accordance with the conventional art;
FIG. 2 is a longitudinal sectional view showing a combination drier and washer according to one embodiment of the present invention;
FIGS. 3 and 4 are detailed views of FIG. 2 , wherein FIG. 3 shows a state in a drying process, and FIG. 4 shows a state when the drying process is finished; and
FIGS. 5 and 6 are sectional views showing a combination drier and washer according to another embodiment of the present invention, wherein FIG. 5 shows a state in a drying process, and FIG. 6 shows a state when the drying process is finished.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Reference will now be made in detail to the preferred embodiments of the present invention, examples of which are illustrated in the accompanying drawings.
A drum-type combination drier and washer according to one embodiment of the present invention, referring to FIG. 2 , comprises a tub 21 located in an case 11 for storing washing water therein; a rotating drum 31 installed to rotate a rotational shaft arranged horizontally in the tub 21 for washing and drying laundry; a driving motor 33 behind the tub 21 for driving the rotating drum 31 ; a drying unit for circulating air in the rotating drum 31 , heating and drying laundry which finishes washing; and an aeration unit 50 connected with the drying unit towards outside of the case 11 for introducing exterior air into the rotating drum 31 by being closed in a drying process and by being opened when the drying process is finished.
The drying unit includes: an air circulation duct 32 connected from a rear bottom portion of the tub 21 to a frontal portion; a blower 41 arranged on the air circulation duct 32 for forcibly circulating air; a heater 43 arranged on the air circulation duct 32 for heating circulating air; and a condensing water supply tube connected to an opening of the air circulation duct 32 for supplying condensing water so as to condense water of air discharged from the tub 21 .
The air circulation duct 32 includes a condensing tube 35 having one end connected to a lower portion of the tub 21 and the other end upwardly prolonged in the case 11 and connected to the blower 41 ; and an air tube 39 having one end connected to the blower 41 and the other end connected to a frontal portion of the tub 21 .
Herein, the condensing water supply tube 37 is connected to an upper portion of the condensing water tube 35 , and the aeration unit 50 is formed at an interconnected spot between the condensing water supply tube 37 and the condensing water tube 35 .
The aeration unit 50 includes: a condensing water stay container 51 located at an interconnected spot between the condensing tube 35 and the condensing water supply tube 37 for containing condensing water therein in a drying process; and an aeration tube 61 having one end exposed to outside of the case 11 and the other end connected to and communicated with the condensing water stay container 51 for introducing condensing water contained in the condensing water stay container 51 in a drying process.
The condensing water stay container 51 , referring to FIG. 3 , includes: a container portion 53 having open portion connected to and communicated with the condensing tube 35 ; and a bulkhead portion 55 in the container portion 53 having a predetermined height difference with an upper portion of the container portion 53 so as to form a supply opening 57 .
At a bottom of the bulkhead portion 55 , a drain hole 59 is formed for discharging the whole condensing water instead of containing the condensing water in the container portion 53 when the drying process is finished. Herein, the drain hole 59 is formed to have a sectional flow area comparatively smaller than the supply opening 57 and the condensing water supply tube 37 .
Once a drying process starts and the blower 41 is driven, air discharged from the tub 21 is introduced upwardly in the condensing tube 35 , and air via the blower 41 flows along the air tube 39 is heated by the heater 43 , and returns to the tub 21 .
If a drying process starts, condensing water is supplied from the condensing water supply tube 37 into the condensing water stay container 51 , and some of the supplied condensing water is discharged to the condensing tube 35 through the drain hole 59 . Since supply amount of the condensing water from the condensing water supply tube 37 is much larger than that discharged to the drain hole 59 , condensing water is filled in the condensing water stay space S formed by the bulkhead portion 55 .
If the condensing water supplied from the condensing water supply tube 37 fills the condensing water stay space S, additionally-supplied condensing water is discharged to inside of the condensing tube 35 through the supply opening 57 and the drain hole 59 formed at an upper portion of the bulkhead portion 55 . Air absorbing water in the tub 21 flows upwardly along the condensing tube 35 containing water via the tub 21 is cooled by condensing water, and water in the air is condensed, introduced into a lower region of the tub 21 with the condensing water, discharged outward through the drain hole 27 , thereby making a dry processing.
Meanwhile, if the dry processing is finished, as shown in FIG. 4 , condensing water is not supplied from the condensing water supplying tube 37 any longer, and the condensing water remaining in the condensing water stay space S is discharged into the condensing tube 35 through the drain hole 59 . Also, if the remained condensing water contained in the condensing water stay space S and the aeration tube 61 is all drained, inside of the tub 21 is aerated with exterior air through the aeration tube 61 , the condensing tube 35 , and the air tube 39 .
FIGS. 5 and 6 are sectional views illustrating a combination drier and washer according to another embodiment of the present invention, wherein FIG. 5 shows a state in a dry processing, and FIG. 6 shows a state when the dry processing is finished.
The combination drier and washer according to another embodiment of the present invention comprises: a container portion 63 arranged between the condensing water supply tube 37 and the condensing tube 35 and interconnected for containing condensing water therein; and an air tube 61 having one end connected to outside of the case 11 and the other end engaged in the container portion 63 so as to introduce condensing water in a dry processing without aeration from outside and so as to discharge the condensing water and then aerate when the dry processing is finished.
Sectional areas of the lower region of the container portion 63 gradually decreases towards a down direction thereof. Also, a supply opening 64 a is formed at an upper portion of the container portion 63 , and connected with the condensing water supply tube 37 . A drain hole 64 b is formed at a lower portion to discharge condensing water. The drain hole 64 b is connected to a connecting tube 65 of which one end is connected to inside of the condensing tube 35 . An aeration hole 64 c is formed above the drain hole 64 b for connecting the aeration tube 61 . Also, a supply opening 64 d is formed above the aeration hole 64 c with a predetermined height difference so as to discharge condensing water to the condensing tube 35 region.
If a dry processing starts, as shown in FIG. 5 , condensing water is supplied from the condensing water supply tube 37 to inside of the container portion 63 , and some of the supplied condensing water is discharged into the condensing tube 35 through the drain hole 64 b and some is introduced into the aeration tube 61 , so that aeration is not generated between inside of the tub 21 and outside, thereby preventing air from being leaked.
Condensing water is continuously supplied into the condensing portion 63 and then water level is reached to the supply opening 64 d , the condensing water is discharged into the condensing tube 35 through the supply opening 64 d . Then, the condensing water introduced to the condensing tube 35 condenses water in the air and is introduced into a lower region of the tub 21 , thereby being discharged outward through the drain tube 27 .
In the meantime, if a drying process is finished and condensing water is not supplied any more, as shown in FIG. 6 , the whole condensing water introduced in the container portion 63 and the aeration tube 61 is discharged through the drain hole 64 b . According to this, the aeration tube 61 is opened, and the tub 21 is aerated with exterior air through the aeration tub 61 , condensing tube 35 , and the aeration tube 39 .
As aforementioned, according to the present invention, air of high temperature is not leaked outward in a drying process, and aerated with exterior air when the drying process is finished, thereby preventing a suffocation accident when a child or a pet is confined therein.
As the present invention may be embodied in several forms without departing from the spirit or essential characteristics thereof, it should also be understood that the above-described embodiments are not limited by any of the details of the foregoing description, unless otherwise specified, but rather should be construed broadly within its spirit and scope as defined in the appended claims, and therefore all changes and modifications that fall within the metes and bounds of the claims, or equivalence of such metes and bounds are therefore intended to be embraced by the appended claims. | An aeration apparatus for a combination drier and washer comprises an air circulation duct connected from one portion of a tub to the other portion for circulating air in the tub; an aeration tube connected from the air circulation duct to outside of the case for introducing exterior air; and an opening/closing unit provided at a spot where the air circulation duct and the aeration tube meet for opening and closing the aeration tube, wherein the air circulation duct is connected to a condensing water supply tube for supplying condensing water to condense water in air, and the opening/closing unit is constructed to open and close the aeration tube by condensing water supplied by the condensing water supply tube. During drying, the drying space is closed to improve drying efficiency. Afterward, air is introduced to prevent accidents. | 3 |
FIELD OF THE INVENTION
The present invention relates to the enzyme pantothenate synthetase, and in particular its crystal structure and the use of this structure in drug discovery.
BACKGROUND OF THE INVENTION
Pantothenic acid (vitamin B 5 ) is found in coenzyme A (CoA) and the acyl carrier protein (ACP), both of which are involved in fatty acid metabolism.
Pantothenic acid can be synthesised by plants and microorganisms but animals are apparently unable to make the vitamin, and require it in their diet. However, all organisms are able to convert pantothenic acid to its metabolically active form, coenzyme A.
The pathway for the synthesis of pantothenic acid is shown in FIG. 1 . It provides a potential target for the treatment of infectious disease, since inhibitors of the pathway should be damaging to bacteria and fungi but not to human or animal subjects infected by bacteria.
Of specific interest is pantothenate synthetase (D-pantoate: β-alanine ligase (AMP-forming); EC 6.3.2.1) This enzyme catalyses the condensation between β-alanine and pantoic acid, the final steps in pantothenic acid biosynthesis. Inhibitors (whether competitive, non-competitive, uncompetitive or irreversible) of pantothenate synthetase would be of significant technical and commercial interest.
Purification of pantothenate synthetase (PS) to homogeneity was achieved by Miyatake et. al, ( J. Biochem ., 79, (1976), 673-678). The enzyme was reported to require stoichiometric amounts of ATP as an energy source which is hydrolysed to AMP and inorganic pyrophosphate. The mechanism of the enzymic reaction involves pantoate adenylate as an intermediate.
However, until now no one has successfully determined the structure of PS. This has prevented PS inhibitors being developed via structure-based drug design methodologies. Knowledge of the structure of PS would significantly assist the rational design of novel therapeutics based on PS inhibitors.
SUMMARY OF THE INVENTION
The present invention is at least partly based on overcoming several technical hurdles: we have (i) produced PS crystals of suitable quality, including crystals of selenium atom PS derivatives, for performing X-ray diffraction analyses, (ii) collected X-ray diffraction data from the crystals, (iii) determined the three-dimensional structure of PS, and (iv) identified sites on the enzyme which are likely to be involved in the enzymic reaction.
In a first aspect, the present invention provides a crystal of PS having a monoclinic space group P2 1 , and unit cell dimensions of a=66.0±0.2 Å, b=78.1±0.2 Å, c=77.1±0.2 Å and β=103.7±0.2°. Preferably the PS is a dimer.
In a second aspect, the invention also provides a crystal of PS having the three dimensional atomic coordinates of Table 1.
In a third aspect, the invention provides a method for crystallizing a selenium atom PS derivative which comprises producing PS by recombinant production in a bacterial host (e.g. E. coli ) in the presence of selenomethionine, recovering a selenium atom PS derivative from the host and growing crystals from the recovered selenium atom PS derivative.
Thus, the selenium atom PS derivative and PS produced by crystallising native PS (see the detailed description below) are provided as crystallised proteins suitable for X-ray diffraction analysis.
The crystals may be grown by any suitable method, e.g. the hanging drop method.
In a fourth aspect, the present invention provides a method for identifying a potential inhibitor of PS comprising the steps of:
a. employing a three-dimensional structure of PS, or at least one sub-domain thereof, to characterise at least one PS active site, the three-dimensional structure being defined by atomic coordinate data according to Table 1; and
b. identifying the potential inhibitor by designing or selecting a compound for interaction with the active site.
By “sub-domain” is meant at least one complete element of secondary structure, i.e. an alpha helix or a beta sheet, as described in the detailed description below.
If more than one PS active site is characterised and a plurality of respective compounds are designed or selected, the potential inhibitor may formed by linking the respective compounds into a larger compound which maintains the relative positions and orientations of the respective compounds at the active sites. The larger compound may be formed as a real molecule or by computer modelling.
In any event, the determination of the three-dimensional structure of PS provides a basis for the design of new and specific ligands for PS. For example, knowing the three-dimensional structure of PS, computer modelling programs may be used to design different molecules expected to interact with possible or confirmed active sites, such as binding sites or other structural or functional features of PS.
More specifically, a potential modulator of PS activity can be examined through the use of computer modelling using a docking program such as GRAM, DOCK, or AUTODOCK (see Walters et al., Drug Discovery Today , Vol.3, No.4, (1998), 160-178, and Dunbrack et al., Folding and Design , 2, (1997), 27-42) to identify potential inhibitors of PS. This procedure can include computer fitting of potential inhibitors to PS to ascertain how well the shape and the chemical structure of the potential inhibitor will bind to the enzyme.
Also computer-assisted, manual examination of the active site structure of PS may be performed. The use of programs such as GRID (Goodford, J. Med. Chem ., 28, (1985), 849-857)n—a program that determines probable interaction sites between molecules with various functional groups and the enzyme surface—may also be used to analyse the active site to predict partial structures of inhibiting compounds.
Computer programs can be employed to estimate the attraction, repulsion, and steric hindrance of the two binding partners (e.g. the PS and a potential inhibitor). Generally the tighter the fit, the fewer the steric hindrances, and the greater the attractive forces, the more potent the potential modulator since these properties are consistent with a tighter binding constant. Furthermore, the more specificity in the design of a potential drug, the more likely it is that the drug will not interact with other proteins as well. This will tend to minimise potential side-effects due to unwanted interactions with other proteins.
Alternatively, step b. may involve selecting the compound by computationally screening a database of compounds for interaction with the active site. For example, a 3-D descriptor for the potential inhibitor may be derived, the descriptor including geometric and functional constraints derived from the architecture and chemical nature of the active site. The descriptor may then be used to interrogate the compound database, a potential inhibitor being a compound that has a good match to the features of the descriptor. In effect, the descriptor is a type of virtual pharmacophore.
Having designed or selected possible binding partners, these can then be screened for activity. Consequently, the method preferably further comprises the further steps of:
c. obtaining or synthesising the potential inhibitor; and
d. contacting the potential inhibitor with PS to determine the ability of the potential inhibitor to interact with PS.
More preferably, in step d. the potential inhibitor is contacted with PS in the presence of a substrate, and typically a buffer, to determine the ability of said potential inhibitor to inhibit PS. The substrate may be e.g. pantoic acid (or a salt thereof), β-alanine (or a salt thereof), or ATP. So, for example, an assay mixture for PS may be produced which comprises the potential inhibitor, substrate and buffer.
Instead of, or in addition to, performing e.g. a chemical assay, the method may comprise the further steps of:
c. obtaining or synthesising said potential inhibitor;
d. forming a complex of PS and said potential inhibitor; and
e. analysing said complex by X-ray crystallography to determine the ability of said potential inhibitor to interact with PS. Detailed structural information can then be obtained about the binding of the potential inhibitor to PS, and in the light of this information adjustments can be made to the structure or functionality of the potential inhibitor, e.g. to improve binding to the active site. Steps c. to e. may be repeated and re-repeated as necessary.
In a fifth aspect, the invention includes a compound which is identified as an inhibitor of PS by the method of the fourth aspect.
In a sixth aspect, the invention provides a method of analysing a PS-ligand complex comprising the step of employing (i) X-ray crystallographic diffraction data from the PS-ligand complex and (ii) a three-dimensional structure of PS, or at least one subdomain thereof, to generate a difference Fourier electron density map of the complex, the three-dimensional structure being defined by atomic coordinate data according to Table 1.
Therefore, PS-ligand complexes can be crystallised and analysed using X-ray diffraction methods, e.g. according to the approach described by Greer et al., J. of Medicinal Chemistry , Vol. 37, (1994), 1035-1054, and difference Fourier electron density maps can be calculated based on X-ray diffraction patterns of soaked or co-crystallised PS and the solved structure of uncomplexed PS. These maps can then be used to determine whether and where a particular ligand binds to PS and/or changes the conformation of PS.
Electron density maps can be calculated using programs such as those from the CCP4 computing package (Collaborative Computational Project 4. The CCP4 Suite: Programs for Protein Crystallography, Acta Crystallographica , D50, (1994), 760-763.). For map visualisation and model building programs such as “O” (Jones et al., Acta Crystallograhy , A47, (1991), 110-119) can be used.
In a seventh aspect, the present invention provides computer readable media with either (a) atomic coordinate data according to Table 1 recorded thereon, said data defining the three-dimensional structure of PS or at least one sub-domain thereof, or (b) structure factor data for PS recorded thereon, the structure factor data being derivable from the atomic coordinate data of Table 1.
As used herein, “computer readable media” refers to any media which can be read and accessed directly by a computer. Such media include, but are not limited to: magnetic storage media such as floppy discs, hard disc storage medium and magnetic tape; optical storage media such as optical discs or CD-ROM; electrical storage media such as RAM and ROM; and hybrids of these categories such as magnetic/optical storage media.
By providing such computer readable media, the atomic coordinate data can be routinely accessed to model PS or a sub-domain thereof. For example, RASMOL (Sayle et al., TIBS , Vol. 20, (1995), 374) is a publicly available computer software package which allows access and analysis of atomic coordinate data for structure determination and/or rational drug design.
On the other hand, structure factor data, which are derivable from atomic coordinate data (see e.g. Blundell et al., in Protein Crystallography , Academic Press, New York, London and San Francisco, (1976)), are particularly useful for calculating e.g. difference Fourier electron density maps.
In an eighth aspect, the present invention provides systems, particularly a computer systems, intended to generate structures and/or perform rational drug design for PS or PS ligand complexes, the systems containing either (a) atomic coordinate data according to Table 1, said data defining the three-dimensional structure of PS or at least one sub-domain thereof, or (b) structure factor data for PS, said structure factor data being derivable from the atomic coordinate data of Table 1.
Examples of such systems are microcomputer workstations available from Silicon Graphics Incorporated and Sun Microsystems running Unix based, Windows NT or IBM OS/2 operating systems.
As used herein, “a computer system” refers to the hardware means, software means and data storage means used to analyse the atomic coordinate data of the present invention. The minimum hardware means of the computer-based systems of the present invention comprises a central processing unit (CPU), input means, output means and data storage means. Desirably a monitor is provided to visualise structure data. The data storage means may be RAM or means for accessing computer readable media of the sixth aspect of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows schematically the pathway for the synthesis of pantothenic acid,
FIGS. 2 a-c show the general structure of PS, being respectively (a) a “cartoon” of the dimer, (b) a schematic diagram of the monomer topology with numbering of secondary structures, and (c) a schematic plot of hydrogen bonding patterns between secondary structures,
FIG. 3 is a stereo pair of images showing schematically the core of the dimerisation interface, and
FIG. 4 shows a Connolly surface generated around the proposed PS active site.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is founded on the determination of the three dimensional atomic structure of PS.
The structure is defined in Table 1 which gives atomic coordinate data for PS, which we have crystallised as a dimer, and associated water molecules. In Table 1 “Atom type” refers to the respective element, the first letter defining the element; “X, Y, Z” define, with respect to the crystallographic axes, the atomic position (in Å) of the respective atom; “Occ.” is the occupancy of the atom in the respective position; and “B” is a temperature factor (in Å 2 ) which accounts for movement of the atom around its atomic centre.
The atomic positions in Table 1 are given to three decimal places. However, for the avoidance of doubt it is hereby mentioned that varying the atomic positions of the atoms of the structure by up to about 0.2 Å in any direction will result in a structure which is substantially the same as the structure of Table 1 in terms of both its structural characteristics and utility e.g. for structure-based drug design.
PS Structural Characterization
We have found that the structure of a PS monomer consists of two major domains, joined at about residue 176 (FIGS. 2 a-c ). Domain N (so called because it contains the N terminal) has an alpha-beta-alpha architecture; six parallel β-strands with 1′-3-2-1-4-5 topology alternate with α-helices to form a Rossman fold with central β-sheet sandwiched between two layers of α-helices (FIG. 2 b ). The helices (α1′, 1, 2, 3 and 4) pack against the β-sheet in a right-handed way. The secondary structural elements have been numbered in FIGS. 2 a and b, with elements that are insertions or additions to the “standard” nucleotide-binding Rossman fold (discussed below under “Identification of Likely Active Sites”) denoted by primes. Strand β5 leads directly into the short β-hairpin and 3 10 helix motif (β6, β7 and ε 10 7), which lies at the head of domain C (containing the C terminal) and is likely to be involved in phosphate binding (see below). The rest of the domain has a simple two-layer organisation: a helix-turn-helix layered above a flat sheet of three anti-parallel β-strands (α8 and 9, β10-12). This sheet faces a prominent cleft in domain N, the predicted catalytic region (see below), making the whole structure resemble somewhat a pot (domain N) with its lid (domain C) on a hinge, a common arrangement in two-domain enzymes.
We have also found that the two monomers, A and B, of PS are related by a non-crystallographic quasi 2-fold rotational symmetry (NCS) axis. The dimerisation interface has a surface area of 1340 Å 2 and the core of the interface is shown in FIG. 3 . The centre of the nearly symmetrical dimerisation interface is unusual: below a 2-strand β-sheet (βD from A and B) Val109, Met166 and Phe168 form a hydrophobic pocket around weakly H-bonded polar clusters of Ser135, conserved Asn139 and three water molecules, one of which lies on the NCS axis. Above the β-sheet Tyr108, Asp110 and Arg128 form a tight charged cluster, and the rest of the interface consists of salt bridges (His106 to Asp165; Arg11 to Asp169) and extensive water-mediated H-bonding interactions. The average B-factor of monomer B is about 4 Å 2 greater than that of A, which on the whole contains fewer disordered stretches. Also conformational differences between the monomers which can be explained by crystal packing arrangements are found at residues 173-180 and 187-193.
For residues B187-193, electron density was poor, and the apparent backbone connectivity could not be reconciled with stereochemical and Ramachandran constraints. The loop was eventually modelled using the same residues from monomer A (which are well ordered), and transformed by the operation that superimposes domain C of monomer A onto monomer B. However, it is likely that residues A187-193 are only ordered because the bottom of the dimerisation region is crystallographically packed tightly against this region and that the disordered seen in B is more realistic for the apo-enzyme in vivo.
Residues 239-244 also have entirely different but defined backbone conformations in the two monomers, and this difference is not readily explained by crystal packing. However, there appears to be no functional significance in the anomaly.
Solving the PS Crystal Structure
To solve the PS crystal structure, molecular replacement was not possible because prior to our determination of the PS structure similarities between the amino acid sequence of E. coli PS and that of proteins with known structures were not evident. Therefore, phase information needed to be obtained ab initio.
The phase problem was first approached by the Multiple Isomorphous Replacement technique, and crystals of PS were soaked with a range of heavy atom salts at a range of concentrations. However, the majority of these conditions resulted in crystal damage.
Eventually, production of selenomethionine PS (SeMet PS) was attempted, the selenium atoms being introduced into the protein prior to crystallisation by recombinant production of the protein in the presence of L-selenomethionine. This was successfully accomplished and is discussed in more detail below. X-ray analysis was performed on PS and SeMet PS crystals.
1. Production and Purification of PS
Native PS
DNA encoding the PanC gene was engineered into a pUC19 expression vector. E. coil cells were transformed using the plasmid.
Colonies of transformed cells were inoculated directly into LB medium containing ampicillin (100 mg/ml) and IPTG (70 mg/ml); induction of expression was continuous. The cultures were shaken (200 rpm on an orbital shaker) overnight at 37° C., when the cells were retrieved by centrifugation of the culture medium and the cell pellet stored frozen at −80° C.
Selenomethionine PS
The same E. coli strain was used as for native expression, but the methionine pathway inhibition system (see van Duyne et al., J. Mol. Biol ., 229, (1993), 105-124) was used for selenomethionine incorporation. Cells were grown on a minimal, defined medium (see Table 2) containing selenomethionine as well as six other amino acids, whose presence inhibits the natural pathways for methionine synthesis. A starter culture (100 ml) of the same medium as above, but without selenomethionine or the inhibitory amino acids, was inoculated with transformed cells and grown at 37° C. to log growth phase. 1 ml of this culture was used to inoculate baffled 2/Erlemeyer flasks (250 ml complete medium per flask) which were shaken at 37° C. overnight and harvested as for native protein.
Purification
Harvested cells were suspended in 20-40 ml TD buffer (50 mM Tris/HCl pH 7.5±0.1 mM dithiothreitol) sonicated at maximum intensity for 8 times 15 seconds, with 15 second breaks, and cell debris removed by centrifugation (30 minutes, 15000×g).
The supernatant was stirred at 4° C. while (NH 4 ) 2 SO 4 was added slowly over ca. 15 minutes to a final concentration of 29.1% (w/v); after a further 30 minutes of stirring, precipitated contaminants were removed by centrifugation (30 minutes, 15000×g). The solution was dialysed overnight against TD buffer (at least 21).
The dialysed protein solution was loaded at 4° C. onto an anion exchange column (Pharmacia Q-Sepharose, 16/10) and eluted with TD buffer against a NaCl gradient of 0 to 500 mM in 75 minutes, at a flow rate of 5 ml/min. The protein eluted between 0.21 and 0.24M NaCl. The protein-containing fractions were selected from SDS-PAGE analysis, and concentrated to ca 1 ml.
The concentrated fractions were loaded at 4° C. onto a size exclusion column (Pharmacia S200HR), and eluted with TD buffer containing NaCl at 500 mM. The fractions containing PS were confirmed by SDS-PAGE analysis. The fractions were pooled and dialysed overnight against TD buffer (at least 21).
The dialysed protein solution was loaded at room temperature onto an affinity column (Pharmacia Blue Sepharose HiLoad 16/10) and eluted with at least five column volumes of TD buffer containing 10 mM ATP. This effectively eluted all the protein, although this was not monitored directly.
ATP was removed from the eluant by repeated cycles (at least 5) of concentration (in a stirred cell concentrator (Amicon® Ultrafiltration Cell) under pressure in an N 2 atmosphere) and dilution with TD buffer; ATP content was monitored by the UV spectrum (220-300nm) of the solution. The protein was finally concentrated (Ultrafree® concentrator) to a concentration of between 20 and 30 mg/ml. At this concentration, the solution could be aliquoted and frozen directly at −80° C. without damage to the protein.
For the purification of the SeMet protein, some precautions were taken to minimise oxidation of the selenium in the protein. The DTT concentration in all buffers was raised to 5 mM, all buffers were thoroughly purged with N 2 gas before use, and the whole procedure was completed as fast as possible, within two days. The SeMet preparations of PS were subjected to Electrospray Mass Spectrometry (ESMS) to confirm the incorporation of selenomethionine during the expression.
2. Preparation of Crystals
Crystals of PS and SeMet PS were grown using the hanging drop vapour diffusion method. Protein (20 mg/ml) was mixed on a 1:1 ratio with crystallisation solution containing 4-7% (w/w) Polyethylene Glycol 4000 and 50 mM Tris/HCl buffer at pH8. Crystals formed within 2-4 days at 19° C. Crystallisation of SeMet PS, was performed using a nearly identical protocol, but additionally, 2 mM DTT was added to the crystallisation solution before mixing the drop.
Crystals ideally have approximate dimensions of 600×200×50 μm. Under non-optimal conditions, crystals grow in clusters and are generally much thinner in the 3 rd dimension (10-20 μm).
Crystals of PS were cryo-protected using a protocol of gradual soaking in the cryo-protectant, glycerol. A crystal was placed in 20μl of crystallisation solution, and the concentration of glycerol is gradually increased to 28% (v/v) in 4% increments.
3. Structural Determination
Multi-wavelength data sets were collected from a cryo-cooled crystal of SeMet PS, on beam line X-25 of the NSLS at Brookhaven National Laboratories on Long Island, USA. This is a high-flux station with good intensity and wavelength stability. The presence of selenomethionine in the protein was confirmed independently by electrospray mass spectrometry. Before the experiment, a large number of crystals were extensively screened for highest resolution, low mosaicity and low background scatter.
Terminal radiation-induced diffraction decay was evident in the first crystal to be exposed, which influenced data collection from the second, final SeMet crystal.
In addition to the three data sets collected from SeMet crystals, a data set was collected from a large native crystal, which had been established to be nearly isomorphous with the SeMet crystals used. In order to have complete but also high resolution data, the same oscillation range was exposed twice, the first for measuring low resolution data (i.e. short exposures), and the second for the highest resolution possible (long exposures). All data were processed using MOSFLM (Leslie, Joint CCP 4 and EESF - EACMB Newsletter on Protein Crystallography , Vol.26, Daresbury Laboratory, UK) and scaled with SCALA (Collaborative Computational Project 4. The CCP4 Suite: Programs for Protein Crystallography, Acta Crystallographica , D50, (1994), 760-763).
The selenium atoms were located using the program SnB (Weeks et al., J. of Applied Crystallography , 32, (1999), 120-124) and their positions refined using SHARP (LaFortelle et al., Methods in Enzymology , 276, (1997), 472-494 and LaFortelle et al., Maximum Likelihood Refinement in a Graphical environment, with SHARP, in CCP4 study week-end: Recent Advances in Phasing , ed. Wilson et al., Daresbury Laboratory, UK). The final model contained 19 selenium sites which were used to provide initial phasing. Solvent flattening and phase extension techniques were used to produce an interpretable electron density map.
The program O was used for model building. The experimental, solvent flattened electron density map was readily interpretable and secondary structural elements were clearly defined in the electron density bones (calculated with MAPMAN, see Kleywegt et al., Acta Crystallographica , D52, (1996b), 826-828). The main chain of one monomer could be traced nearly continuously, using the secondary structure template building functionality in O, and the selenium atoms identified using SHARP providing guidance for chain-tracing.
The complete main chain model of monomer A was manually rotated to correspond with the bones of the second monomer (B). Since the relative orientation of the two domains was slightly different in monomer B, it was optimised by rigid body refinement (using REFMAC, see Murshudov et al., Acta Crystallographica , D53, (1997), 24-255), keeping separate the two domains (residues 1-176 and 177-283).
The model was improved by three iterated cycles of restrained and individual isotropic maximum likelihood refinement with REFMAC (40-1.7 Å resolution) together with manual rebuilding in 0. σ A -weighted 2F obs −F calc and F obs −F calc maps were used (Read, Acta Crystallographica , A42, (1986), 140-149), the former frequently informative even when contoured at only 0.8-0.9 map standard deviations. For difficult parts of the model, maps and models resulting from simulated annealing in CNS (Brunger et al., Acta Crystallographica , D54, (1998), 905-921) were also considered. Ordered water molecules were modelled by automated cycles of water addition and removal by ARP (Perrakis et al., Acta Crystallographica , D55, (1999), 1765-1770) and refinement by REFMAC, with a final cycle of refinement with bulk solvent correction using CNS to ensure good geometry.
The final model consists of 4290 non-hydrogen protein atoms, and 384 water molecules. All residues were modelled, but electron density was poor for C-terminal residues (A283, B282-3), as well as residues B187-193; the B-factors of these residues are high, approaching 80 Å 2 . Residues A251-259, B63-68 and B251-259, though visible, are also not well ordered and have B-factors approaching 60 Å 2 . Two residues (A4 and A273) have alternative conformations, and 12 surface-exposed side chains are disordered and were modelled as the most common rotamer at zero occupancy.
Table 3 provides model parameters and refinement statistics for a version of the model which is essentially the same as that of Table 1 but contains more water molecules and also two ethanediol molecules and a Tris molecule. Residues B188-192 of this version of the model were reconstructed using BUSTER (Bricogne, Methods in Enzymology , 276, (1997), 361-423) in its implementation with TNT (Tronrud, Methods in Enzymology , 277, (1997), 306-319) instead of by the symmetry operation described above under “PS Structural Characterization”. The program DDQ (van den Akker et al., Acta Crystallographica , D55, (1999), 206-218) was used to assess local and global accuracy and satisfactory completion of refinement, by considering difference density peaks arising from the final model. σ A -weighted difference maps were calculated in REFMAC, excluding water molecules from the model. Quality of the model and its geometry were assessed by OOPS (Kleywegt et al., OOPS-a-daisy, CCP 4 /ESF - EACBM Newsletter on Protein Crystallography , 30, (1994), 20-24), PROCHECK (Laskowski et al., J. Applied Crystallography , 26, (1993), 283-291) and WHATCHECK (Hooft et al., Nature , 381, (1996), 272). No serious deviations from expected values are present, and warnings either correspond to well-defined justifiable features or else poorly-visible features that have high B-factors anyway. There are no Ramachandran outliers, and 92.2% of residues lie in most favoured regions of the plot.
Identification of Likely Active Sites
Having solved the PS crystal structure it is now evident that in terms of their C α coordinates, the ATP-binding domains of (i) class I amino-acid tRNA synthetases (tRS) (i.e. EtRS from Thermus thermophilus , Nureki et al., Science , 267, (1995) 1958-1965; QtRS from E. coli , Perona et al., Biochemistry , 32, (1993) 8758-8771; MtRS from Thermus aquaticus , Mechulam et al., J. of Molecular Biology , 294, (1999), 1287-1297; and YtRS from Bacillus stearothermophilus , Brick et al., J. of Molecular Biology , 208, (1989), 83-98), (ii) phosphopantetheine adenylyltransferase (PPAT) from E. coli (Izard et al., EMBO Journal , 18, (1999), 2021-2030) and (iii) CTP:glycerol-3-phosphate cytidylyltransferase (CGT) from B. subtilis (Weber et al., Structure with Folding and Design , 7, (1999), 1113-1124) are structurally similar to domain N of PS.
More specifically, the particular class of Rossman fold which characterises tRS, CGT and PPAT consists of five β-strands in a central sheet and a cleft between β-strands β1 and β4 at the adenosine-binding site (see FIG. 2 c ). PS also has these features. In addition, in all four cases strand β5 is followed by catalytically important residues which form the KMSKS motif discussed below), and for both PS and tRS strand β5 leads directly into the next domain.
Furthermore, two sequence motifs, HIGH and KMSKS (Barker et al., FEBS Letters , 145, (1982), 191-193), are conserved in tRS proteins and also in the wider superfamily. From mutational studies (First et al., in Biochemistry , 32, (1993), 13644-13663) these motifs are known to be involved in ATP binding: the HIGH motif binds the adenine portion of ATP (cytidine in CGT) and the KMSKS motif stabilises the β- and γ-phosphate groups. These motifs are also found in PS and correspond respectively to residues 34-37 and 185-189.
The location of the bound ATP adenine in the structure of QtRS corresponds to within 2 to 3 Å of the positions of the bound nucleotides in YtRS, PPAT and CGT, i.e. in the cleft between strands β1 and β4 of the Rossman fold and against the top of helix α1 (the location of the HIGH motif). When this domain of QtRS is aligned with domain N of PS the HIGH (actually HDGH in PS) residues line up very well and the QtRS-bound ATP fits nearly perfectly into the same cleft in PS. Despite this excellent match, there is a difference in the positions of the helices ε 10 7 (in PS) and αI (in QtRS) relative to the Rossman domain. This is the location of the KMSKS motif. However, by changing conservatively the φ/φ-angles of residues Val175, Pro176, Ile177 and Met178 which form the PS inter-domain linker main chain, domain C can be rotated sufficiently to align the KMSKS residues with their QtRS counterparts and thus involve them in phosphate binding.
FIG. 4 shows a Connolly surface generated around the proposed PS active site. It opens besides the ATP ribose group and the walls are formed by fully conserved residues, which are largely hydrophobic but include some polar groups. The catalytically essential Mg 2+ ion is shown at its most likely position where it is bound to OG Ser188 , OH Tyr71 , O μ1 ATP and O γ1 ATP . This is also the proposed Mg 2+ binding position in PPAT. Slightly more speculatively, the most favourable conformer of pantoate is shown positioned in a cavity where it appears to satisfy the hydrophobic and hydrogen-bonding interactions of the substrate, as well as being suitably positioned for attack on ATP.
Binding positions for β-alanine may also be proposed, but with less certainty than the binding positions of ATP and pantoate. For example, the β-alanine carboxylate may bind in a conserved, positively charged pocket to Arg123, with Met30, Phe62 and Tyr71 providing a hydrophobic patch to accommodate the two β-alanine methylene groups, and His126 being suitably positioned to deprotonate the NH 3 + group).
Structure-Based Drug Design
Determination of the 3D structure of PS provides important information about the likely active sites of PS, particularly when comparisons are made with similar enzymes. This information may then be used for rational design of PS inhibitors, e.g. by computational techniques which identify possible binding ligands for the active sites, by enabling linked-fragment approaches to drug design, and by enabling the identification and location of bound ligands using X-ray crystallographic analysis. These techniques are discussed in more detail below.
Greer et al. mentioned above describes an iterative approach to ligand design based on repeated sequences of computer modelling, protein-ligand complex formation and X-ray analysis. Thus novel thymidylate synthase inhibitor series were designed de novo by Greer et al., and PS inhibitors may also be designed in the this way. More specifically, using e.g. GRID on the solved 3D structure of PS, a ligand (e.g. a potential inhibitor) for PS may be designed that complements the functionalities of the PS active site(s). The ligand can then be synthesised, formed into a complex with PS, and the complex then analysed by X-ray crystallography to identify the actual position of the bound ligand. The structure and/or functional groups of the ligand can then be adjusted, if necessary, in view of the results of the X-ray analysis, and the synthesis and analysis sequence repeated until an optimised ligand is obtained. Related approaches to structure-based drug design are also discussed in Bohacek et al., Medicinal Research Reviews , Vol.16, (1996), 3-50.
As a result of the determination of the PS 3D structure, more purely computational techniques for rational drug design may also be used to design PS inhibitors (for an overview of these techniques see e.g. Walters et al. mentioned above). For example, automated ligand-receptor docking programs (discussed e.g. by Jones et al. in Current Opinion in Biotechnology , Vol.6, (1995), 652-656) which require accurate information on the atomic coordinates of target receptors may be used to design potential PS inhibitors.
Linked-fragment approaches to drug design also require accurate information on the atomic coordinates of target receptors. The basic idea behind these approaches is to determine (computationally or experimentally) the binding locations of plural ligands to a target molecule, and then construct a molecular scaffold to connect the ligands together in such a way that their relative binding positions are preserved. The connected ligands thus form a potential lead compound that can be further refined using e.g. the iterative technique of Greer et al. For a virtual linked-fragment approach see Verlinde et al., J. of Computer - Aided Molecular Design , 6, (1992), 131-147, and for NMR and X-ray approaches see Shuker et al., Science , 274, (1996), 1531-1534 and Stout et al., Structure , 6, (1998), 839-848. The use of these approaches to design PS inhibitors is made possible by the determination of the PS structure.
Many of the techniques and approaches to structure-based drug design described above rely at some stage on X-ray analysis to identify the binding position of a ligand in a ligand-protein complex. A common way of doing this is to perform X-ray crystallography on the complex, produce a difference Fourier electron density map, and associate a particular pattern of electron density with the ligand. However, in order to produce the map (as explained e.g. by Blundell et al. mentioned above) it is necessary to know beforehand the protein 3D structure (or at least the protein structure factors). Therefore, determination of the PS structure also allows difference Fourier electron density maps of PS-ligand complexes to be produced, which can greatly assist the process of rational drug design.
The approaches to structure-based drug design described above all require initial identification of possible compounds for interaction with target bio-molecule (in this case PS). Sometimes these compounds are known e.g. from the research literature. However, when they are not, or when novel compounds are wanted, a first stage of the drug design program may involve computer-based in silico screening of compound databases (such as the Cambridge Structural Database) with the aim of identifying compounds which interact with the active site or sites of the target bio-molecule. Screening selection criteria may be based on pharmacokinetic properties such as metabolic stability and toxicity. However, determination of the PS structure allows the architecture and chemical nature of each PS active site to be identified, which in turn allows the geometric and functional constraints of a descriptor for the potential inhibitor to be derived. The descriptor is, therefore, a type of virtual 3-D pharmacophore, which can also be used as selection criteria or filter for database screening.
While the invention has been described in conjunction with the exemplary embodiments described above, many equivalent modifications and variations will be apparent to those skilled in the art when given this disclosure. Accordingly, the exemplary embodiments of the invention set forth are considered to be illustrative and not limiting. Various changes to the described embodiments may be made without departing from the spirit and scope of the invention.
References
The references listed below are incorporated by reference.
Barker et al., FEBS Letters , 145, (1982), 191-193.
Bohacek et al., Medicinal Research Reviews , Vol.16, (1996), 3-50.
Brick et al., J. of Molecular Biology , 208, (1989), 83-98.
Bricogne, Methods in Enzymology , 276, (1997), 361-423.
Brunger et al., Acta Crystallographica , D54, (1998), 905-921.
Blundell et al., in Protein Crystallography , Academic Press, New York, London and San Francisco, (1976).
Collaborative Computational Project 4. The CCP4 Suite: Programs for Protein Crystallography, Acta Crystallographica , D50, (1994), 760-763.
Dunbrack et al., Folding and Design , 2, (1997), 27-42.
First et al., in Biochemistry , 32, (1993), 13644-13663.
Goodford, J. Med. Chem ., 28, (1985), 849-857.
Greer et al., J. of Medicinal Chemistry , Vol. 37, (1994), 1035-1054.
Hooft et al., Nature , 381, (1996), 272.
Izard et al., EMBO Journal , 18, (1999), 2021-2030.
Jones et al., Acta Crystallograhy , A47, (1991), 110-119.
Jones et al. in Current Opinion in Biotechnology , Vol.6, (1995), 652-656.
Kleywegt et al., OOPS-a-daisy, CCP 4 /ESF - EACBM Newsletter on Protein Crystallography , 30, (1994), 20-24.
Kleywegt et al., Acta Crystallographica , D52, (1996b), 826-828.
LaFortelle et al., Methods in Enzymology , 276, (1997), 472-494.
LaFortelle et al., Maximum Likelihood Refinement in a Graphical environment, with SHARP, in CCP4 study week-end: Recent Advances in Phasing , ed. Wilson et al., Daresbury Laboratory, UK.
Leslie, Joint CCP 4 and EESF - EACMB Newsletter on Protein Crystallography , Vol.26, Daresbury Laboratory, UK.
Laskowski et al., J. Applied Crystallography , 26, (1993), 283-291.
Mechulam et al., J. of Molecular Biology , 294, (1999), 1287-1297.
Miyatake et. al, J. Biochem ., 79, (1976), 673-678.
Murshudov et al., Acta Crystallographica , D53, (1997), 24-255.
Nureki et al., Science , 267, (1995) 1958-1965.
Perona et al., Biochemistry , 32, (1993) 8758-8771.
Perrakis et al., Acta Crystallographica , D55, (1999), 1765-1770.
Read, Acta Crystallographica, A42, (1986), 140-149.
Sayle et al., TIBS , Vol. 20, (1995), 374.
Shuker et al., Science , 274, (1996), 1531-1534.
Stout et al., Structure , 6, (1998), 839-848.
Tronrud, Methods in Enzymology , 277, (1997), 306-319. van den Akker et al., Acta Crystallographica , D55, (1999), 206-218.
van Duyne et al., J. Mol. Biol ., 229, (1993), 105-124.
Verlinde et al., J. of Computer - Aided Molecular Design , 6, (1992), 131-147.
Walters et al., Drug Discovery Today , Vol.3, No.4, (1998), 160-178.
Weber et al., Structure with Folding and Design , 7, (1999), 1113-1124.
Weeks et al., J. of Applied Crystallography , 32, (1999), 120-124.
TABLE 1
REMARK Written by O version 6.2.1
REMARK Sun Dec 19 17:28:32 1999
CRYST1/ 66.031 78.075 77.126 90.00 103.71 90.00
ORIGX1
1.000000
0.000000
0.000000
0.00000
ORIGX2
0.000000
1.000000
0.000000
0.00000
ORIGX3
0.000000
0.000000
1.000000
0.00000
SCALE1
0.015144
0.000000
0.003694
0.00000
SCALE2
0.000000
0.012808
0.000000
0.00000
SCALE3
0.000000
0.000000
0.013346
0.00000
Atom
Atomic
type
X
Y
Z
Occ.
B
No.
Monomer A
ATOM
1
N
MET
A
1
21.480
5.652
9.350
1.00
40.77
7
ATOM
2
CA
MET
A
1
22.828
6.214
9.115
1.00
37.51
6
ATOM
3
C
MET
A
1
23.471
6.721
10.394
1.00
37.12
6
ATOM
4
O
MET
A
1
22.954
7.659
10.999
1.00
37.52
8
ATOM
5
CB
MET
A
1
22.777
7.385
8.130
1.00
35.78
6
ATOM
6
CG
MET
A
1
24.222
7.748
7.741
1.00
33.60
6
ATOM
7
SD
MET
A
1
24.158
8.882
6.335
1.00
30.36
16
ATOM
8
CE
MET
A
1
23.874
10.429
7.197
1.00
27.91
6
ATOM
9
N
LEU
A
2
24.565
6.125
10.835
1.00
33.76
7
ATOM
10
CA
LEU
A
2
25.238
6.573
12.014
1.00
33.24
6
ATOM
11
C
LEU
A
2
26.150
7.745
11.696
1.00
32.31
6
ATOM
12
O
LEU
A
2
26.856
7.637
10.679
1.00
31.54
8
ATOM
13
CB
LEU
A
2
26.138
5.467
12.571
1.00
36.11
6
ATOM
14
CG
LEU
A
2
25.578
4.098
12.886
1.00
40.23
6
ATOM
15
CD1
LEU
A
2
26.741
3.164
13.253
1.00
39.01
6
ATOM
16
CD2
LEU
A
2
24.566
4.121
14.018
1.00
40.87
6
ATOM
17
N
ILE
A
3
26.233
8.778
12.481
1.00
30.54
7
ATOM
18
CA
ILE
A
3
27.148
9.869
12.303
1.00
30.81
6
ATOM
19
C
ILE
A
3
28.090
9.801
13.509
1.00
31.50
6
ATOM
20
O
ILE
A
3
27.616
9.918
14.642
1.00
31.89
8
ATOM
21
CB
ILE
A
3
26.523
11.280
12.249
1.00
31.52
6
ATOM
22
CG1
ILE
A
3
25.579
11.383
11.041
1.00
34.35
6
ATOM
23
CG2
ILE
A
3
27.610
12.348
12.227
1.00
33.27
6
ATOM
24
CD1
ILE
A
3
24.913
12.769
11.018
1.00
34.98
6
ATOM
25
N
ILE
A
4
29.350
9.493
13.296
1.00
26.66
7
ATOM
26
CA
ILE
A
4
30.352
9.345
14.340
1.00
27.86
6
ATOM
27
C
ILE
A
4
31.314
10.510
14.337
1.00
28.36
6
ATOM
28
O
ILE
A
4
31.896
10.956
13.322
1.00
26.38
8
ATOM
29
CB
ILE
A
4
31.105
7.998
14.143
1.00
27.57
6
ATOM
30
CG1
ILE
A
4
30.125
6.847
13.972
0.50
27.40
6
ATOM
31
CG2
ILE
A
4
32.067
7.779
15.312
0.50
26.53
6
ATOM
32
CD1
ILE
A
4
29.201
6.526
15.113
0.50
28.00
6
ATOM
33
N
GLU
A
5
31.633
11.053
15.537
1.00
25.12
7
ATOM
34
CA
GLU
A
5
32.526
12.186
15.655
1.00
28.91
6
ATOM
35
C
GLU
A
5
33.843
11.934
16.357
1.00
26.18
6
ATOM
36
O
GLU
A
5
34.724
12.779
16.300
1.00
27.45
8
ATOM
37
CB
GLU
A
5
31.769
13.303
16.441
1.00
31.10
6
ATOM
38
CG
GLU
A
5
30.611
13.871
15.627
1.00
34.62
6
ATOM
39
CD
GLU
A
5
29.795
14.929
16.355
1.00
40.38
6
ATOM
40
OE1
GLU
A
5
30.263
15.579
17.306
1.00
41.78
8
ATOM
41
OE2
GLU
A
5
28.625
15.153
15.971
1.00
43.11
8
ATOM
42
N
THR
A
6
33.976
10.823
17.094
1.00
27.41
7
ATOM
43
CA
THR
A
6
35.188
10.587
17.848
1.00
27.21
6
ATOM
44
C
THR
A
6
35.969
9.345
17.384
1.00
26.94
6
ATOM
45
O
THR
A
6
35.294
8.397
16.960
1.00
25.74
8
ATOM
46
CB
THR
A
6
34.867
10.400
19.351
1.00
29.81
6
ATOM
47
OG1
THR
A
6
34.175
9.170
19.608
1.00
30.13
8
ATOM
48
CG2
THR
A
6
33.967
11.528
19.852
1.00
29.59
6
ATOM
49
N
LEU
A
7
37.249
9.359
17.679
1.00
27.76
7
ATOM
50
CA
LEU
A
7
38.052
8.175
17.280
1.00
27.99
6
ATOM
51
C
LEU
A
7
37.684
6.899
18.006
1.00
29.61
6
ATOM
52
O
LEU
A
7
37.546
5.845
17.381
1.00
26.94
8
ATOM
53
CB
LEU
A
7
39.526
8.515
17.460
1.00
28.02
6
ATOM
54
CG
LEU
A
7
40.011
9.725
16.678
1.00
31.71
6
ATOM
55
CD1
LEU
A
7
41.523
9.840
16.799
1.00
34.04
6
ATOM
56
CD2
LEU
A
7
39.612
9.641
15.219
1.00
32.76
6
ATOM
57
N
PRO
A
8
37.434
6.913
19.313
1.00
30.58
7
ATOM
58
CA
PRO
A
8
37.081
5.687
20.013
1.00
29.86
6
ATOM
59
C
PRO
A
8
35.814
5.062
19.505
1.00
28.23
6
ATOM
60
O
PRO
A
8
35.701
3.845
19.394
1.00
25.90
8
ATOM
61
CB
PRO
A
8
37.001
6.107
21.485
1.00
31.83
6
ATOM
62
CG
PRO
A
8
37.816
7.345
21.593
1.00
31.44
6
ATOM
63
CD
PRO
A
8
37.601
8.053
20.243
1.00
30.62
6
ATOM
64
N
LEU
A
9
34.754
5.838
19.239
1.00
27.49
7
ATOM
65
CA
LEU
A
9
33.489
5.349
18.746
1.00
28.03
6
ATOM
66
C
LEU
A
9
33.625
4.896
17.281
1.00
25.69
6
ATOM
67
O
LEU
A
9
32.960
3.907
16.978
1.00
26.00
8
ATOM
68
CB
LEU
A
9
32.376
6.393
18.920
1.00
31.67
6
ATOM
69
CG
LEU
A
9
32.089
6.741
20.400
1.00
35.64
6
ATOM
70
CD1
LEU
A
9
31.037
7.824
20.573
1.00
35.73
6
ATOM
71
CD2
LEU
A
9
31.636
5.493
21.154
1.00
37.26
6
ATOM
72
N
LEU
A
10
34.532
5.512
16.526
1.00
25.45
7
ATOM
73
CA
LEU
A
10
34.763
5.045
15.154
1.00
23.19
6
ATOM
74
C
LEU
A
18
35.461
3.678
15.228
1.00
23.87
6
ATOM
75
O
LEU
A
10
35.017
2.730
14.592
1.00
23.85
8
ATOM
76
CB
LEU
A
10
35.577
6.082
14.350
1.00
21.87
6
ATOM
77
CG
LEU
A
10
36.012
5.560
12.953
1.00
22.51
6
ATOM
78
CD1
LEU
A
10
34.829
5.397
12.007
1.00
22.75
6
ATOM
79
CD2
LEU
A
10
37.072
6.488
12.337
1.00
23.02
6
ATOM
80
N
ARG
A
11
36.423
3.571
16.150
1.00
25.14
7
ATOM
81
CA
ARG
A
11
37.191
2.304
16.232
1.00
28.37
6
ATOM
82
C
ARG
A
11
36.236
1.209
16.642
1.00
29.20
6
ATOM
83
O
ARG
A
11
36.288
0.113
16.066
1.00
27.74
8
ATOM
84
CB
ARG
A
11
38.399
2.556
17.142
1.00
31.48
6
ATOM
85
CG
ARG
A
11
39.141
1.279
17.544
1.00
36.42
6
ATOM
86
CD
ARG
A
11
40.384
1.586
18.401
1.00
40.76
6
ATOM
87
NE
ARG
A
11
40.948
0.327
18.857
1.00
44.29
7
ATOM
88
CZ
ARG
A
11
40.627
−0.524
19.819
1.00
45.48
6
ATOM
89
NH1
ARG
A
11
39.610
−0.297
20.644
1.00
47.34
7
ATOM
90
NH2
ARG
A
11
41.306
−1.656
20.008
1.00
45.04
7
ATOM
91
N
GLN
A
12
35.347
1.474
17.591
1.00
26.32
7
ATOM
92
CA
GLN
A
12
34.364
0.453
17.968
1.00
28.52
6
ATOM
93
C
GLN
A
12
33.550
−0.050
16.798
1.00
27.48
6
ATOM
94
O
GLN
A
12
33.340
−1.248
16.579
1.00
25.61
8
ATOM
95
CB
GLN
A
12
33.450
1.032
19.051
1.00
30.81
6
ATOM
96
CG
GLN
A
12
32.364
0.022
19.483
1.00
34.43
6
ATOM
97
CD
GLN
A
12
31.513
0.662
20.570
1.00
37.80
6
ATOM
98
OE1
GLN
A
12
31.804
0.354
21.743
1.00
43.75
8
ATOM
99
NE2
GLN
A
12
30.545
1.495
20.293
1.00
38.11
7
ATOM
100
N
GLN
A
13
32.938
0.879
16.025
1.00
25.56
7
ATOM
101
CA
GLN
A
13
32.110
0.497
14.901
1.00
24.82
6
ATOM
102
C
GLN
A
13
32.889
−0.235
13.804
1.00
23.46
6
ATOM
103
O
GLN
A
13
32.360
−1.209
13.326
1.00
24.23
8
ATOM
104
CB
GLN
A
13
31.427
1.706
14.213
1.00
28.90
6
ATOM
105
CG
GLN
A
13
30.471
2.397
15.154
1.00
34.73
6
ATOM
106
CD
GLN
A
13
29.201
1.611
15.405
1.00
37.69
6
ATOM
107
OE1
GLN
A
13
28.697
0.913
14.519
1.00
40.12
8
ATOM
108
NE2
GLN
A
13
28.765
1.760
16.646
1.00
39.64
7
ATOM
109
N
ILE
A
14
34.075
0.258
13.493
1.00
21.48
7
ATOM
110
CA
ILE
A
14
34.904
−0.413
12.482
1.00
23.36
6
ATOM
111
C
ILE
A
14
35.252
−1.833
12.978
1.00
23.78
6
ATOM
112
O
ILE
A
14
35.100
−2.754
12.163
1.00
24.98
8
ATOM
113
CB
ILE
A
14
36.157
0.388
12.154
1.00
24.05
6
ATOM
114
CG1
ILE
A
14
35.752
1.756
11.492
1.00
23.68
6
ATOM
115
CG2
ILE
A
14
37.152
−0.372
11.258
1.00
23.44
6
ATOM
116
CD1
ILE
A
14
34.981
1.571
10.185
1.00
22.33
6
ATOM
117
N
ARG
A
15
35.691
−1.946
14.210
1.00
24.68
7
ATOM
118
CA
ARG
A
15
36.062
−3.331
14.658
1.00
24.36
6
ATOM
119
C
ARG
A
15
34.868
−4.230
14.500
1.00
24.62
6
ATOM
120
O
ARG
A
15
34.925
−5.358
13.991
1.00
26.61
8
ATOM
121
CB
ARG
A
15
36.618
−3.304
16.087
1.00
24.77
6
ATOM
122
CG
ARG
A
15
38.037
−2.760
16.169
1.00
29.78
6
ATOM
123
CD
ARG
A
15
38.488
−2.556
17.609
1.00
31.54
6
ATOM
124
NE
ARG
A
15
38.632
−3.872
18.241
1.00
34.58
7
ATOM
125
CZ
ARG
A
15
39.603
−4.741
17.996
1.00
36.36
6
ATOM
126
NH1
ARG
A
15
48.588
−4.484
17.142
1.00
37.87
7
ATOM
127
NH2
ARG
A
15
39.609
−5.896
18.638
1.00
37.41
7
ATOM
128
N
ARG
A
16
33.681
−3.788
14.925
1.00
23.16
7
ATOM
129
CA
ARG
A
16
32.495
−4.643
14.843
1.00
24.97
6
ATOM
130
C
ARG
A
16
32.091
−5.007
13.453
1.00
26.58
6
ATOM
131
O
ARG
A
16
31.688
−6.112
13.134
1.00
25.54
8
ATOM
132
CB
ARG
A
16
31.335
−3.905
15.565
1.00
26.81
6
ATOM
133
CG
ARG
A
16
31.739
−3.858
17.037
1.00
30.82
6
ATOM
134
CD
ARG
A
16
30.609
−3.393
17.953
1.00
35.27
6
ATOM
135
NE
ARG
A
16
31.145
−3.440
19.331
1.00
38.72
7
ATOM
136
CZ
ARG
A
16
30.380
−3.407
20.431
1.00
41.50
6
ATOM
137
NH1
ARG
A
16
29.057
−3.350
20.279
1.00
41.64
7
ATOM
138
NH2
ARG
A
16
30.986
−3.478
21.616
1.00
40.81
7
ATOM
139
N
LEU
A
17
32.236
−4.016
12.503
1.00
25.60
7
ATOM
140
CA
LEU
A
17
31.869
−4.342
11.148
1.00
25.51
6
ATOM
141
C
LEU
A
17
32.796
−5.382
10.547
1.00
25.77
6
ATOM
142
O
LEU
A
17
32.287
−6.296
9.882
1.00
27.72
8
ATOM
143
CB
LEU
A
17
31.929
−3.067
10.251
1.00
26.53
6
ATOM
144
CG
LEU
A
17
30.763
−2.131
10.574
1.00
28.03
6
ATOM
145
CD1
LEU
A
17
31.127
−0.707
10.125
1.00
29.84
6
ATOM
146
CD2
LEU
A
17
29.455
−2.554
9.941
1.00
30.48
6
ATOM
147
N
ARG
A
18
34.062
−5.187
10.811
1.00
25.72
7
ATOM
148
CA
ARG
A
18
35.021
−6.172
10.278
1.00
26.50
6
ATOM
149
C
ARG
A
18
34.894
−7.544
10.989
1.00
27.79
6
ATOM
150
O
ARG
A
18
34.993
−8.564
10.329
1.00
26.32
8
ATOM
151
CB
ARG
A
18
36.436
−5.665
10.405
1.00
28.86
6
ATOM
152
CG
ARG
A
18
36.506
−4.291
9.685
1.00
31.17
6
ATOM
153
CD
ARG
A
18
37.972
−4.010
9.471
1.00
36.04
6
ATOM
154
NE
ARG
A
18
38.502
−4.834
8.364
1.00
39.73
7
ATOM
155
CZ
ARG
A
18
39.788
−5.197
8.409
1.00
41.34
6
ATOM
156
NH1
ARG
A
18
40.523
−4.806
9.456
1.00
42.67
7
ATOM
157
NH2
ARG
A
18
40.324
−5.921
7.432
1.00
41.84
7
ATOM
158
N
MET
A
19
34.537
−7.458
12.259
1.00
25.78
7
ATOM
159
CA
MET
A
19
34.344
−8.735
13.010
1.00
27.53
6
ATOM
160
C
MET
A
19
33.230
−9.524
12.371
1.00
26.64
6
ATOM
161
O
MET
A
19
33.236
−10.747
12.181
1.00
25.81
8
ATOM
162
CB
MET
A
19
34.097
−8.377
14.473
1.00
24.76
6
ATOM
163
CG
MET
A
19
33.680
−9.547
15.350
1.00
26.87
6
ATOM
164
SD
MET
A
19
31.960
−10.075
15.286
1.00
24.59
16
ATOM
165
CE
MET
A
19
31.123
−8.581
15.796
1.00
28.15
6
ATOM
166
N
GLU
A
20
32.202
−8.844
11.855
1.00
28.38
7
ATOM
167
CA
GLU
A
20
31.083
−9.471
11.156
1.00
28.35
6
ATOM
168
C
GLU
A
20
31.345
−9.875
9.720
1.00
31.76
6
ATOM
169
O
GLU
A
20
30.395
−10.362
9.077
1.00
32.53
8
ATOM
170
CB
GLU
A
20
29.874
−8.502
11.103
1.00
30.90
6
ATOM
171
CG
GLU
A
20
29.474
−8.103
12.493
1.00
31.14
6
ATOM
172
N
GLY
A
21
32.531
−9.676
9.217
1.00
29.46
7
ATOM
173
CA
GLY
A
21
32.968
−10.045
7.901
1.00
30.44
6
ATOM
174
C
GLY
A
21
32.503
−9.016
6.844
1.00
28.10
6
ATOM
175
O
GLY
A
21
32.465
−9.457
5.705
1.00
30.38
8
ATOM
176
N
LYS
A
22
32.195
−7.815
7.269
1.00
27.01
7
ATOM
177
CA
LYS
A
22
31.684
−6.909
6.184
1.00
26.80
6
ATOM
178
C
LYS
A
22
32.855
−6.293
5.441
1.00
26.41
6
ATOM
179
O
LYS
A
22
33.844
−5.944
6.097
1.00
27.41
8
ATOM
180
CB
LYS
A
22
30.773
−5.883
6.825
1.00
27.50
6
ATOM
181
CG
LYS
A
22
29.392
−6.529
7.152
1.00
32.21
6
ATOM
182
CD
LYS
A
22
28.721
−5.570
8.118
1.00
37.87
6
ATOM
183
CE
LYS
A
22
27.207
−5.752
8.159
1.00
42.38
6
ATOM
184
NZ
LYS
A
22
26.574
−4.400
8.447
1.00
46.00
7
ATOM
185
N
ARG
A
23
32.737
−6.159
4.128
1.00
26.60
7
ATOM
186
CA
ARG
A
23
33.781
−5.503
3.325
1.00
27.62
6
ATOM
187
C
ARG
A
23
33.468
−4.008
3.350
1.00
25.54
6
ATOM
188
O
ARG
A
23
32.293
−3.677
3.209
1.00
25.62
8
ATOM
189
CB
ARG
A
23
33.784
−6.101
1.934
1.00
31.46
6
ATOM
190
CG
ARG
A
23
34.506
−5.433
0.801
1.00
39.27
6
ATOM
191
CD
ARG
A
23
34.206
−5.965
−0.610
1.00
43.15
6
ATOM
192
NE
ARG
A
23
35.366
−5.731
−1.466
1.00
45.63
7
ATOM
193
CZ
ARG
A
23
36.577
−6.268
−1.262
1.00
46.18
6
ATOM
194
NH1
ARG
A
23
36.841
−7.101
−0.272
1.00
47.31
7
ATOM
195
NH2
ARG
A
23
37.537
−5.954
−2.117
1.00
48.28
7
ATOM
196
N
VAL
A
24
34.412
−3.165
3.697
1.00
23.62
7
ATOM
197
CA
VAL
A
24
34.196
−1.743
3.900
1.00
22.06
6
ATOM
198
C
VAL
A
24
34.785
−0.891
2.782
1.00
17.49
6
ATOM
199
O
VAL
A
24
35.924
−1.166
2.392
1.00
18.13
8
ATOM
200
CB
VAL
A
24
34.830
−1.279
5.218
1.00
22.91
6
ATOM
201
CG1
VAL
A
24
34.677
0.198
5.452
1.00
24.86
6
ATOM
202
CG2
VAL
A
24
34.173
−2.010
6.405
1.00
24.10
6
ATOM
203
N
ALA
A
25
34.023
0.099
2.315
1.00
17.82
7
ATOM
204
CA
ALA
A
25
34.597
0.939
1.279
1.00
18.16
6
ATOM
205
C
ALA
A
25
34.593
2.272
2.004
1.00
18.48
6
ATOM
206
O
ALA
A
25
33.673
2.667
2.768
1.00
22.08
8
ATOM
207
CB
ALA
A
25
33.863
1.032
−0.030
1.00
20.30
6
ATOM
208
N
LEU
A
26
35.579
3.142
1.726
1.00
16.71
7
ATOM
209
CA
LEU
A
26
35.791
4.438
2.266
1.00
16.65
6
ATOM
210
C
LEU
A
26
35.819
5.507
1.152
1.00
17.57
6
ATOM
211
O
LEU
A
26
36.497
5.321
0.146
1.00
18.90
8
ATOM
212
CB
LEU
A
26
37.120
4.628
3.038
1.00
18.22
6
ATOM
213
CG
LEU
A
26
37.458
6.066
3.461
1.00
18.69
6
ATOM
214
CD1
LEU
A
26
36.500
6.657
4.511
1.00
20.43
6
ATOM
215
CD2
LEU
A
26
38.B87
6.061
4.006
1.00
20.45
6
ATOM
216
N
VAL
A
27
35.065
6.569
1.318
1.00
16.54
7
ATOM
217
CA
VAL
A
27
35.028
7.712
0.418
1.00
16.69
6
ATOM
218
C
VAL
A
27
35.493
8.915
1.208
1.00
15.96
6
ATOM
219
O
VAL
A
27
34.643
9.495
1.891
1.00
17.62
8
ATOM
220
CB
VAL
A
27
33.636
8.038
−0.196
1.00
18.00
6
ATOM
221
CG1
VAL
A
27
33.738
9.238
−1.157
1.00
21.63
6
ATOM
222
CG2
VAL
A
27
33.057
6.801
−0.869
1.00
20.05
6
ATOM
223
N
PRO
A
28
36.728
9.403
1.100
1.00
18.63
7
ATOM
224
CA
PRO
A
28
37.265
10.543
1.776
1.00
19.42
6
ATOM
225
C
PRO
A
28
36.814
11.864
1.198
1.00
20.36
6
ATOM
226
O
PRO
A
28
36.941
11.994
−0.024
1.00
21.38
8
ATOM
227
CB
PRO
A
28
38.775
10.466
1.589
1.00
23.04
6
ATOM
228
CG
PRO
A
28
39.036
9.147
0.945
1.00
23.71
6
ATOM
229
CD
PRO
A
28
37.765
8.641
0.309
1.00
19.69
6
ATOM
230
N
THR
A
29
36.209
12.765
1.957
1.00
20.05
7
ATOM
231
CA
THR
A
29
35.752
14.046
1.426
1.00
20.41
6
ATOM
232
C
THR
A
29
36.036
15.159
2.439
1.00
18.55
6
ATOM
233
O
THR
A
29
36.271
14.922
3.618
1.00
19.34
8
ATOM
234
CB
THR
A
29
34.254
14.069
1.053
1.00
21.16
6
ATOM
235
OG1
THR
A
29
33.512
14.439
2.242
1.00
19.82
8
ATOM
236
CG2
THR
A
29
33.658
12.762
0.537
1.00
20.33
6
ATOM
237
N
MET
A
30
35.897
16.391
2.003
1.00
20.47
7
ATOM
238
CA
MET
A
30
35.998
17.616
2.811
1.00
20.82
6
ATOM
239
C
MET
A
30
34.587
18.281
2.815
1.00
23.33
6
ATOM
240
O
MET
A
30
34.465
19.488
3.115
1.00
23.42
8
ATOM
241
CB
MET
A
30
37.065
18.623
2.375
1.00
21.06
6
ATOM
242
CG
MET
A
30
38.446
17.925
2.357
1.00
21.02
6
ATOM
243
SD
MET
A
30
39.740
19.108
2.816
1.00
24.24
16
ATOM
244
CE
MET
A
30
39.431
20.461
1.687
1.00
26.95
6
ATOM
245
N
GLY
A
31
33.576
17.477
2.616
1.00
21.21
7
ATOM
246
CA
GLY
A
31
32.189
17.985
2.705
1.00
24.38
6
ATOM
247
C
GLY
A
31
31.835
18.946
1.563
1.00
24.71
6
ATOM
248
O
GLY
A
31
32.498
18.909
0.524
1.00
22.94
8
ATOM
249
N
ASN
A
32
30.712
19.650
1.637
1.00
24.08
7
ATOM
250
CA
ASN
A
32
30.269
20.550
0.552
1.00
22.88
6
ATOM
251
C
ASN
A
32
29.995
19.636
−0.655
1.00
22.70
6
ATOM
252
O
ASN
A
32
30.519
19.801
−1.762
1.00
25.35
8
ATOM
253
CB
ASN
A
32
31.269
21.654
0.253
1.00
27.38
6
ATOM
254
CG
ASN
A
32
30.612
22.708
−0.658
1.00
31.01
6
ATOM
255
OD1
ASN
A
32
29.390
22.842
−0.531
1.00
33.26
8
ATOM
256
ND2
ASN
A
32
31.392
23.283
−1.538
1.00
31.51
7
ATOM
257
N
LEU
A
33
29.250
18.551
−0.428
1.00
22.17
7
ATOM
258
CA
LEU
A
33
29.111
17.438
−1.343
1.00
20.92
6
ATOM
259
C
LEU
A
33
28.300
17.796
−2.594
1.00
23.49
6
ATOM
260
O
LEU
A
33
27.325
18.519
−2.397
1.00
25.06
8
ATOM
261
CB
LEU
A
33
28.479
16.200
−0.668
1.00
21.06
6
ATOM
262
CG
LEU
A
33
29.372
15.713
0.501
1.00
21.76
6
ATOM
263
CD1
LEU
A
33
28.821
14.431
1.108
1.00
24.92
6
ATOM
264
CD2
LEU
A
33
30.834
15.495
0.073
1.00
21.13
6
ATOM
265
N
HIS
A
34
28.691
17.217
−3.706
1.00
21.31
7
ATOM
266
CA
HIS
A
34
27.929
17.454
−4.953
1.00
19.68
6
ATOM
267
C
HIS
A
34
27.793
16.165
−5.698
1.00
21.69
6
ATOM
268
O
HIS
A
34
28.073
15.035
−5.218
1.00
21.01
8
ATOM
269
CB
HIS
A
34
28.648
18.575
−5.722
1.00
20.00
6
ATOM
270
CG
HIS
A
34
30.062
18.267
−6.078
1.00
23.69
6
ATOM
271
ND1
HIS
A
34
30.449
17.170
−6.770
1.00
26.07
7
ATOM
272
CD2
HIS
A
34
31.211
18.953
−5.778
1.00
26.19
6
ATOM
273
CE1
HIS
A
34
31.776
17.161
−6.890
1.00
27.03
6
ATOM
274
NE2
HIS
A
34
32.262
18.221
−6.296
1.00
27.65
7
ATOM
275
N
ASP
A
35
27.277
16.218
−6.957
1.00
20.96
7
ATOM
276
CA
ASP
A
35
26.992
15.008
−7.685
1.00
21.21
6
ATOM
277
C
ASP
A
35
28.213
14.132
−7.962
1.00
20.16
6
ATOM
278
O
ASP
A
35
28.006
12.921
−8.079
1.00
22.17
8
ATOM
279
CB
ASP
A
35
26.386
15.393
−9.061
1.00
23.09
6
ATON
280
CG
ASP
A
35
24.959
15.842
−8.957
1.00
26.28
6
ATOM
281
OD1
ASP
A
35
24.273
15.662
−7.929
1.00
27.10
8
ATOM
282
OD2
ASP
A
35
24.439
16.326
−10.018
1.00
25.60
8
ATOM
283
N
GLY
A
36
29.375
14.766
−8.056
1.00
21.98
7
ATOM
284
CA
GLY
A
36
30.620
14.030
−8.244
1.00
21.77
6
ATOM
285
C
GLY
A
36
30.786
13.041
−7.065
1.00
22.77
6
ATOM
286
O
GLY
A
36
31.157
11.870
−7.245
1.00
22.33
8
ATOM
287
N
HIS
A
37
30.620
13.573
−5.849
1.00
22.48
7
ATOM
288
CA
HIS
A
37
30.753
12.759
−4.642
1.00
19.90
6
ATOM
289
C
HIS
A
37
29.688
11.715
−4.564
1.00
20.48
6
ATOM
290
O
HIS
A
37
29.886
10.568
−4.111
1.00
20.51
8
ATOM
291
CB
HIS
A
37
30.659
13.645
−3.371
1.00
20.77
6
ATOM
292
CG
HIS
A
37
31.604
14.773
−3.310
1.00
23.28
6
ATOM
293
ND1
HIS
A
37
32.947
14.667
−2.929
1.00
28.53
7
ATOM
294
CD2
HIS
A
37
31.407
16.089
−3.544
1.00
19.82
6
ATOM
295
CE1
HIS
A
37
33.536
15.843
−2.870
1.00
23.53
6
ATOM
296
NE2
HIS
A
37
32.585
16.736
−3.250
1.00
26.84
7
ATOM
297
N
MET
A
38
28.469
11.976
−5.080
1.00
19.18
7
ATOM
298
CA
MET
A
38
27.409
10.961
−5.035
1.00
19.76
6
ATOM
299
C
MET
A
38
27.795
9.798
−5.955
1.00
22.39
6
ATOM
300
O
MET
A
38
27.476
8.670
−5.614
1.00
21.94
8
ATOM
301
CB
MET
A
38
26.038
11.520
−5.422
1.00
23.14
6
ATOM
302
CG
MET
A
38
25.482
12.594
−4.447
1.00
25.87
6
ATOM
303
SD
MET
A
38
25.332
11.996
−2.726
1.00
28.93
16
ATOM
304
CE
MET
A
38
26.690
12.846
−1.980
1.00
25.74
6
ATOM
305
N
LYS
A
39
28.493
10.034
−7.069
1.00
19.54
7
ATOM
306
CA
LYS
A
39
28.943
8.945
−7.921
1.00
21.23
6
ATOM
307
C
LYS
A
39
29.995
8.090
−7.205
1.00
19.48
6
ATOM
308
O
LYS
A
39
29.947
6.878
−7.283
1.00
19.63
8
ATOM
309
CB
LYS
A
39
29.524
9.474
−9.236
1.00
23.04
6
ATOM
310
CG
LYS
A
39
29.977
8.354
−10.200
1.00
23.73
6
ATOM
311
CD
LYS
A
39
28.831
7.464
−10.663
1.00
29.69
6
ATOM
312
CE
LYS
A
39
29.392
6.340
−11.576
1.00
32.23
6
ATOM
313
NZ
LYS
A
39
28.207
5.549
−12.095
1.00
35.95
7
ATOM
314
N
LEU
A
40
30.869
8.716
−6.387
1.00
18.59
7
ATOM
315
CA
LEU
A
40
31.829
7.935
−5.587
1.00
19.30
6
ATOM
316
C
LEU
A
40
31.065
7.001
−4.652
1.00
17.32
6
ATOM
317
O
LEU
A
40
31.433
5.818
−4.467
1.00
19.58
8
ATOM
318
CB
LEU
A
40
32.725
8.865
−4.822
1.00
20.84
6
ATOM
319
CG
LEU
A
40
33.577
9.868
−5.641
1.00
21.98
6
ATOM
320
CD1
LEU
A
40
34.510
10.649
−4.714
1.00
19.78
6
ATOM
321
CD2
LEU
A
40
34.368
9.211
−6.759
1.00
22.47
6
ATOM
322
N
VAL
A
41
30.079
7.532
−3.957
1.00
19.06
7
ATOM
323
CA
VAL
A
41
29.260
6.732
−3.016
1.00
18.09
6
ATOM
324
C
VAL
A
41
28.598
5.614
−3.736
1.00
17.62
6
ATOM
325
O
VAL
A
41
28.537
4.470
−3.258
1.00
19.88
8
ATOM
326
CB
VAL
A
41
28.253
7.674
−2.265
1.00
20.51
6
ATOM
327
CG1
VAL
A
41
27.211
6.841
−1.514
1.00
21.02
6
ATOM
328
CG2
VAL
A
41
29.010
8.629
−1.336
1.00
19.99
6
ATOM
329
N
ASP
A
42
28.010
5.882
−4.952
1.00
18.32
7
ATOM
330
CA
ASP
A
42
27.355
4.768
−5.614
1.00
20.18
6
ATOM
331
C
ASP
A
42
28.312
3.653
−5.995
1.00
20.77
6
ATOM
332
O
ASP
A
42
27.977
2.483
−5.943
1.00
22.32
8
ATOM
333
CB
ASP
A
42
26.667
5.238
−6.920
1.00
22.54
6
ATOM
334
CG
ASP
A
42
25.531
6.164
−6.652
1.00
24.06
6
ATOM
335
OD1
ASP
A
42
24.908
6.188
−5.570
1.00
27.49
8
ATOM
336
OD2
ASP
A
42
25.140
6.976
−7.558
1.00
30.83
8
ATOM
337
N
GLU
A
43
29.539
4.041
−6.419
1.00
20.92
7
ATOM
338
CA
GLU
A
43
30.528
3.015
−6.753
1.00
22.39
6
ATOM
339
C
GLU
A
43
30.924
2.224
−5.512
1.00
21.74
6
ATOM
340
O
GLU
A
43
31.185
1.036
−5.623
1.00
23.66
8
ATOM
341
CB
GLU
A
43
31.816
3.583
−7.342
1.00
23.36
6
ATOM
342
CG
GLU
A
43
31.560
4.030
−8.792
1.00
32.68
6
ATOM
343
CD
GLU
A
43
31.450
2.806
−9.705
1.00
34.94
6
ATOM
344
OE1
GLU
A
43
32.113
1.776
−9.517
1.00
39.24
8
ATOM
345
OE2
GLU
A
43
30.590
2.908
−10.606
1.00
42.50
8
ATOM
346
N
ALA
A
44
31.103
2.914
−4.372
1.00
21.59
7
ATOM
347
CA
ALA
A
44
31.413
2.228
−3.131
1.00
20.24
6
ATOM
348
C
ALA
A
44
30.241
1.299
−2.736
1.00
22.05
6
ATOM
349
O
ALA
A
44
30.575
0.162
−2.324
1.00
23.77
8
ATOM
350
CB
ALA
A
44
31.698
3.226
−2.025
1.00
19.63
6
ATOM
351
N
LYS
A
45
29.033
1.800
−2.843
1.00
24.11
7
ATOM
352
CA
LYS
A
45
27.888
0.912
−2.499
1.00
26.00
6
ATOM
353
C
LYS
A
45
27.912
−0.215
−3.471
1.00
27.19
6
ATOM
354
O
LYS
A
45
27.573
−1.297
−2.970
1.00
28.01
8
ATOM
355
CB
LYS
A
45
26.550
1.612
−2.555
1.00
28.17
6
ATOM
356
CG
LYS
A
45
26.331
2.723
−1.544
1.00
33.53
6
ATOM
357
CD
LYS
A
45
25.613
2.271
−0.277
1.00
40.20
6
ATOM
358
CE
LYS
A
45
24.365
1.437
−0.586
1.00
42.16
6
ATOM
359
NZ
LYS
A
45
23.332
1.467
0.475
1.00
47.05
7
ATOM
360
N
ALA
A
46
28.221
−0.250
−4.714
1.00
25.90
7
ATOM
361
CA
ALA
A
46
28.227
−1.457
−5.529
1.00
26.79
6
ATOM
362
C
ALA
A
46
29.360
−2.424
−5.183
1.00
29.75
6
ATOM
363
O
ALA
A
46
29.233
−3.661
−5.395
1.00
28.75
8
ATOM
364
CB
ALA
A
46
28.360
−1.038
−6.984
1.00
28.50
6
ATOM
365
N
ARG
A
47
30.492
−1.922
−4.680
1.00
26.27
7
ATOM
366
CA
ARG
A
47
31.649
−2.782
−4.511
1.00
25.06
6
ATOM
367
C
ARG
A
47
31.816
−3.283
−3.103
1.00
25.85
6
ATOM
368
O
ARG
A
47
32.669
−4.158
−2.954
1.00
29.00
8
ATOM
369
CB
ARG
A
47
32.921
−1.993
−4.921
1.00
26.64
6
ATOM
370
CG
ARG
A
47
32.973
−1.664
−6.407
1.00
30.45
6
ATOM
371
CD
ARG
A
47
34.079
−0.626
−6.688
1.00
30.96
6
ATOM
372
NE
ARG
A
47
33.831
−0.063
−8.068
1.00
36.09
7
ATOM
373
CZ
ARG
A
47
34.612
−0.526
−9.051
1.00
37.23
6
ATOM
374
NH1
ARG
A
47
35.552
−1.422
−8.779
1.00
37.53
7
ATOM
375
NH2
ARG
A
47
34.458
−0.076
−10.277
1.00
38.83
7
ATOM
376
N
ALA
A
48
31.118
−2.729
−2.117
1.00
23.59
7
ATOM
377
CA
ALA
A
48
31.382
−3.211
−0.762
1.00
23.32
6
ATOM
378
C
ALA
A
48
30.099
−3.421
0.008
1.00
23.85
6
ATOM
379
O
ALA
A
48
29.048
−2.891
−0.355
1.00
26.50
8
ATOM
380
CB
ALA
A
48
32.316
−2.196
−0.069
1.00
24.37
6
ATOM
381
N
ASP
A
49
30.163
−4.115
1.146
1.00
22.20
7
ATOM
382
CA
ASP
A
49
28.925
−4.271
1.916
1.00
26.00
6
ATOM
383
C
ASP
A
49
28.562
−3.133
2.803
1.00
26.80
6
ATOM
384
O
ASP
A
49
27.400
−2.841
3.120
1.00
28.51
8
ATOM
385
CB
ASP
A
49
29.066
−5.563
2.775
1.00
31.27
6
ATOM
386
CG
ASP
A
49
29.809
−6.700
2.149
1.00
35.17
6
ATOM
387
OD1
ASP
A
49
30.741
−7.285
2.759
1.00
35.30
8
ATOM
388
OD2
ASP
A
49
29.459
−7.142
1.032
1.00
39.32
8
ATOM
389
N
VAL
A
50
29.551
−2.305
3.185
1.00
21.71
7
ATOM
390
CA
VAL
A
50
29.379
−1.186
4.072
1.00
24.23
6
ATOM
391
C
VAL
A
50
30.120
0.032
3.514
1.00
22.66
6
ATOM
392
O
VAL
A
50
31.259
−0.150
3.088
1.00
23.46
8
ATOM
393
CB
VAL
A
50
29.980
−1.492
5.460
1.00
28.04
6
ATOM
394
CG1
VAL
A
50
29.862
−0.274
6.353
1.00
30.12
6
ATOM
395
CG2
VAL
A
50
29.310
−2.723
6.087
1.00
31.57
6
ATOM
396
N
VAL
A
51
29.462
1.181
3.484
1.00
20.55
7
ATOM
397
CA
VAL
A
51
30.124
2.367
2.940
1.00
18.63
6
ATOM
398
C
VAL
A
51
30.317
3.377
4.038
1.00
19.83
6
ATOM
399
O
VAL
A
51
29.382
3.743
4.754
1.00
19.84
8
ATOM
400
CB
VAL
A
51
29.292
3.029
1.830
1.00
21.12
6
ATOM
401
CG1
VAL
A
51
29.993
4.288
1.310
1.00
22.56
6
ATOM
402
CG2
VAL
A
51
29.015
2.098
0.666
1.00
23.68
6
ATOM
403
N
VAL
A
52
31.527
3.878
4.198
1.00
18.34
7
ATOM
404
CA
VAL
A
52
31.884
4.890
5.151
1.00
18.76
6
ATOM
405
C
VAL
A
52
32.298
6.183
4.450
1.00
20.80
6
ATOM
406
O
VAL
A
52
33.147
6.104
3.559
1.00
21.14
8
ATOM
407
CB
VAL
A
52
33.088
4.473
6.034
1.00
20.37
6
ATOM
408
CG1
VAL
A
52
33.539
5.585
6.978
1.00
19.87
6
ATOM
409
CG2
VAL
A
52
32.719
3.217
6.820
1.00
21.14
6
ATOM
410
N
VAL
A
53
31.712
7.325
4.777
1.00
18.75
7
ATOM
411
CA
VAL
A
53
32.134
8.568
4.131
1.06
18.32
6
ATOM
412
C
VAL
A
53
32.759
9.411
5.215
1.00
18.55
6
ATOM
413
O
VAL
A
53
32.055
9.630
6.225
1.00
19.86
8
ATOM
414
CB
VAL
A
53
30.949
9.327
3.473
1.00
18.40
6
ATOM
415
CG1
VAL
A
53
31.462
10.680
2.967
1.00
20.65
6
ATOM
416
CG2
VAL
A
53
30.322
8.469
2.396
1.00
17.69
6
ATOM
417
N
SER
A
54
33.913
9.963
4.996
1.00
16.45
7
ATOM
418
CA
SER
A
54
34.482
10.911
5.946
1.00
20.30
6
ATOM
419
C
SER
A
54
34.280
12.349
5.478
1.00
21.22
6
ATOM
420
O
SER
A
54
34.281
12.545
4.254
1.00
18.83
8
ATOM
421
CB
SER
A
54
35.971
10.631
6.156
1.00
21.31
6
ATOM
422
OG
SER
A
54
36.695
10.788
4.949
1.00
21.56
8
ATOM
423
N
ILE
A
55
33.909
13.223
6.394
1.00
21.28
7
ATOM
424
CA
ILE
A
55
33.699
14.621
6.108
1.00
19.86
6
ATOM
425
C
ILE
A
55
34.649
15.356
7.100
1.00
20.76
6
ATOM
426
O
ILE
A
55
34.344
15.342
8.300
1.00
22.84
8
ATOM
427
CB
ILE
A
55
32.273
15.102
6.291
1.00
21.61
6
ATOM
428
CG1
ILE
A
55
31.333
14.422
5.255
1.00
21.20
6
ATOM
429
CG2
ILE
A
55
32.222
16.614
6.139
1.00
22.98
6
ATOM
430
CD1
ILE
A
55
29.854
14.691
5.584
1.00
24.15
6
ATOM
431
N
PHE
A
56
35.723
15.883
6.577
1.00
17.70
7
ATOM
432
CA
PHE
A
56
36.699
16.589
7.404
1.00
18.93
6
ATOM
433
C
PHE
A
56
37.459
17.589
6.579
1.00
20.83
6
ATOM
434
O
PHE
A
56
38.263
17.314
5.680
1.00
21.50
8
ATOM
435
CB
PHE
A
56
37.671
15.557
8.060
1.00
17.73
6
ATOM
436
CG
PHE
A
56
38.721
16.209
8.950
1.00
19.66
6
ATOM
437
CD1
PHE
A
56
38.297
16.881
10.098
1.00
20.08
6
ATOM
438
CD2
PHE
A
56
40.059
16.144
8.616
1.00
20.24
6
ATOM
439
CE1
PHE
A
56
39.261
17.479
10.909
1.00
19.99
6
ATOM
440
CE2
PHE
A
56
41.029
16.743
9.433
1.00
20.35
6
ATOM
441
CZ
PHE
A
56
40.591
17.409
10.573
1.00
21.50
6
ATOM
442
N
VAL
A
57
37.284
18.883
6.949
1.00
21.60
7
ATOM
443
CA
VAL
A
57
38.009
19.978
6.334
1.00
23.17
6
ATOM
444
C
VAL
A
57
39.362
20.006
7.039
1.00
25.23
6
ATOM
445
O
VAL
A
57
39.473
20.469
8.172
1.00
24.88
8
ATOM
446
CB
VAL
A
57
37.247
21.325
6.458
1.00
23.78
6
ATOM
447
CG1
VAL
A
57
38.051
22.403
5.763
1.00
24.08
6
ATOM
448
CG2
VAL
A
57
35.853
21.178
5.874
1.00
23.56
6
ATOM
449
N
ASN
A
58
40.343
19.429
6.377
1.00
24.28
7
ATOM
450
CA
ASN
A
58
41.667
19.181
6.907
1.00
22.31
6
ATOM
451
C
ASN
A
58
42.545
20.385
6.858
1.00
23.05
6
ATOM
452
O
ASN
A
58
43.072
20.747
5.806
1.00
24.44
8
ATOM
453
CB
ASN
A
58
42.250
18.045
6.040
1.00
21.07
6
ATOM
454
CG
ASN
A
58
43.684
17.738
6.385
1.00
22.18
6
ATOM
455
OD1
ASN
A
58
44.133
17.942
7.521
1.00
23.39
8
ATOM
456
ND2
ASN
A
58
44.431
17.254
5.415
1.00
20.86
7
ATOM
457
N
PRO
A
59
42.863
21.002
8.000
1.00
24.30
7
ATOM
458
CA
PRO
A
59
43.727
22.187
7.996
1.00
25.81
6
ATOM
459
C
PRO
A
59
45.060
22.042
7.348
1.00
26.27
6
ATOM
460
O
PRO
A
59
45.679
22.957
6.784
1.00
27.28
8
ATOM
461
CB
PRO
A
59
43.869
22.509
9.493
1.00
24.50
6
ATOM
462
CG
PRO
A
59
42.719
21.834
10.171
1.00
26.42
6
ATOM
463
CD
PRO
A
59
42.427
20.600
9.337
1.00
24.44
6
ATOM
464
N
MET
A
60
45.602
20.784
7.391
1.00
27.24
7
ATOM
465
CA
MET
A
60
46.952
20.529
6.856
1.00
28.64
6
ATOM
466
C
MET
A
60
47.008
20.656
5.361
1.00
31.51
6
ATOM
467
O
MET
A
60
48.101
20.868
4.822
1.00
31.68
8
ATOM
468
CB
MET
A
60
47.374
19.171
7.462
1.00
28.13
6
ATOM
469
CG
MET
A
60
48.810
18.867
7.264
1.00
32.00
6
ATOM
470
SD
MET
A
60
49.373
17.277
7.999
1.00
31.44
16
ATOM
471
CE
MET
A
60
50.665
17.068
6.848
1.00
31.98
6
ATOM
472
N
GLN
A
61
45.847
20.601
4.648
1.00
30.53
7
ATOM
473
CA
GLN
A
61
45.972
20.8D0
3.202
1.00
33.22
6
ATOM
474
C
GLN
A
61
45.492
22.174
2.780
1.00
35.82
6
ATON
475
O
GLN
A
61
45.183
22.463
1.611
1.00
39.20
8
ATOM
476
CB
GLN
A
61
45.264
19.567
2.566
1.00
31.83
6
ATOM
477
CG
GLN
A
61
43.747
19.745
2.433
1.00
29.02
6
ATOM
478
CD
GLN
A
61
43.189
18.320
2.094
1.00
28.13
6
ATOM
479
OE1
GLN
A
61
43.302
17.290
2.731
1.00
24.18
8
ATOM
480
NE2
GLN
A
61
42.486
18.326
0.963
1.00
28.14
7
ATOM
481
N
PHE
A
62
45.576
23.209
3.658
1.00
33.24
7
ATOM
482
CA
PHE
A
62
45.219
24.574
3.275
1.00
33.76
6
ATOM
483
C
PHE
A
62
46.434
25.502
3.390
1.00
35.21
6
ATOM
484
O
PHE
A
62
47.120
25.382
4.405
1.00
33.54
8
ATOM
485
CB
PHE
A
62
44.138
25.218
4.136
1.00
31.27
6
ATOM
486
CG
PHE
A
62
42.754
24.742
3.809
1.00
30.27
6
ATOM
487
CD1
PHE
A
62
42.301
23.528
4.291
1.00
29.03
6
ATOM
488
CD2
PHE
A
62
41.930
25.486
2.975
1.00
29.79
6
ATOM
489
CE1
PHE
A
62
41.037
23.065
3.956
1.00
28.62
6
ATOM
490
CE2
PHE
A
62
40.682
25.043
2.637
1.00
28.83
6
ATOM
491
CZ
PHE
A
62
40.223
23.823
3.112
1.00
28.44
6
ATOM
492
N
ASP
A
63
46.598
26.394
2.439
1.00
40.06
7
ATOM
493
CA
ASP
A
63
47.689
27.339
2.350
1.00
42.93
6
ATOM
494
C
ASP
A
63
47.787
28.342
3.485
1.00
44.06
6
ATOM
495
O
ASP
A
63
48.906
28.726
3.827
1.00
43.96
8
ATOM
496
CB
ASP
A
63
47.575
28.206
1.085
1.00
47.09
6
ATOM
497
CG
ASP
A
63
47.423
27.434
−0.198
1.00
51.39
6
ATOM
498
OD1
ASP
A
63
47.397
26.169
−0.162
1.00
54.46
8
ATOM
499
OD2
ASP
A
63
47.317
28.098
−1.257
1.00
52.58
8
ATOM
500
N
ARG
A
64
46.669
28.845
3.990
1.00
43.31
7
ATOM
501
CA
ARG
A
64
46.717
29.795
5.095
1.00
44.44
6
ATOM
502
C
ARG
A
64
45.451
29.635
5.923
1.00
41.86
6
ATOM
503
O
ARG
A
64
44.424
29.201
5.428
1.00
38.21
8
ATOM
504
CB
ARG
A
64
46.808
31.240
4.660
1.00
47.55
6
ATOM
505
CG
ARG
A
64
48.161
31.803
4.295
1.00
52.46
6
ATOM
506
CD
ARG
A
64
47.938
33.125
3.520
1.00
55.58
6
ATOM
507
NE
ARG
A
64
47.067
32.875
2.441
1.00
58.62
7
ATOM
508
CZ
ARG
A
64
46.215
32.846
1.486
1.00
60.36
6
ATOM
509
NH1
ARG
A
64
45.436
33.900
1.230
1.00
62.10
7
ATOM
510
NH2
ARG
A
64
46.118
31.748
0.742
1.00
60.56
7
ATOM
511
N
PRO
A
65
45.506
30.080
7.169
1.00
41.07
7
ATOM
512
CA
PRO
A
65
44.375
30.002
8.068
1.00
41.23
6
ATOM
513
C
PRG
A
65
43.127
30.709
7.584
1.00
41.03
6
ATOM
514
O
PRO
A
65
42.000
30.258
7.847
1.00
39.31
8
ATOM
515
CB
PRO
A
65
44.911
30.622
9.356
1.00
42.70
6
ATOM
516
CG
PRO
A
65
46.398
30.368
9.281
1.00
43.00
6
ATOM
517
CD
PRO
A
65
46.709
30.642
7.823
1.00
42.34
6
ATOM
518
N
GLU
A
66
43.274
31.789
6.810
1.00
41.59
7
ATOM
519
CA
GLU
A
66
42.070
32.514
6.362
1.00
42.96
6
ATOM
520
C
GLU
A
66
41.347
31.757
5.259
1.00
40.61
6
ATOM
521
O
GLU
A
66
40.120
31.853
5.153
1.00
38.18
8
ATOM
522
CB
GLU
A
66
42.463
33.934
5.932
1.00
48.02
6
ATOM
523
CG
GLU
A
66
43.670
33.931
5.016
1.00
54.67
6
ATOM
524
CD
GLU
A
66
44.083
35.290
4.503
1.00
59.02
6
ATOM
525
OE1
GLU
A
66
44.156
36.244
5.323
1.00
62.04
8
ATOM
526
OE2
GLU
A
66
44.334
35.389
3.276
1.00
60.81
8
ATOM
527
N
ASP
A
67
42.108
30.969
4.481
1.00
38.50
7
ATOM
528
CA
ASP
A
67
41.447
30.178
3.439
1.00
37.14
6
ATOM
529
C
ASP
A
67
40.655
29.082
4.122
1.00
34.07
6
ATOM
530
O
ASP
A
67
39.529
28.761
3.792
1.00
30.58
8
ATOM
531
CB
ASP
A
67
42.413
29.550
2.449
1.00
41.16
6
ATOM
532
CG
ASP
A
67
43.388
30.540
1.846
1.00
44.61
6
ATOM
533
OD1
ASP
A
67
43.068
31.742
1.741
1.00
46.57
8
ATOM
534
OD2
ASP
A
67
44.487
30.073
1.482
1.00
47.46
8
ATOM
535
N
LEU
A
68
41.286
28.452
5.142
1.00
31.94
7
ATOM
536
CA
LEU
A
68
40.581
27.433
5.887
1.00
30.62
6
ATOM
537
C
LEU
A
68
39.303
27.981
6.477
1.00
30.54
6
ATOM
538
O
LEU
A
68
38.243
27.345
6.533
1.00
30.35
8
ATOM
539
CB
LEU
A
68
41.523
26.893
7.001
1.00
29.74
6
ATOM
540
CG
LEU
A
68
40.908
25.958
8.016
1.00
30.11
6
ATOM
541
CD1
LEU
A
68
40.510
24.577
7.474
1.00
30.95
6
ATOM
542
CD2
LEU
A
68
41.899
25.712
9.149
1.00
31.60
6
ATOM
543
N
ALA
A
69
39.345
29.225
7.012
1.00
29.90
7
ATOM
544
CA
ALA
A
69
38.146
29.740
7.662
1.00
32.87
6
ATOM
545
C
ALA
A
69
37.021
29.993
6.663
1.00
34.82
6
ATOM
546
O
ALA
A
69
35.855
29.854
7.018
1.00
35.59
8
ATOM
547
CB
ALA
A
69
38.487
31.030
8.425
1.00
32.66
6
ATOM
548
N
ARG
A
70
37.345
30.321
5.431
1.00
34.63
7
ATOM
549
CA
ARG
A
70
36.337
30.625
4.423
1.00
37.34
6
ATOM
550
C
ARG
A
70
35.777
29.350
3.803
1.00
36.74
6
ATOM
551
O
ARG
A
70
34.726
29.502
3.165
1.00
35.73
8
ATOM
552
CB
ARG
A
70
36.923
31.526
3.334
1.00
38.93
6
ATOM
553
CG
ARG
A
70
37.284
32.923
3.813
1.00
41.54
6
ATOM
554
CD
ARG
A
70
37.555
33.855
2.643
1.00
43.19
6
ATOM
555
NE
ARG
A
70
38.731
33.447
1.880
1.00
47.13
7
ATOM
556
CZ
ARG
A
70
39.977
33.789
2.190
1.00
47.82
6
ATOM
557
NH1
ARG
A
70
40.213
34.544
3.252
1.00
51.37
7
ATOM
558
NH2
ARG
A
70
40.984
33.371
1.435
1.00
48.98
7
ATOM
559
N
TYR
A
71
36.419
28.197
3.875
1.00
32.87
7
ATOM
560
CA
TYR
A
71
35.941
26.999
3.187
1.00
31.99
6
ATOM
561
C
TYR
A
71
34.522
26.700
3.578
1.00
30.54
6
ATOM
562
O
TYR
A
71
34.125
26.714
4.739
1.00
30.28
8
ATOM
563
CB
TYR
A
71
36.927
25.840
3.502
1.00
29.15
6
ATOM
564
CG
TYR
A
71
36.753
24.730
2.482
1.00
29.96
6
ATOM
565
CD1
TYR
A
71
37.363
24.753
1.233
1.00
30.99
6
ATOM
566
CD2
TYR
A
71
35.931
23.658
2.815
1.00
29.82
6
ATOM
567
CE1
TYR
A
71
37.166
23.667
0.356
1.00
33.09
6
ATOM
568
CE2
TYR
A
71
35.713
22.625
1.927
1.00
31.04
6
ATOM
569
CZ
TYR
A
71
36.332
22.650
0.702
1.00
31.47
6
ATOM
570
OH
TYR
A
71
36.163
21.647
−0.214
1.00
34.74
8
ATOM
571
N
PRO
A
72
33.687
26.356
2.591
1.00
33.76
7
ATOM
572
CA
PRO
A
72
32.271
26.095
2.809
1.00
35.62
6
ATOM
573
C
PRO
A
72
31.987
24.932
3.712
1.00
36.23
6
ATOM
574
O
PRO
A
72
32.552
23.855
3.521
1.00
37.45
8
ATOM
575
CB
PRO
A
72
31.695
25.904
1.408
1.00
36.05
6
ATOM
576
CG
PRO
A
72
32.853
25.628
0.524
1.00
36.68
6
ATOM
577
CD
PRO
A
72
34.044
26.284
1.155
1.00
35.26
6
ATOM
578
N
ARG
A
73
31.114
25.089
4.705
1.00
35.24
7
ATOM
579
CA
ARG
A
73
30.752
23.978
5.580
1.00
35.44
6
ATOM
580
C
ARG
A
73
29.254
23.808
5.446
1.00
36.32
6
ATOM
581
O
ARG
A
73
28.544
24.827
5.569
1.00
36.64
8
ATOM
582
CB
ARG
A
73
31.232
24.214
7.012
1.00
37.96
6
ATOM
583
CG
ARG
A
73
32.778
24.055
6.985
1.00
38.27
6
ATOM
584
CD
ARG
A
73
33.433
24.599
8.180
1.00
39.86
6
ATOM
585
NE
ARG
A
73
34.854
24.417
8.347
1.00
37.69
7
ATOM
586
CZ
ARG
A
73
35.799
25.216
7.876
1.00
38.63
6
ATOM
587
NH1
ARG
A
73
37.047
24.918
8.212
1.00
36.16
7
ATOM
588
NH2
ARG
A
73
35.534
26.279
7.132
1.00
38.20
7
ATOM
589
N
THR
A
74
28.763
22.645
5.057
1.00
34.43
7
ATOM
590
CA
THR
A
74
27.358
22.363
4.859
1.00
34.04
6
ATOM
591
C
THR
A
74
27.033
20.953
5.354
1.00
32.80
6
ATOM
592
O
THR
A
74
26.421
20.107
4.689
1.00
31.08
8
ATOM
593
CB
THR
A
74
26.856
22.409
3.403
1.00
36.39
6
ATOM
594
OG1
THR
A
74
27.567
21.394
2.652
1.00
38.24
8
ATOM
595
CG2
THR
A
74
27.020
23.800
2.776
1.00
37.30
6
ATOM
596
N
LEU
A
75
27.405
20.714
6.616
1.00
31.90
7
ATOM
597
CA
LEU
A
75
27.234
19.377
7.168
1.00
30.80
6
ATOM
598
C
LEU
A
75
25.818
18.900
7.129
1.00
30.32
6
ATOM
599
O
LEU
A
75
25.595
17.716
6.815
1.00
29.31
8
ATOM
600
CB
LEU
A
75
27.865
19.401
8.605
1.00
32.17
6
ATOM
601
CG
LEU
A
75
27.986
18.001
9.219
1.00
33.15
6
ATOM
602
CD1
LEU
A
75
28.985
17.154
8.420
1.00
33.59
6
ATOM
603
CD2
LEU
A
75
28.401
18.093
10.663
1.00
32.87
6
ATOM
604
N
GLN
A
76
24.793
19.692
7.502
1.00
29.90
7
ATOM
605
CA
GLN
A
76
23.429
19.175
7.436
1.00
31.72
6
ATOM
606
C
GLN
A
76
23.040
18.695
6.054
1.00
28.82
6
ATOM
607
O
GLN
A
76
22.449
17.626
5.924
1.00
30.69
8
ATOM
608
CB
GLN
A
76
22.423
20.270
7.881
1.00
34.78
6
ATOM
609
CG
GLN
A
76
21.016
19.720
8.042
1.00
40.38
6
ATOM
610
CD
GLN
A
76
20.095
20.836
8.524
1.00
45.28
6
ATOM
611
OE1
GLN
A
76
19.111
21.196
7.859
1.00
48.24
8
ATOM
612
NE2
GLN
A
76
20.453
21.402
9.677
1.00
47.35
7
ATOM
613
N
GLU
A
77
23.274
19.493
5.023
1.00
26.49
7
ATOM
614
CA
GLU
A
77
22.946
19.111
3.656
1.00
27.35
6
ATOM
615
C
GLU
A
77
23.777
17.906
3.193
1.00
27.59
6
ATOM
616
O
GLU
A
77
23.263
17.064
2.463
1.00
27.03
8
ATOM
617
CB
GLU
A
77
23.227
20.280
2.718
1.00
28.83
6
ATOM
618
CG
GLU
A
77
22.722
19.997
1.302
1.00
32.09
6
ATOM
619
N
ASP
A
78
25.048
17.886
3.617
1.00
26.66
7
ATOM
620
CA
ASP
A
78
25.875
16.706
3.239
1.00
26.91
6
ATOM
621
C
ASP
A
78
25.226
15.431
3.735
1.00
26.68
6
ATOM
622
O
ASP
A
78
25.042
14.448
3.018
1.00
24.38
8
ATOM
623
CB
ASP
A
78
27.275
16.820
3.796
1.00
25.18
6
ATOM
624
CG
ASP
A
78
28.116
17.931
3.332
1.00
28.50
6
ATOM
625
OD1
ASP
A
78
27.681
18.573
2.312
1.00
28.92
8
ATOM
626
OD2
ASP
A
78
29.179
18.397
3.774
1.00
29.90
8
ATOM
627
N
CYS
A
79
24.883
15.488
5.051
1.00
27.85
7
ATOM
628
CA
CYS
A
79
24.304
14.292
5.666
1.00
30.04
6
ATOM
629
C
CYS
A
79
22.949
13.894
5.111
1.00
29.71
6
ATOM
630
O
CYS
A
79
22.684
12.715
4.944
1.00
29.58
8
ATOM
631
CB
CYS
A
79
24.188
14.507
7.183
1.00
31.67
6
ATOM
632
SG
CYS
A
79
25.844
14.386
7.916
1.00
33.92
16
ATOM
633
N
GLU
A
80
22.134
14.874
4.734
1.00
30.93
7
ATOM
634
CA
GLU
A
80
20.899
14.555
4.007
1.00
32.01
6
ATOM
635
C
GLU
A
80
21.197
13.812
2.705
1.00
29.17
6
ATOM
636
O
GLU
A
80
20.524
12.822
2.413
1.00
29.08
8
ATOM
637
CB
GLU
A
80
20.135
15.852
3.756
1.00
36.34
6
ATOM
638
CG
GLU
A
80
19.379
16.349
4.985
1.00
43.73
6
ATOM
639
CD
GLU
A
80
18.700
17.700
4.818
1.00
48.86
6
ATOM
640
OE1
GLU
A
80
18.432
18.156
3.670
1.00
51.62
8
ATOM
641
OE2
GLU
A
80
18.442
18.338
5.884
1.00
51.33
8
ATOM
642
N
LYS
A
81
22.175
14.264
1.921
1.00
26.79
7
ATOM
643
CA
LYS
A
81
22.522
13.581
0.676
1.00
27.73
6
ATOM
644
C
LYS
A
81
23.067
12.161
0.921
1.00
27.62
6
ATOM
645
O
LYS
A
81
22.686
11.291
0.147
1.00
25.90
8
ATOM
646
CB
LYS
A
81
23.541
14.390
−0.112
1.00
27.61
6
ATOM
647
CG
LYS
A
81
23.036
15.708
−0.702
1.00
27.05
6
ATOM
648
CD
LYS
A
81
24.149
16.381
−1.485
1.00
29.23
6
ATOM
649
CE
LYS
A
81
23.586
17.726
−1.958
1.00
31.40
6
ATOM
650
NZ
LYS
A
81
24.290
18.189
−3.180
1.00
33.21
7
ATOM
651
N
LEU
A
82
23.941
12.067
1.932
1.00
25.01
7
ATOM
652
CA
LEU
A
82
24.428
10.653
2.208
1.00
25.50
6
ATOM
653
C
LEU
A
82
23.359
9.729
2.719
1.00
24.46
6
ATOM
654
O
LEU
A
82
23.296
8.571
2.335
1.00
25.35
8
ATOM
655
CB
LEU
A
82
25.616
10.767
3.179
1.00
24.87
6
ATOM
656
CG
LEU
A
82
26.765
11.600
2.627
1.00
25.74
6
ATOM
657
CD1
LEU
A
82
27.854
11.923
3.663
1.00
24.08
6
ATOM
658
CD2
LEU
A
82
27.412
10.853
1.463
1.00
24.64
6
ATOM
659
N
ASN
A
83
22.437
10.262
3.549
1.00
27.59
7
ATOM
660
CA
ASN
A
83
21.352
9.467
4.081
1.00
29.62
6
ATOM
661
C
ASN
A
83
20.400
9.086
2.941
1.00
31.66
6
ATOM
662
O
ASN
A
83
20.066
7.899
2.966
1.00
31.60
8
ATOM
663
CB
ASN
A
83
20.649
10.212
5.205
1.00
32.77
6
ATOM
664
CG
ASN
A
83
19.718
9.324
6.010
1.00
37.49
6
ATOM
665
OD1
ASN
A
83
18.788
9.898
6.588
1.00
42.54
8
ATOM
666
ND2
ASN
A
83
19.899
8.019
6.093
1.00
37.69
7
ATOM
667
N
LYS
A
84
20.176
9.954
1.933
1.00
31.56
7
ATOM
668
CA
LYS
A
84
19.397
9.440
0.781
1.00
33.04
6
ATOM
669
C
LYS
A
84
20.155
8.440
−0.069
1.00
34.14
6
ATOM
670
O
LYS
A
84
19.531
7.661
−0.824
1.00
34.69
8
ATOM
671
CB
LYS
A
84
18.915
10.637
−0.071
1.00
36.71
6
ATOM
672
CG
LYS
A
84
17.639
11.350
0.339
1.00
42.14
6
ATOM
673
CD
LYS
A
84
17.457
12.707
−0.355
1.00
45.16
6
ATOM
674
CE
LYS
A
84
16.334
13.494
0.303
1.00
48.19
6
ATOM
675
NZ
LYS
A
84
16.337
14.928
−0.105
1.00
50.51
7
ATOM
676
N
ARG
A
85
21.483
8.305
0.021
1.00
34.32
7
ATOM
677
CA
ARG
A
85
22.276
7.344
−0.773
1.00
33.70
6
ATOM
678
C
ARG
A
85
22.620
6.057
−0.050
1.00
34.60
6
ATOM
679
O
ARG
A
85
23.358
5.112
−0.377
1.00
36.33
8
ATOM
680
CB
ARG
A
85
23.529
8.099
−1.166
1.00
34.84
6
ATOM
681
CG
ARG
A
85
24.040
7.946
−2.583
1.00
36.24
6
ATOM
682
CD
ARG
A
85
23.177
8.780
−3.502
1.00
37.79
6
ATOM
683
NE
ARG
A
85
23.549
8.555
−4.891
1.00
36.63
7
ATOM
684
CZ
ARG
A
85
23.122
9.364
−5.853
1.00
37.76
6
ATOM
685
NH1
ARG
A
85
22.368
10.397
−5.507
1.00
38.88
7
ATOM
686
NH2
ARG
A
85
23.473
9.117
−7.100
1.00
37.39
7
ATOM
687
N
LYS
A
86
21.948
5.940
1.093
1.00
33.51
7
ATOM
688
CA
LYS
A
86
21.983
4.881
2.059
1.00
34.48
6
ATOM
689
C
LYS
A
86
23.404
4.563
2.503
1.00
32.25
6
ATOM
690
O
LYS
A
86
23.823
3.405
2.516
1.00
34.37
8
ATOM
691
CB
LYS
A
86
21.290
3.624
1.477
1.00
37.47
6
ATOM
692
CG
LYS
A
86
19.862
3.957
1.034
1.00
42.40
6
ATON
693
CD
LYS
A
86
18.990
4.373
2.205
1.00
46.88
6
ATOM
694
CE
LYS
A
86
18.857
3.256
3.233
1.00
50.03
6
ATOM
695
NZ
LYS
A
86
18.397
3.827
4.543
1.00
52.47
7
ATOM
696
N
VAL
A
87
24.138
5.595
2.885
1.00
29.97
7
ATOM
697
CA
VAL
A
87
25.490
5.405
3.428
1.00
26.05
6
ATOM
698
C
VAL
A
87
25.390
4.849
4.829
1.00
28.43
6
ATOM
699
O
VAL
A
87
24.498
5.233
5.587
1.00
26.14
8
ATOM
700
CB
VAL
A
87
26.199
6.749
3.397
1.00
26.58
6
ATOM
701
CG1
VAL
A
87
27.425
6.848
4.304
1.00
23.69
6
ATOM
702
CG2
VAL
A
87
26.640
7.063
1.961
1.00
25.53
6
ATOM
703
N
ASP
A
88
26.274
3.947
5.231
1.00
25.06
7
ATOM
704
CA
ASP
A
88
26.163
3.320
6.552
1.00
27.11
6
ATOM
705
C
ASP
A
88
26.718
4.129
7.696
1.00
26.68
6
ATOM
706
O
ASP
A
88
26.108
4.221
8.763
1.00
27.00
8
ATOM
707
CB
ASP
A
88
26.899
1.986
6.461
1.00
29.00
6
ATOM
708
CG
ASP
A
88
26.332
1.114
5.377
1.00
31.90
6
ATOM
709
OD1
ASP
A
88
25.301
0.444
5.714
1.00
34.25
8
ATOM
710
OD2
ASP
A
88
26.819
1.060
4.237
1.00
30.16
8
ATOM
711
N
LEU
A
89
27.798
4.864
7.483
1.00
21.05
7
ATOM
712
CA
LEU
A
89
28.448
5.620
8.532
1.00
22.89
6
ATOM
713
C
LEU
A
89
29.085
6.879
7.997
1.00
25.24
6
ATOM
714
O
LEU
A
89
29.775
6.771
6.967
1.00
24.36
8
ATOM
715
CB
LEU
A
89
29.561
4.723
9.069
1.00
27.61
6
ATOM
716
CG
LEU
A
89
30.275
5.099
10.342
1.00
31.35
6
ATOM
717
CD1
LEU
A
89
30.916
3.857
10.963
1.00
34.98
6
ATOM
718
CD2
LEU
A
89
31.363
6.137
10.099
1.00
33.01
6
ATOM
719
N
VAL
A
90
28.910
7.987
8.677
1.00
22.49
7
ATOM
720
CA
VAL
A
90
29.577
9.200
8.296
1.00
23.34
6
ATOM
721
C
VAL
A
90
30.551
9.518
9.431
1.00
24.94
6
ATOM
722
O
VAL
A
90
30.041
9.581
10.575
1.00
25.44
8
ATOM
723
CB
VAL
A
90
28.602
10.366
8.153
1.00
21.61
6
ATOM
724
CG1
VAL
A
90
29.294
11.692
7.966
1.00
23.24
6
ATOM
725
CG2
VAL
A
90
27.695
10.065
6.945
1.00
24.01
6
ATOM
726
N
PHE
A
91
31.819
9.736
9.120
1.00
20.62
7
ATOM
727
CA
PHE
A
91
32.779
10.106
10.131
1.00
21.25
6
ATOM
728
C
PHE
A
91
33.008
11.589
9.966
1.00
22.65
6
ATOM
729
O
PHE
A
91
33.612
12.028
8.957
1.00
20.89
8
ATOM
730
CB
PHE
A
91
34.059
9.254
9.968
1.00
20.01
6
ATOM
731
CG
PHE
A
91
35.181
9.639
10.897
1.00
20.02
6
ATOM
732
CD1
PHE
A
91
34.954
9.716
12.277
1.00
20.82
6
ATOM
733
CD2
PHE
A
91
36.465
9.830
10.421
1.00
21.38
6
ATOM
734
CE1
PHE
A
91
36.004
10.045
13.150
1.00
21.05
6
ATOM
735
CE2
PHE
A
91
37.503
10.196
11.281
1.00
23.76
6
ATOM
736
CZ
PHE
A
91
37.261
10.233
12.631
1.00
21.99
6
ATOM
737
N
ALA
A
92
32.580
12.382
10.985
1.00
23.09
7
ATOM
738
CA
ALA
A
92
32.750
13.824
10.898
1.00
23.04
6
ATOM
739
C
ALA
A
92
33.406
14.387
12.142
1.00
24.15
6
ATOM
740
O
ALA
A
92
32.699
14.986
12.979
1.00
24.45
8
ATOM
741
CB
ALA
A
92
31.368
14.496
10.717
1.00
23.41
6
ATOM
742
N
PRO
A
93
34.701
14.252
12.284
1.00
23.10
7
ATOM
743
CA
PRO
A
93
35.387
14.638
13.507
1.00
21.87
6
ATOM
744
C
PRO
A
93
35.695
16.093
13.560
1.00
23.67
6
ATOM
745
O
PRO
A
93
35.740
16.790
12.510
1.00
24.71
8
ATOM
746
CB
PRO
A
93
36.687
13.798
13.426
1.00
21.94
6
ATOM
747
CG
PRO
A
93
37.002
13.904
11.930
1.00
23.58
6
ATOM
748
CD
PRO
A
93
35.643
13.553
11.336
1.00
21.29
6
ATOM
749
N
SER
A
94
35.940
16.664
14.752
1.00
23.63
7
ATOM
750
CA
SER
A
94
36.447
18.022
14.812
1.00
26.17
6
ATOM
751
C
SER
A
94
37.939
18.117
14.561
1.00
26.12
6
ATOM
752
O
SER
A
94
38.700
17.126
14.588
1.00
25.24
8
ATOM
753
CB
SER
A
94
36.151
18.617
16.207
1.00
26.90
6
ATOM
754
OG
SER
A
94
36.930
17.871
17.168
1.00
27.23
8
ATOM
755
N
VAL
A
95
38.487
19.308
14.308
1.00
25.69
7
ATOM
756
CA
VAL
A
95
39.900
19.519
14.115
1.00
25.50
6
ATOM
757
C
VAL
A
95
40.639
19.107
15.409
1.00
28.17
6
ATOM
758
O
VAL
A
95
41.692
18.475
15.307
1.00
27.54
8
ATOM
759
CB
VAL
A
95
40.319
20.963
13.788
1.00
27.40
6
ATOM
760
CG1
VAL
A
95
41.808
21.236
13.929
1.00
27.91
6
ATOM
761
CG2
VAL
A
95
39.873
21.263
12.346
1.00
26.36
6
ATOM
762
N
LYS
A
96
40.047
19.405
16.570
1.00
26.82
7
ATOM
763
CA
LYS
A
96
40.718
18.994
17.823
1.00
28.89
6
ATOM
764
C
LYS
A
96
40.773
17.474
17.962
1.00
28.61
6
ATOM
765
O
LYS
A
96
41.723
16.951
18.539
1.00
27.95
8
ATOM
766
CB
LYS
A
96
40.013
19.550
19.066
1.00
29.19
6
ATOM
767
N
GLU
A
97
39.756
16.765
17.486
1.00
28.36
7
ATOM
768
CA
GLU
A
97
39.748
15.295
17.583
1.00
29.80
6
ATOM
769
C
GLU
A
97
40.830
14.674
16.708
1.00
29.13
6
ATOM
770
O
GLU
A
97
41.565
13.752
17.126
1.00
29.24
8
ATOM
771
CB
GLU
A
97
38.365
14.782
17.214
1.00
29.05
6
ATOM
772
CG
GLU
A
97
38.194
13.265
17.303
1.00
28.83
6
ATOM
773
CD
GLU
A
97
38.133
12.796
18.762
1.00
30.81
6
ATOM
774
OE1
GLU
A
97
38.046
13.687
19.649
1.00
32.00
8
ATOM
775
OE2
GLU
A
97
38.132
11.592
19.080
1.00
28.32
8
ATOM
776
N
ILE
A
98
41.066
15.194
15.516
1.00
26.74
7
ATOM
777
CA
ILE
A
98
42.110
14.673
14.641
1.00
24.88
6
ATOM
778
C
ILE
A
98
43.483
15.219
14.955
1.00
26.67
6
ATOM
779
O
ILE
A
98
44.485
14.459
14.852
1.00
24.09
8
ATOM
780
CB
ILE
A
98
41.817
14.972
13.147
1.00
23.79
6
ATOM
781
CG1
ILE
A
98
40.483
14.337
12.789
1.00
22.35
6
ATOM
782
CG2
ILE
A
98
42.971
14.486
12.252
1.00
22.39
6
ATOM
783
CD1
ILE
A
98
40.431
12.804
12.865
1.00
24.57
6
ATOM
784
N
TYR
A
99
43.603
16.493
15.375
1.00
24.39
7
ATOM
785
CA
TYR
A
99
44.886
17.127
15.585
1.00
26.57
6
ATOM
786
C
TYR
A
99
44.917
17.788
16.978
1.00
26.98
6
ATOM
787
O
TYR
A
99
44.959
18.984
17.080
1.00
29.92
8
ATOM
788
CB
TYR
A
99
45.244
18.185
14.514
1.00
24.58
6
ATOM
789
CG
TYR
A
99
45.318
17.673
13.080
1.00
24.59
6
ATOM
790
CD1
TYR
A
99
44.461
18.086
12.085
1.00
23.63
6
ATOM
791
CD2
TYR
A
99
46.371
16.838
12.709
1.00
23.01
6
ATOM
792
CE1
TYR
A
99
44.573
17.677
10.760
1.00
23.55
6
ATOM
793
CE2
TYR
A
99
46.491
16.358
11.405
1.00
25.75
6
ATOM
794
CZ
TYR
A
99
45.593
16.773
10.447
1.00
24.33
6
ATOM
795
OH
TYR
A
99
45.814
16.340
9.160
1.00
22.62
8
ATOM
796
N
PRO
A
100
44.891
17.004
18.020
1.00
29.54
7
ATOM
797
CA
PRO
A
100
44.819
17.563
19.401
1.00
30.81
6
ATOM
798
C
PRO
A
100
46.024
18.411
19.723
1.00
33.04
6
ATOM
799
O
PRO
A
100
45.855
19.351
20.545
1.00
34.95
8
ATOM
800
CB
PRO
A
100
44.652
16.358
20.291
1.00
32.03
6
ATOM
801
CG
PRO
A
100
45.376
15.277
19.517
1.00
31.65
6
ATOM
802
CD
PRO
A
100
44.894
15.532
18.081
1.00
29.86
6
ATOM
803
N
ASN
A
101
47.177
18.234
19.116
1.00
30.09
7
ATOM
804
CA
ASN
A
101
48.364
19.030
19.406
1.00
29.38
6
ATOM
805
C
ASN
A
101
48.732
19.925
18.258
1.00
28.34
6
ATOM
806
O
ASN
A
101
49.831
20.474
18.133
1.00
29.73
8
ATOM
807
CB
ASN
A
101
49.573
18.111
19.726
1.00
32.63
6
ATOM
808
CG
ASN
A
101
49.136
17.044
20.693
1.00
32.29
6
ATOM
809
OD1
ASN
A
101
49.095
15.839
20.358
1.00
35.88
8
ATOM
810
ND2
ASN
A
101
48.725
17.480
21.868
1.00
33.54
7
ATOM
811
N
GLY
A
102
47.764
20.158
17.344
1.00
28.24
7
ATOM
812
CA
GLY
A
102
48.018
20.969
16.192
1.00
28.54
6
ATOM
813
C
GLY
A
102
48.572
20.122
15.054
1.00
28.73
6
ATOM
814
O
GLY
A
102
48.848
18.918
15.212
1.00
28.80
8
ATOM
815
N
THR
A
103
48.797
20.786
13.929
1.00
28.45
7
ATOM
816
CA
THR
A
103
49.271
20.035
12.755
1.00
27.44
6
ATOM
817
C
THR
A
103
50.751
20.121
12.584
1.00
27.75
6
ATOM
818
O
THR
A
103
51.419
19.270
11.979
1.00
28.24
8
ATOM
819
CB
THR
A
103
48.585
20.545
11.461
1.00
28.39
6
ATOM
820
OG1
THR
A
103
49.011
21.911
11.287
1.00
29.31
8
ATOM
821
CG2
THR
A
103
47.081
20.410
11.575
1.00
25.68
6
ATOM
822
N
GLU
A
104
51.410
21.114
13.189
1.00
26.94
7
ATOM
823
CA
GLU
A
104
52.843
21.274
12.953
1.00
30.65
6
ATOM
824
C
GLU
A
104
53.682
20.149
13.572
1.00
27.87
6
ATOM
825
O
GLU
A
104
54.755
19.902
13.010
1.00
30.98
8
ATOM
826
CB
GLU
A
104
53.353
22.617
13.515
1.00
34.13
6
ATOM
827
CG
GLU
A
104
52.613
23.746
12.784
1.00
40.22
6
ATOM
828
CD
GLU
A
104
51.319
24.211
13.411
1.00
44.21
6
ATOM
829
OE1
GLU
A
104
50.583
23.551
14.187
1.00
42.68
8
ATOM
830
OE2
GLU
A
104
50.972
25.409
13.090
1.00
48.99
8
ATOM
831
N
THR
A
105
53.210
19.618
14.686
1.00
24.87
7
ATOM
832
CA
THR
A
105
54.112
18.554
15.230
1.00
25.37
6
ATOM
833
C
THR
A
105
53.586
17.170
14.962
1.00
24.14
6
ATOM
834
O
THR
A
105
54.100
16.162
15.504
1.00
23.64
8
ATOM
835
CB
THR
A
105
54.301
18.763
16.735
1.00
24.29
6
ATOM
836
OG1
THR
A
105
53.037
18.773
17.363
1.00
27.37
8
ATOM
837
CG2
THR
A
105
55.020
20.098
16.999
1.00
27.01
6
ATOM
838
N
HIS
A
106
52.456
17.094
14.251
1.00
22.37
7
ATOM
839
CA
HIS
A
106
51.897
15.760
13.955
1.00
22.53
6
ATOM
840
C
HIS
A
106
52.748
15.031
12.927
1.00
20.08
6
ATOM
841
O
HIS
A
106
53.289
15.552
11.960
1.00
22.95
8
ATOM
842
CB
HIS
A
106
50.457
15.962
13.432
1.00
20.21
6
ATOM
843
CG
HIS
A
106
49.534
14.791
13.386
1.00
19.83
6
ATOM
844
ND1
HIS
A
106
49.650
13.883
12.350
1.00
19.73
7
ATOM
845
CD2
HIS
A
106
48.484
14.387
14.112
1.00
18.64
6
ATOM
846
CE1
HIS
A
106
48.695
13.003
12.509
1.00
17.48
6
ATOM
847
NE2
HIS
A
106
47.914
13.255
13.533
1.00
19.68
7
ATOM
848
N
THR
A
107
52.772
13.689
13.062
1.00
21.05
7
ATOM
849
CA
THR
A
107
53.466
12.840
12.117
1.00
20.53
6
ATOM
850
C
THR
A
107
52.946
13.066
10.697
1.00
20.02
6
ATOM
851
O
THR
A
107
51.730
13.301
10.684
1.00
20.34
8
ATOM
852
CB
THR
A
107
53.232
11.366
12.525
1.00
21.22
6
ATOM
853
OG1
THR
A
107
53.808
11.185
13.848
1.00
22.21
8
ATOM
854
CG2
THR
A
107
53.856
10.364
11.540
1.00
21.83
6
ATOM
855
N
TYR
A
108
53.769
13.113
9.699
1.00
20.01
7
ATOM
856
CA
TYR
A
108
53.224
13.286
8.347
1.00
22.77
6
ATOM
857
C
TYR
A
108
53.796
12.231
7.405
1.00
21.91
6
ATOM
858
O
TYR
A
108
54.794
11.532
7.605
1.00
19.88
8
ATOM
859
CB
TYR
A
108
53.505
14.695
7.860
1.00
23.51
6
ATOM
860
CG
TYR
A
108
54.978
15.076
7.762
1.00
24.54
6
ATOM
861
CD1
TYR
A
108
55.707
14.832
6.624
1.00
25.82
6
ATOM
862
CD2
TYR
A
108
55.623
15.677
8.857
1.00
26.49
6
ATOM
863
CE1
TYR
A
108
57.051
15.146
6.526
1.00
29.12
6
ATOM
864
CE2
TYR
A
108
56.970
16.024
8.781
1.00
29.06
6
ATOM
865
CZ
TYR
A
108
57.664
15.733
7.631
1.00
29.44
6
ATOM
866
OH
TYR
A
108
58.995
16.072
7.478
1.00
32.47
8
ATOM
867
N
VAL
A
109
53.052
12.125
6.280
1.00
19.53
7
ATOM
868
CA
VAL
A
109
53.431
11.213
5.194
1.00
20.38
6
ATOM
869
C
VAL
A
109
53.653
12.022
3.954
1.00
24.73
6
ATOM
870
O
VAL
A
109
52.756
12.811
3.553
1.00
23.81
8
ATOM
871
CB
VAL
A
109
52.263
10.230
4.964
1.00
20.04
6
ATOM
872
CG1
VAL
A
109
52.619
9.362
3.731
1.00
23.57
6
ATOM
873
CG2
VAL
A
109
51.946
9.420
6.209
1.00
17.72
6
ATOM
874
N
ASP
A
110
54.753
11.885
3.237
1.00
25.18
7
ATOM
875
CA
ASP
A
110
55.054
12.663
2.047
1.00
28.26
6
ATOM
876
C
ASP
A
110
55.453
11.784
0.881
1.00
25.00
6
ATOM
877
O
ASP
A
110
56.220
10.815
1.006
1.00
23.50
8
ATOM
878
CB
ASP
A
110
56.199
13.596
2.383
1.00
34.46
6
ATOM
879
CG
ASP
A
110
56.031
15.027
1.970
1.00
42.11
6
ATOM
880
OD1
ASP
A
110
56.945
15.774
2.403
1.00
48.30
8
ATOM
881
OD2
ASP
A
110
55.098
15.496
1.290
1.00
46.79
8
ATOM
882
N
VAL
A
111
54.851
11.964
−0.272
1.00
24.14
7
ATOM
883
CA
VAL
A
111
55.111
11.236
−1.493
1.00
23.80
6
ATOM
884
C
VAL
A
111
56.023
12.085
−2.363
1.00
24.56
6
ATOM
885
O
VAL
A
111
55.572
13.037
−3.027
1.00
25.12
8
ATOM
886
CB
VAL
A
111
53.771
10.929
−2.218
1.00
23.25
6
ATOM
887
CG1
VAL
A
111
54.020
10.068
−3.456
1.00
22.00
6
ATOM
888
CG2
VAL
A
111
52.810
10.285
−1.246
1.00
22.35
6
ATOM
889
N
PRO
A
112
57.278
11.687
−2.453
1.00
26.28
7
ATOM
890
CA
PRO
A
112
58.274
12.438
−3.222
1.00
27.97
6
ATOM
891
C
PRO
A
112
57.906
12.619
−4.650
1.00
30.72
6
ATOM
892
O
PRO
A
112
57.272
11.711
−5.253
1.00
30.37
8
ATOM
893
CB
PRO
A
112
59.532
11.573
−3.106
1.00
27.29
6
ATOM
894
CG
PRO
A
112
59.413
10.926
−1.769
1.00
27.60
6
ATOM
895
CD
PRO
A
112
57.905
10.536
−1.762
1.00
24.64
6
ATOM
896
N
GLY
A
113
58.211
13.800
−5.209
1.00
30.66
7
ATOM
897
CA
GLY
A
113
57.940
14.000
−6.614
1.00
32.72
6
ATOM
898
C
GLY
A
113
56.543
14.464
−6.926
1.00
31.39
6
ATOM
899
O
GLY
A
113
56.346
15.614
−7.280
1.00
30.61
8
ATOM
900
N
LEU
A
114
55.558
13.575
−6.772
1.00
27.67
7
ATOM
901
CA
LEU
A
114
54.192
13.922
−7.023
1.00
28.50
6
ATOM
902
C
LEU
A
114
53.677
15.086
−6.186
1.00
29.37
6
ATOM
903
O
LEU
A
114
52.810
15.829
−6.657
1.00
33.05
8
ATOM
904
CB
LEU
A
114
53.283
12.710
−6.702
1.00
29.66
6
ATOM
905
CG
LEU
A
114
53.515
11.551
−7.669
1.00
31.75
6
ATOM
906
CD1
LEU
A
114
52.703
10.351
−7.233
1.00
31.73
6
ATOM
907
CD2
LEU
A
114
53.134
11.977
−9.059
1.00
35.50
6
ATOM
908
N
SER
A
115
54.161
15.180
−4.965
1.00
26.50
7
ATOM
909
CA
SER
A
115
53.664
16.206
−4.063
1.00
27.52
6
ATOM
910
C
SER
A
115
54.245
17.582
−4.400
1.00
30.00
6
ATOM
911
O
SER
A
115
53.590
18.536
−3.932
1.00
28.18
8
ATOM
912
CB
SER
A
115
53.978
15.885
−2.599
1.00
25.46
6
ATOM
913
OG
SER
A
115
55.407
15.846
−2.464
1.00
30.73
8
ATOM
914
N
THR
A
116
55.312
17.617
−5.177
1.00
30.25
7
ATOM
915
CA
THR
A
116
55.884
18.969
−5.426
1.00
32.64
6
ATOM
916
C
THR
A
116
55.854
19.345
−6.870
1.00
33.28
6
ATOM
917
O
THR
A
116
56.516
20.337
−7.260
1.00
37.48
8
ATOM
918
CB
THR
A
116
57.318
19.018
−4.839
1.00
31.68
6
ATOM
919
OG1
THR
A
116
58.066
17.923
−5.419
1.00
33.81
8
ATOM
920
CG2
THR
A
116
57.348
18.863
−3.344
1.00
30.91
6
ATOM
921
N
MET
A
117
55.075
18.691
−7.725
1.00
34.70
7
ATOM
922
CA
MET
A
117
54.978
19.104
−9.116
1.00
36.76
6
ATOM
923
C
MET
A
117
53.599
19.679
−9.408
1.00
35.12
6
ATOM
924
O
MET
A
117
52.722
19.561
−8.569
1.00
34.04
8
ATOM
925
CB
MET
A
117
55.258
17.952
−10.067
1.00
38.70
6
ATOM
926
CG
MET
A
117
54.494
16.690
−9.707
1.00
41.51
6
ATOM
927
SD
MET
A
117
55.327
15.244
−10.403
1.00
45.13
16
ATOM
928
CE
MET
A
117
55.643
15.848
−12.065
1.00
43.90
6
ATOM
929
N
LEU
A
118
53.449
20.272
−10.578
1.00
35.18
7
ATOM
930
CA
LEU
A
118
52.173
20.846
−10.995
1.00
36.73
6
ATOM
931
C
LEU
A
118
51.570
21.660
−9.877
1.00
36.48
6
ATOM
932
O
LEU
A
118
52.236
22.552
−9.330
1.00
36.60
8
ATOM
933
CB
LEU
A
118
51.252
19.706
−11.478
1.00
38.22
6
ATOM
934
CG
LEU
A
118
51.872
18.829
−12.571
1.00
39.36
6
ATOM
935
CD1
LEU
A
118
51.001
17.679
−13.051
1.00
41.36
6
ATOM
936
CD2
LEU
A
118
52.194
19.710
−13.783
1.00
41.80
6
ATOM
937
N
GLU
A
119
50.329
21.339
−9.481
1.00
38.80
7
ATOM
938
CA
GLU
A
119
49.645
22.049
−8.411
1.00
37.83
6
ATOM
939
C
GLU
A
119
50.401
22.088
−7.102
1.00
38.27
6
ATOM
940
O
GLU
A
119
50.416
23.101
−6.393
1.00
38.36
8
ATOM
941
CB
GLU
A
119
48.255
21.394
−8.141
1.00
41.10
6
ATOM
942
CG
GLU
A
119
47.470
22.109
−7.049
1.00
41.69
6
ATOM
943
CD
GLU
A
119
46.082
21.559
−6.784
1.00
44.93
6
ATOM
944
OE1
GLU
A
119
45.654
20.593
−7.453
1.00
40.85
8
ATOM
945
OE2
GLU
A
119
45.379
22.098
−5.892
1.00
45.21
8
ATOM
946
N
GLY
A
120
51.165
21.031
−6.805
1.00
35.61
7
ATOM
947
CA
GLY
A
120
51.945
20.951
−5.595
1.00
33.60
6
ATOM
948
C
GLY
A
120
53.033
22.013
−5.540
1.00
34.42
6
ATOM
949
O
GLY
A
120
53.390
22.405
−4.437
1.00
36.33
8
ATOM
950
N
ALA
A
121
53.588
22.394
−6.677
1.00
35.01
7
ATOM
951
CA
ALA
A
121
54.622
23.437
−6.741
1.00
35.93
6
ATOM
952
C
ALA
A
121
54.069
24.789
−6.295
1.00
39.30
6
ATOM
953
O
ALA
A
121
54.752
25.536
−5.588
1.00
40.98
8
ATOM
954
CB
ALA
A
121
55.189
23.547
−8.150
1.00
32.29
6
ATOM
955
N
SER
A
122
52.818
25.124
−6.644
1.00
41.40
7
ATOM
956
CA
SER
A
122
52.261
26.415
−6.226
1.00
44.40
6
ATOM
957
C
SER
A
122
51.626
26.354
−4.849
1.00
45.24
6
ATOM
958
O
SER
A
122
51.056
27.328
−4.339
1.00
44.99
8
ATOM
959
CB
SER
A
122
51.226
26.909
−7.241
1.00
45.02
6
ATOM
960
OG
SER
A
122
50.178
25.972
−7.432
1.00
46.98
8
ATOM
961
N
ARG
A
123
51.634
25.169
−4.197
1.00
45.65
7
ATOM
962
CA
ARG
A
123
51.045
24.991
−2.876
1.00
44.81
6
ATOM
963
C
ARG
A
123
51.908
24.083
−2.006
1.00
44.93
6
ATOM
964
O
ARG
A
123
51.557
22.916
−1.788
1.00
44.88
8
ATOM
965
CB
ARG
A
123
49.631
24.419
−2.992
1.00
45.81
6
ATOM
966
CG
ARG
A
123
48.629
25.367
−3.630
1.00
46.85
6
ATOM
967
CD
ARG
A
123
47.248
24.736
−3.714
1.00
50.24
6
ATOM
968
NE
ARG
A
123
46.466
24.971
−2.504
1.00
52.21
7
ATOM
969
CZ
ARG
A
123
45.271
24.437
−2.271
1.00
52.64
6
ATOM
970
NH1
ARG
A
123
44.718
23.633
−3.169
1.00
52.96
7
ATOM
971
NH2
ARG
A
123
44.633
24.708
−1.141
1.00
53.34
7
ATOM
972
N
PRO
A
124
52.717
24.827
−1.604
1.00
44.27
7
ATOM
973
CA
PRO
A
124
53.669
24.219
−0.725
1.00
43.54
6
ATOM
974
C
PRO
A
124
53.075
23.501
0.473
1.00
43.43
6
ATOM
975
O
PRO
A
124
52.427
24.264
1.223
1.00
44.21
8
ATOM
976
CB
PRO
A
124
54.534
25.391
−0.224
1.00
43.61
6
ATOM
977
CG
PRO
A
124
54.396
26.439
−1.257
1.00
44.17
6
ATOM
978
CD
PRO
A
124
52.971
26.302
−1.746
1.00
44.92
6
ATOM
979
N
GLY
A
125
53.248
21.897
0.840
1.00
39.19
7
ATOM
980
CA
GLY
A
125
52.585
21.453
2.061
1.00
34.50
6
ATOM
981
C
GLY
A
125
51.230
20.789
1.809
1.00
32.64
6
ATOM
982
O
GLY
A
125
50.689
20.112
2.669
1.00
32.97
8
ATOM
983
N
HIS
A
126
50.594
21.246
0.725
1.00
29.92
7
ATOM
984
CA
HIS
A
126
49.259
20.776
0.381
1.00
29.41
6
ATOM
985
C
HIS
A
126
49.186
19.276
0.256
1.00
29.27
6
ATOM
986
O
HIS
A
126
48.500
18.637
1.071
1.00
29.29
8
ATOM
987
CB
HIS
A
126
48.782
21.451
−0.934
1.00
29.82
6
ATOM
988
CG
HIS
A
126
47.453
20.951
−1.417
1.00
30.87
6
ATOM
989
ND1
HIS
A
126
46.254
21.263
−0.790
1.00
32.42
7
ATOM
990
CD2
HIS
A
126
47.135
20.149
−2.435
1.00
30.12
6
ATOM
991
CE1
HIS
A
126
45.274
20.643
−1.373
1.00
30.81
6
ATOM
992
NE2
HIS
A
126
45.765
19.970
−2.384
1.00
33.87
7
ATOM
993
N
PHE
A
127
49.882
18.662
−0.698
1.00
25.60
7
ATOM
994
CA
PHE
A
127
49.770
17.232
−0.922
1.00
25.14
6
ATOM
995
C
PHE
A
127
50.320
16.367
0.221
1.00
24.25
6
ATOM
996
O
PHE
A
127
49.733
15.332
0.490
1.00
23.64
8
ATOM
997
CB
PHE
A
127
50.454
16.851
−2.264
1.00
25.66
6
ATOM
998
CG
PHE
A
127
49.518
17.250
−3.398
1.00
24.51
6
ATOM
999
CD1
PHE
A
127
49.899
18.239
−4.302
1.00
25.76
6
ATOM
1000
CD2
PHE
A
127
48.239
16.734
−3.509
1.00
26.77
6
ATOM
1001
CE1
PHE
A
127
49.026
18.618
−5.301
1.00
27.57
6
ATOM
1002
CE2
PHE
A
127
47.381
17.086
−4.518
1.00
27.77
6
ATOM
1003
CZ
PHE
A
127
47.749
18.072
−5.444
1.00
28.09
6
ATOM
1004
N
ARG
A
128
51.218
16.966
1.006
1.00
24.68
7
ATOM
1005
CA
ARG
A
128
51.645
16.377
2.261
1.00
23.44
6
ATOM
1006
C
ARG
A
128
50.408
16.283
3.155
1.00
21.06
6
ATOM
1007
O
ARG
A
128
50.190
15.299
3.852
1.00
22.12
8
ATOM
1008
CB
ARG
A
128
52.743
17.172
2.975
1.00
26.43
6
ATOM
1009
CG
ARG
A
128
53.051
16.644
4.371
1.00
28.47
6
ATOM
1010
CD
ARG
A
128
54.116
17.508
5.117
1.00
27.86
6
ATOM
1011
NE
ARG
A
128
55.345
17.336
4.336
1.00
31.98
7
ATOM
1012
CZ
ARG
A
128
56.526
17.872
4.699
1.00
36.93
6
ATOM
1013
NH1
ARG
A
128
56.631
18.561
5.825
1.00
34.28
7
ATOM
1014
NH2
ARG
A
128
57.586
17.630
3.912
1.00
38.42
7
ATOM
1015
N
GLY
A
129
49.588
17.337
3.161
1.00
21.21
7
ATOM
1016
CA
GLY
A
129
48.391
17.274
4.018
1.00
21.01
6
ATOM
1017
C
GLY
A
129
47.468
16.152
3.484
1.00
21.29
6
ATOM
1018
O
GLY
A
129
46.782
15.601
4.321
1.00
21.30
8
ATOM
1019
N
VAL
A
130
47.317
16.084
2.166
1.00
21.70
7
ATOM
1020
CA
VAL
A
130
46.441
15.028
1.634
1.00
21.40
6
ATOM
1021
C
VAL
A
130
46.908
13.587
1.970
1.00
20.52
6
ATOM
1022
O
VAL
A
130
46.140
12.807
2.542
1.00
19.78
8
ATOM
1023
CB
VAL
A
130
46.256
15.179
0.107
1.00
22.23
6
ATOM
1024
CG1
VAL
A
130
45.496
13.992
−0.479
1.00
22.29
6
ATOM
1025
CG2
VAL
A
130
45.587
16.550
−0.161
1.00
22.53
6
ATOM
1026
N
SER
A
131
48.184
13.286
1.709
1.00
22.62
7
ATOM
1027
CA
SER
A
131
48.669
11.951
2.032
1.00
22.39
6
ATOM
1028
C
SER
A
131
48.617
11.685
3.541
1.00
20.26
6
ATOM
1029
O
SER
A
131
48.328
10.545
3.924
1.00
22.14
8
ATOM
1030
CB
SER
A
131
50.095
11.641
1.549
1.00
22.52
6
ATOM
1031
OG
SER
A
131
50.924
12.773
1.784
1.00
24.21
8
ATOM
1032
N
THR
A
132
48.883
12.678
4.393
1.00
17.99
7
ATOM
1033
CA
THR
A
132
48.785
12.419
5.812
1.00
17.46
6
ATOM
1034
C
THR
A
132
47.375
12.119
6.296
1.00
17.48
6
ATOM
1035
O
THR
A
132
47.180
11.104
7.013
1.00
17.25
8
ATOM
1036
CB
THR
A
132
49.386
13.645
6.619
1.00
17.40
6
ATOM
1037
OG1
THR
A
132
50.726
13.812
6.145
1.00
20.91
8
ATOM
1038
CG2
THR
A
132
49.302
13.374
8.096
1.00
18.97
6
ATOM
1039
N
ILE
A
133
46.378
12.918
5.840
1.00
17.51
7
ATOM
1040
CA
ILE
A
133
45.048
12.635
6.366
1.00
17.42
6
ATOM
1041
C
ILE
A
133
44.514
11.317
5.727
1.00
17.76
6
ATOM
1042
O
ILE
A
133
43.831
10.598
6.432
1.00
16.73
8
ATOM
1043
CB
ILE
A
133
44.056
13.814
6.199
1.00
19.04
6
ATOM
1044
CG1
ILE
A
133
42.772
13.574
6.991
1.00
18.12
6
ATOM
1045
CG2
ILE
A
133
43.692
14.007
4.713
1.00
19.62
6
ATOM
1046
CD1
ILE
A
133
43.077
13.562
8.543
1.00
19.23
6
ATOM
1047
N
VAL
A
134
44.834
11.013
4.468
1.00
20.06
7
ATOM
1048
CA
VAL
A
134
44.318
9.805
3.843
1.00
20.66
6
ATOM
1049
C
VAL
A
134
44.943
8.567
4.523
1.00
16.68
6
ATOM
1050
O
VAL
A
134
44.181
7.608
4.840
1.00
16.16
8
ATOM
1051
CB
VAL
A
134
44.556
9.769
2.329
1.00
20.12
6
ATOM
1052
CG1
VAL
A
134
43.968
8.529
1.685
1.00
20.31
6
ATOM
1053
CG2
VAL
A
134
43.953
11.019
1.680
1.00
21.96
6
ATOM
1054
N
SER
A
135
46.232
8.622
4.793
1.00
17.42
7
ATOM
1055
CA
SER
A
135
46.862
7.515
5.554
1.00
18.57
6
ATOM
1056
C
SER
A
135
46.167
7.337
6.870
1.00
18.10
6
ATOM
1057
O
SER
A
135
45.906
6.226
7.307
1.00
17.58
8
ATOM
1058
CB
SER
A
135
48.367
7.725
5.776
1.00
21.85
6
ATOM
1059
OG
SER
A
135
49.165
7.574
4.629
1.00
26.07
8
ATOM
1060
N
LYS
A
136
45.960
8.454
7.642
1.00
17.06
7
ATOM
1061
CA
LYS
A
136
45.344
8.319
8.939
1.00
16.75
6
ATOM
1062
C
LYS
A
136
43.943
7.726
8.855
1.00
16.59
6
ATOM
1063
O
LYS
A
136
43.549
6.804
9.565
1.00
17.77
8
ATOM
1064
CB
LYS
A
136
45.347
9.698
9.654
1.00
17.50
6
ATOM
1065
CG
LYS
A
136
44.778
9.658
11.055
1.00
17.92
6
ATOM
1066
CD
LYS
A
136
45.193
10.949
11.821
1.00
18.19
6
ATOM
1067
CE
LYS
A
136
44.719
10.824
13.255
1.00
20.47
6
ATOM
1068
NZ
LYS
A
136
45.341
11.921
14.099
1.00
21.74
7
ATOM
1069
N
LEU
A
137
43.114
8.215
7.905
1.00
16.58
7
ATOM
1070
CA
LEU
A
137
41.820
7.610
7.620
1.00
16.97
6
ATOM
1071
C
LEU
A
137
41.917
6.145
7.208
1.00
16.87
6
ATOM
1072
O
LEU
A
137
41.086
5.366
7.671
1.00
18.31
8
ATOM
1073
CB
LEU
A
137
41.186
8.426
6.450
1.00
16.26
6
ATOM
1074
CG
LEU
A
137
40.680
9.774
6.970
1.00
19.05
6
ATOM
1075
CD1
LEU
A
137
40.287
10.582
5.686
1.00
19.51
6
ATOM
1076
CD2
LEU
A
137
39.540
9.723
7.939
1.00
20.72
6
ATOM
1077
N
PHE
A
138
42.967
5.788
6.451
1.00
16.58
7
ATOM
1078
CA
PHE
A
138
43.010
4.341
6.127
1.00
18.39
6
ATOM
1079
C
PHE
A
138
43.255
3.486
7.348
1.00
18.60
6
ATOM
1080
O
PHE
A
138
42.757
2.384
7.504
1.00
17.30
8
ATOM
1081
CB
PHE
A
138
44.122
4.115
5.093
1.00
17.12
6
ATOM
1082
CG
PHE
A
138
43.764
4.570
3.689
1.00
18.73
6
ATOM
1083
CD1
PHE
A
138
44.806
4.543
2.766
1.00
17.88
6
ATOM
1084
CD2
PHE
A
138
42.473
4.892
3.307
1.00
18.91
6
ATOM
1085
CE1
PHE
A
138
44.536
4.879
1.448
1.00
20.01
6
ATOM
1886
CE2
PHE
A
138
42.230
5.257
1.997
1.00
19.56
6
ATOM
1087
CZ
PHE
A
138
43.254
5.215
1.074
1.00
19.96
6
ATOM
1088
N
ASN
A
139
44.082
4.007
8.264
1.00
18.42
7
ATOM
1089
CA
ASN
A
139
44.379
3.252
9.498
1.00
18.84
6
ATOM
1090
C
ASN
A
139
43.214
3.179
10.420
1.00
18.89
6
ATOM
1091
O
ASN
A
139
43.006
2.188
11.154
1.00
20.77
8
ATOM
1092
CB
ASN
A
139
45.584
3.896
10.226
1.00
18.65
6
ATOM
1093
CG
ASN
A
139
46.893
3.695
9.486
1.00
21.58
6
ATOM
1094
OD1
ASN
A
139
47.077
2.678
8.835
1.00
23.27
8
ATOM
1095
ND2
ASN
A
139
47.838
4.616
9.605
1.00
23.11
7
ATOM
1096
N
LEU
A
140
42.380
4.245
10.477
1.00
18.73
7
ATOM
1097
CA
LEU
A
140
41.227
4.287
11.337
1.00
19.89
6
ATOM
1098
C
LEU
A
140
40.035
3.500
10.798
1.00
22.66
6
ATOM
1099
O
LEU
A
140
39.348
2.886
11.581
1.00
23.40
8
ATOM
1100
CB
LEU
A
140
40.725
5.736
11.530
1.00
19.74
6
ATOM
1101
CG
LEU
A
140
41.667
6.734
12.211
1.00
20.69
6
ATOM
1102
CD1
LEU
A
140
41.159
8.189
12.222
1.00
20.47
6
ATOM
1103
CD2
LEU
A
140
41.923
6.357
13.687
1.00
21.82
6
ATOM
1104
N
VAL
A
141
39.777
3.644
9.493
1.00
21.89
7
ATOM
1105
CA
VAL
A
141
38.625
2.951
8.912
1.00
18.58
6
ATOM
1106
C
VAL
A
141
38.930
1.566
8.477
1.00
18.27
6
ATOM
1107
O
VAL
A
141
37.992
0.726
8.348
1.00
21.83
8
ATOM
1108
CB
VAL
A
141
38.121
3.897
7.749
1.00
17.89
6
ATOM
1109
CG1
VAL
A
141
37.004
3.204
6.948
1.00
19.45
6
ATOM
1110
CG2
VAL
A
141
37.684
5.229
8.360
1.00
19.31
6
ATOM
1111
N
GLN
A
142
40.157
1.207
8.147
1.00
19.32
7
ATOM
1112
CA
GLN
A
142
40.614
−0.046
7.611
1.00
22.31
6
ATOM
1113
C
GLN
A
142
39.731
−0.535
6.460
1.00
19.60
6
ATOM
1114
O
GLN
A
142
39.182
−1.647
6.518
1.00
20.68
8
ATOM
1115
CB
GLN
A
142
40.661
−1.162
8.674
1.00
23.95
6
ATOM
1116
CG
GLN
A
142
41.594
−0.685
9.829
1.00
28.73
6
ATOM
1117
CD
GLN
A
142
41.536
−1.705
10.951
1.00
34.39
6
ATOM
1118
OE1
GLN
A
142
42.491
−2.469
11.021
1.00
39.24
8
ATOM
1119
NE2
GLN
A
142
40.502
−1.784
11.754
1.00
35.26
7
ATOM
1120
N
PRO
A
143
39.558
0.297
5.442
1.00
18.88
7
ATOM
1121
CA
PRO
A
143
38.717
−0.119
4.346
1.00
18.57
6
ATOM
1122
C
PRO
A
143
39.398
−1.140
3.497
1.00
19.27
6
ATOM
1123
O
PRO
A
143
40.627
−1.225
3.382
1.00
21.22
8
ATOM
1124
CB
PRO
A
143
38.538
1.179
3.558
1.00
17.81
6
ATOM
1125
CG
PRO
A
143
39.829
1.905
3.755
1.00
17.73
6
ATOM
1126
CD
PRO
A
143
40.201
1.627
5.230
1.00
17.54
6
ATOM
1127
N
ASP
A
144
38.648
−1.982
2.768
1.00
17.55
7
ATOM
1128
CA
ASP
A
144
39.097
−2.852
1.720
1.00
20.28
6
ATOM
1129
C
ASP
A
144
39.283
−2.125
0.399
1.00
19.25
6
ATOM
1130
O
ASP
A
144
40.083
−2.459
−0.481
1.00
20.98
8
ATOM
1131
CB
ASP
A
144
38.033
−3.936
1.546
1.00
20.76
6
ATOM
1132
CG
ASP
A
144
37.957
−4.815
2.798
1.00
26.72
6
ATOM
1133
OD1
ASP
A
144
36.961
−4.629
3.528
1.00
28.28
8
ATOM
1134
OD2
ASP
A
144
38.895
−5.587
3.031
1.00
31.50
8
ATOM
1135
N
ILE
A
145
38.477
−1.081
0.131
1.00
17.25
7
ATOM
1136
CA
ILE
A
145
38.375
−0.260
−1.035
1.00
18.60
6
ATOM
1137
C
ILE
A
145
38.239
1.190
−0.687
1.00
18.09
6
ATOM
1138
O
ILE
A
145
37.607
1.491
0.327
1.00
18.47
8
ATOM
1139
CB
ILE
A
145
37.081
−0.719
−1.802
1.00
22.13
6
ATOM
1140
CG1
ILE
A
145
37.350
−2.164
−2.291
1.00
26.63
6
ATOM
1141
CG2
ILE
A
145
36.613
0.193
−2.934
1.00
28.58
6
ATOM
1142
CD1
ILE
A
145
35.987
−2.820
−2.537
1.00
33.01
6
ATOM
1143
N
ALA
A
146
38.745
2.119
−1.471
1.00
18.54
7
ATOM
1144
CA
ALA
A
146
38.555
3.525
−1.287
1.00
17.65
6
ATOM
1145
C
ALA
A
146
38.386
4.174
−2.669
1.00
18.82
6
ATOM
1146
O
ALA
A
146
39.158
3.831
−3.590
1.00
20.86
8
ATOM
1147
CB
ALA
A
146
39.754
4.169
−0.561
1.00
17.02
6
ATOM
1148
N
CYS
A
147
37.421
5.032
−2.758
1.00
17.39
7
ATOM
1149
CA
CYS
A
147
37.059
5.669
−4.042
1.00
19.79
6
ATOM
1150
C
CYS
A
147
37.462
7.132
−4.108
1.00
20.20
6
ATOM
1151
O
CYS
A
147
37.292
7.934
−3.181
1.00
20.69
8
ATOM
1152
CB
CYS
A
147
35.534
5.576
−4.235
1.00
21.84
6
ATOM
1153
SG
CYS
A
147
34.881
3.895
−4.275
1.00
25.91
16
ATOM
1154
N
PHE
A
148
38.073
7.481
−5.256
1.00
20.78
7
ATOM
1155
CA
PHE
A
148
38.521
8.824
−5.534
1.00
20.56
6
ATOM
1156
C
PHE
A
148
38.105
9.201
−6.955
1.00
20.31
6
ATOM
1157
O
PHE
A
148
38.047
8.291
−7.790
1.00
21.33
8
ATOM
1158
CB
PHE
A
148
40.044
8.856
−5.392
1.00
19.98
6
ATOM
1159
CG
PHE
A
148
40.527
8.697
−3.964
1.00
21.76
6
ATOM
1160
CD1
PHE
A
148
40.803
7.418
−3.472
1.00
21.62
6
ATOM
1161
CD2
PHE
A
148
40.682
9.781
−3.137
1.00
24.08
6
ATOM
1162
CE1
PHE
A
148
41.217
7.237
−2.164
1.00
21.64
6
ATOM
1163
CE2
PHE
A
148
41.150
9.580
−1.833
1.00
22.23
6
ATOM
1164
CZ
PHE
A
148
41.384
8.321
−1.337
1.00
21.48
6
ATOM
1165
N
GLY
A
149
37.874
10.485
−7.215
1.00
19.66
7
ATOM
1166
CA
GLY
A
149
37.457
10.782
−8.630
1.00
19.28
6
ATOM
1167
C
GLY
A
149
38.663
10.981
−9.537
1.00
21.16
6
ATOM
1168
O
GLY
A
149
39.696
11.548
−9.117
1.00
25.03
8
ATOM
1169
N
GLU
A
150
38.524
10.707
−10.848
1.00
21.70
7
ATOM
1170
CA
GLU
A
150
39.588
10.939
−11.809
1.00
25.98
6
ATOM
1171
C
GLU
A
150
39.777
12.386
−12.160
1.00
25.10
6
ATOM
1172
O
GLU
A
150
40.841
12.764
−12.668
1.00
26.55
8
ATOM
1173
CB
GLU
A
150
39.316
10.178
−13.146
1.00
28.34
6
ATOM
1174
CG
GLU
A
150
39.447
8.683
−12.924
1.00
30.38
6
ATOM
1175
CD
GLU
A
150
39.464
7.923
−14.241
1.00
36.75
6
ATOM
1176
OE1
GLU
A
150
39.222
8.536
−15.309
1.00
39.43
8
ATOM
1177
OE2
GLU
A
150
39.770
6.715
−14.171
1.00
39.37
8
ATOM
1178
N
LYS
A
151
38.795
13.240
−11.874
1.00
25.17
7
ATOM
1179
CA
LYS
A
151
38.970
14.660
−12.162
1.00
28.17
6
ATOM
1180
C
LYS
A
151
40.159
15.229
−11.400
1.00
29.47
6
ATOM
1181
O
LYS
A
151
40.955
16.017
−11.930
1.00
29.69
8
ATOM
1182
CB
LYS
A
151
37.710
15.423
−11.787
1.00
30.49
6
ATOM
1183
CG
LYS
A
151
37.865
16.877
−12.255
1.00
34.63
6
ATOM
1184
CD
LYS
A
151
37.021
17.827
−11.434
1.00
40.81
6
ATOM
1185
CE
LYS
A
151
37.161
19.249
−12.007
1.00
42.71
6
ATOM
1186
NZ
LYS
A
151
35.905
20.032
−11.825
1.00
46.87
7
ATOM
1187
N
ASP
A
152
40.274
14.877
−10.114
1.00
26.84
7
ATOM
1188
CA
ASP
A
152
41.456
15.268
−9.322
1.00
26.83
6
ATOM
1189
C
ASP
A
152
42.545
14.241
−9.529
1.00
26.30
6
ATOM
1190
O
ASP
A
152
42.933
13.366
−8.715
1.00
24.28
8
ATOM
1191
CB
ASP
A
152
41.078
15.419
−7.846
1.00
29.39
6
ATOM
1192
N
PHE
A
153
43.137
14.340
−10.746
1.00
24.76
7
ATOM
1193
CA
PHE
A
153
44.063
13.342
−11.241
1.00
24.28
6
ATOM
1194
C
PHE
A
153
45.350
13.353
−10.435
1.00
24.40
6
ATOM
1195
O
PHE
A
153
45.891
12.270
−10.274
1.00
24.91
8
ATOM
1196
CB
PHE
A
153
44.385
13.509
−12.748
1.00
26.30
6
ATOM
1197
CG
PHE
A
153
45.137
14.809
−12.939
1.00
29.67
6
ATOM
1198
CD1
PHE
A
153
46.517
14.828
−13.025
1.00
30.48
6
ATOM
1199
CD2
PHE
A
153
44.443
16.015
−13.033
1.00
32.69
6
ATOM
1200
CE1
PHE
A
153
47.203
16.017
−13.147
1.00
31.59
6
ATOM
1201
CE2
PHE
A
153
45.124
17.212
−13.186
1.00
33.09
6
ATOM
1202
CZ
PHE
A
153
46.511
17.215
−13.241
1.00
34.20
6
ATOM
1203
N
GLN
A
154
45.781
14.510
−9.931
1.00
25.98
7
ATOM
1204
CA
GLN
A
154
47.028
14.521
−9.174
1.00
22.85
6
ATOM
1205
C
GLN
A
154
46.851
13.825
−7.837
1.00
22.38
6
ATOM
1206
O
GLN
A
154
47.695
13.032
−7.413
1.00
22.53
8
ATOM
1207
CB
GLN
A
154
47.542
15.952
−8.933
1.00
24.08
6
ATOM
1208
CG
GLN
A
154
48.929
15.967
−8.287
1.00
26.39
6
ATOM
1209
CD
GLN
A
154
49.688
17.287
−8.508
1.00
28.37
6
ATOM
1210
OE1
GLN
A
154
49.098
18.244
−8.993
1.00
28.49
8
ATOM
1211
NE2
GLN
A
154
50.978
17.318
−8.158
1.00
26.87
7
ATOM
1212
N
GLN
A
155
45.747
14.096
−7.174
1.00
21.22
7
ATOM
1213
CA
GLN
A
155
45.470
13.411
−5.896
1.00
21.76
6
ATOM
1214
C
GLN
A
155
45.362
11.902
−6.092
1.00
21.39
6
ATOM
1215
O
GLN
A
155
45.852
11.100
−5.289
1.00
20.96
8
ATOM
1216
CB
GLN
A
155
44.157
13.885
−5.251
1.00
23.33
6
ATOM
1217
CG
GLN
A
155
44.285
15.020
−4.241
0.50
22.16
6
ATOM
1218
CD
GLN
A
155
43.185
14.991
−3.184
0.50
22.84
6
ATOM
1219
OE1
GLN
A
155
42.574
13.952
−2.872
0.50
25.23
8
ATOM
1220
NE2
GLN
A
155
42.921
16.140
−2.600
0.50
20.85
7
ATOM
1221
N
LEU
A
156
44.752
11.455
−7.214
1.00
20.25
7
ATOM
1222
CA
LEU
A
156
44.592
10.045
−7.465
1.00
18.93
6
ATOM
1223
C
LEU
A
156
45.938
9.367
−7.681
1.00
20.91
6
ATOM
1224
O
LEU
A
156
46.240
8.334
−7.081
1.00
20.99
8
ATOM
1225
CB
LEU
A
156
43.684
9.840
−8.695
1.00
20.06
6
ATOM
1226
CG
LEU
A
156
43.409
8.396
−9.060
1.00
21.79
6
ATOM
1227
CD1
LEU
A
156
42.773
7.624
−7.893
1.00
20.19
6
ATOM
1228
CD2
LEU
A
156
42.493
8.367
−10.300
1.00
23.41
6
ATOM
1229
N
ALA
A
157
46.790
9.991
−8.498
1.00
21.27
7
ATOM
1230
CA
ALA
A
157
48.139
9.424
−8.654
1.00
20.85
6
ATOM
1231
C
ALA
A
157
48.896
9.402
−7.339
1.00
22.15
6
ATOM
1232
O
ALA
A
157
49.617
8.451
−7.039
1.00
23.09
8
ATOM
1233
CB
ALA
A
157
48.919
10.292
−9.658
1.00
21.65
6
ATOM
1234
N
LEU
A
158
48.771
10.447
−6.537
1.00
21.63
7
ATOM
1235
CA
LEU
A
158
49.507
10.508
−5.235
1.00
20.79
6
ATOM
1236
C
LEU
A
158
49.117
9.373
−4.311
1.00
22.51
6
ATOM
1237
O
LEU
A
158
49.950
8.663
−3.702
1.00
22.35
8
ATOM
1238
CB
LEU
A
158
49.227
11.847
−4.583
1.00
23.18
6
ATOM
1239
CG
LEU
A
158
49.828
12.175
−3.211
1.00
25.19
6
ATOM
1240
CD1
LEU
A
158
51.099
12.952
−3.381
1.00
28.19
6
ATOM
1241
CD2
LEU
A
158
48.782
12.989
−2.433
1.00
26.28
6
ATOM
1242
N
ILE
A
159
47.765
9.231
−4.212
1.00
18.01
7
ATOM
1243
CA
ILE
A
159
47.322
8.127
−3.317
1.00
19.99
6
ATOM
1244
C
ILE
A
159
47.680
6.760
−3.864
1.00
18.66
6
ATOM
1245
O
ILE
A
159
48.038
5.871
−3.083
1.00
19.24
8
ATOM
1246
CB
ILE
A
159
45.805
8.275
−3.083
1.00
23.08
6
ATOM
1247
CG1
ILE
A
159
45.455
9.626
−2.443
1.00
21.73
6
ATOM
1248
CG2
ILE
A
159
45.232
7.181
−2.187
1.00
23.20
6
ATOM
1249
CD1
ILE
A
159
46.056
9.774
−1.063
1.00
27.28
6
ATOM
1250
N
ARG
A
160
47.514
6.493
−5.148
1.00
20.78
7
ATOM
1251
CA
ARG
A
160
47.956
5.202
−5.694
1.00
20.24
6
ATOM
1252
C
ARG
A
160
49.422
4.914
−5.397
1.00
21.57
6
ATOM
1253
O
ARG
A
160
49.738
3.802
−4.971
1.00
19.80
8
ATOM
1254
CB
ARG
A
160
47.708
5.074
−7.218
1.00
21.86
6
ATOM
1255
CG
ARG
A
160
46.192
5.007
−7.567
1.00
21.60
6
ATOM
1256
CD
ARG
A
160
46.195
4.575
−9.066
1.00
25.76
6
ATOM
1257
NE
ARG
A
160
44.867
4.625
−9.678
1.00
29.84
7
ATOM
1258
CZ
ARG
A
160
43.905
3.713
−9.455
1.00
32.53
6
ATOM
1259
NH1
ARG
A
160
44.040
2.653
−8.651
1.00
32.58
7
ATOM
1260
NH2
ARG
A
160
42.788
3.911
−10.168
1.00
34.80
7
ATOM
1261
N
LYS
A
161
50.322
5.905
−5.460
1.00
20.74
7
ATOM
1262
CA
LYS
A
161
51.733
5.714
−5.164
1.00
19.39
6
ATOM
1263
C
LYS
A
161
51.925
5.506
−3.674
1.00
19.31
6
ATOM
1264
O
LYS
A
161
52.628
4.596
−3.191
1.00
22.15
8
ATOM
1265
CB
LYS
A
161
52.523
6.929
−5.649
1.00
21.10
6
ATOM
1266
CG
LYS
A
161
54.009
6.900
−5.202
1.00
24.79
6
ATOM
1267
CD
LYS
A
161
54.612
5.615
−5.820
1.00
28.31
6
ATOM
1268
CE
LYS
A
161
56.100
5.758
−6.162
1.00
31.56
6
ATOM
1269
NZ
LYS
A
161
56.913
6.424
−5.128
1.00
26.44
7
ATOM
1270
N
MET
A
162
51.191
6.312
−2.834
1.00
20.30
7
ATOM
1271
CA
MET
A
162
51.287
6.115
−1.383
1.00
18.85
6
ATOM
1272
C
MET
A
162
50.851
4.750
−0.908
1.00
21.35
6
ATOM
1273
O
MET
A
162
51.504
4.085
−0.089
1.00
20.93
8
ATOM
1274
CB
MET
A
162
50.412
7.231
−0.702
1.00
21.14
6
ATOM
1275
CG
MET
A
162
50.512
7.132
0.818
1.00
21.47
6
ATOM
1276
SD
MET
A
162
49.291
8.186
1.642
1.00
23.59
16
ATOM
1277
CE
MET
A
162
47.948
6.994
1.780
1.00
27.52
6
ATOM
1278
N
VAL
A
163
49.808
4.217
−1.577
1.00
19.66
7
ATOM
1279
CA
VAL
A
163
49.304
2.897
−1.214
1.00
20.50
6
ATOM
1280
C
VAL
A
163
50.289
1.806
−1.612
1.00
19.37
6
ATOM
1281
O
VAL
A
163
50.554
0.867
−0.837
1.00
20.07
8
ATOM
1282
CB
VAL
A
163
47.914
2.672
−1.873
1.00
21.79
6
ATOM
1283
CG1
VAL
A
163
47.540
1.204
−1.894
1.00
22.15
6
ATOM
1284
CG2
VAL
A
163
46.897
3.536
−1.100
1.00
22.77
6
ATOM
1285
N
ALA
A
164
50.784
1.931
−2.837
1.00
21.03
7
ATOM
1286
CA
ALA
A
164
51.773
0.937
−3.276
1.00
22.98
6
ATOM
1287
C
ALA
A
164
53.006
0.925
−2.380
1.00
23.44
6
ATOM
1288
O
ALA
A
164
53.478
−0.126
−1.927
1.00
23.96
8
ATOM
1289
CB
ALA
A
164
52.136
1.263
−4.719
1.00
23.95
6
ATOM
1290
N
ASP
A
165
53.552
2.121
−2.154
1.00
21.54
7
ATOM
1291
CA
ASP
A
165
54.788
2.231
−1.387
1.00
23.74
6
ATOM
1292
C
ASP
A
165
54.639
1.784
0.052
1.00
24.26
6
ATOM
1293
O
ASP
A
165
55.440
1.000
0.544
1.00
24.84
8
ATOM
1294
CB
ASP
A
165
55.321
3.664
−1.384
1.00
22.61
6
ATOM
1295
CG
ASP
A
165
55.980
4.130
−2.662
1.00
24.69
6
ATOM
1296
OD1
ASP
A
165
56.269
3.286
−3.531
1.00
24.19
8
ATOM
1297
OD2
ASP
A
165
56.220
5.356
−2.781
1.00
24.88
8
ATOM
1298
N
MET
A
166
53.590
2.288
0.725
1.00
21.43
7
ATOM
1299
CA
MET
A
166
53.378
2.007
2.157
1.00
20.10
6
ATOM
1300
C
MET
A
166
52.785
0.652
2.486
1.00
21.04
6
ATOM
1301
O
MET
A
166
52.605
0.347
3.671
1.00
21.28
8
ATOM
1302
CB
MET
A
166
52.540
3.142
2.751
1.00
20.75
6
ATOM
1303
CG
MET
A
166
53.288
4.458
2.868
1.00
22.14
6
ATOM
1304
SD
MET
A
166
55.034
4.259
3.242
1.00
26.84
16
ATOM
1305
CE
MET
A
166
54.959
3.835
4.983
1.00
27.47
6
ATOM
1306
N
GLY
A
167
52.458
−0.170
1.510
1.00
20.03
7
ATOM
1307
CA
GLY
A
167
51.975
−1.522
1.790
1.00
22.00
6
ATOM
1308
C
GLY
A
167
50.526
−1.606
2.218
1.00
20.49
6
ATOM
1309
O
GLY
A
167
50.190
−2.660
2.782
1.00
24.46
8
ATOM
1310
N
PHE
A
168
49.685
−0.585
2.002
1.00
21.54
7
ATOM
1311
CA
PHE
A
168
48.287
−0.824
2.403
1.00
20.47
6
ATOM
1312
C
PHE
A
168
47.645
−1.917
1.546
1.00
19.05
6
ATOM
1313
O
PHE
A
168
47.704
−1.739
0.320
1.00
20.71
8
ATOM
1314
CB
PHE
A
168
47.563
0.509
2.296
1.00
21.24
6
ATOM
1315
CG
PHE
A
168
47.788
1.632
3.277
1.00
20.78
6
ATOM
1316
CD1
PHE
A
168
48.548
2.751
2.932
1.00
22.23
6
ATOM
1317
CD2
PHE
A
168
47.186
1.509
4.509
1.00
21.78
6
ATOM
1318
CE1
PHE
A
168
48.736
3.747
3.913
1.00
20.66
6
ATOM
1319
CE2
PHE
A
168
47.353
2.544
5.432
1.00
19.66
6
ATOM
1320
CZ
PHE
A
168
48.085
3.665
5.136
1.00
20.15
6
ATOM
1321
N
ASP
A
169
46.769
−2.693
2.126
1.00
22.42
7
ATOM
1322
CA
ASP
A
169
46.084
−3.767
1.356
1.00
22.89
6
ATOM
1323
C
ASP
A
169
44.743
−3.167
0.938
1.00
23.53
6
ATOM
1324
O
ASP
A
169
43.705
−3.617
1.427
1.00
23.13
8
ATOM
1325
CB
ASP
A
169
45.975
−5.057
2.147
1.00
28.05
6
ATOM
1326
CG
ASP
A
169
45.399
−6.229
1.376
1.00
32.61
6
ATOM
1327
OD1
ASP
A
169
45.492
−6.192
0.129
1.00
35.09
8
ATOM
1328
OD2
ASP
A
169
44.838
−7.159
1.975
1.00
37.69
8
ATOM
1329
N
ILE
A
170
44.751
−2.104
0.146
1.00
21.02
7
ATOM
1330
CA
ILE
A
170
43.499
−1.409
−0.181
1.00
21.69
6
ATOM
1331
C
ILE
A
170
43.372
−1.265
−1.677
1.00
21.49
6
ATOM
1332
O
ILE
A
170
44.334
−0.773
−2.304
1.00
22.63
8
ATOM
1333
CB
ILE
A
170
43.443
−0.013
0.493
1.00
21.71
6
ATOM
1334
CG1
ILE
A
170
43.459
−0.124
2.030
1.00
21.39
6
ATOM
1335
CG2
ILE
A
170
42.221
0.770
0.037
1.00
22.28
6
ATOM
1336
CD1
ILE
A
170
43.745
1.240
2.694
1.00
23.40
6
ATOM
1337
N
GLU
A
171
42.206
−1.583
−2.244
1.00
22.35
7
ATOM
1338
CA
GLU
A
171
41.960
−1.346
−3.656
1.00
22.51
6
ATOM
1339
C
GLU
A
171
41.609
0.133
−3.871
1.00
22.05
6
ATOM
1340
O
GLU
A
171
40.625
0.577
−3.278
1.00
20.97
8
ATOM
1341
CB
GLU
A
171
40.841
−2.288
−4.152
1.00
21.82
6
ATOM
1342
CG
GLU
A
171
40.514
−1.978
−5.601
1.00
28.71
6
ATOM
1343
CD
GLU
A
171
39.364
−2.857
−6.098
1.00
34.21
6
ATOM
1344
OE1
GLU
A
171
38.911
−3.740
−5.361
1.00
36.00
8
ATOM
1345
OE2
GLU
A
171
38.953
−2.650
−7.272
1.00
38.31
8
ATOM
1346
N
ILE
A
172
42.352
0.886
−4.680
1.00
20.37
7
ATOM
1347
CA
ILE
A
172
42.017
2.294
−4.940
1.00
19.10
6
ATOM
1348
C
ILE
A
172
41.196
2.347
−6.217
1.00
23.26
6
ATOM
1349
O
ILE
A
172
41.716
1.875
−7.239
1.00
26.08
8
ATOM
1350
CB
ILE
A
172
43.306
3.159
−5.019
1.00
22.26
6
ATOM
1351
CG1
ILE
A
172
44.060
2.969
−3.686
1.00
21.42
6
ATOM
1352
CG2
ILE
A
172
42.975
4.587
−5.345
1.00
23.49
6
ATOM
1353
CD1
ILE
A
172
43.283
3.498
−2.483
1.00
22.09
6
ATOM
1354
N
VAL
A
173
39.937
2.751
−6.114
1.00
20.87
7
ATOM
1355
CA
VAL
A
173
39.045
2.789
−7.278
1.00
23.09
6
ATOM
1356
C
VAL
A
173
39.073
4.218
−7.811
1.00
23.54
6
ATOM
1357
O
VAL
A
173
38.637
5.125
−7.058
1.00
23.05
8
ATOM
1358
CB
VAL
A
173
37.637
2.318
−6.861
1.00
22.84
6
ATOM
1359
CG1
VAL
A
173
36.675
2.449
−8.040
1.00
24.23
6
ATOM
1360
CG2
VAL
A
173
37.756
0.893
−6.307
1.00
23.19
6
ATOM
1361
N
GLY
A
174
39.480
4.451
−9.055
1.00
22.79
7
ATOM
1362
CA
GLY
A
174
39.509
5.765
−9.652
1.00
22.28
6
ATOM
1363
C
GLY
A
174
38.217
5.872
−10.462
1.00
25.76
6
ATOM
1364
O
GLY
A
174
37.972
4.984
−11.306
1.00
25.34
8
ATOM
1365
N
VAL
A
175
37.340
6.803
−10.087
1.00
22.69
7
ATOM
1366
CA
VAL
A
175
35.996
6.810
−10.712
1.00
21.96
6
ATOM
1367
C
VAL
A
175
36.025
7.779
−11.858
1.00
22.74
6
ATOM
1368
O
VAL
A
175
36.298
8.938
−11.632
1.00
19.20
8
ATOM
1369
CB
VAL
A
175
34.977
7.161
−9.632
1.00
21.95
6
ATOM
1370
CG1
VAL
A
175
33.557
7.328
−10.233
1.00
23.84
6
ATOM
1371
CG2
VAL
A
175
34.914
6.111
−8.501
1.00
20.67
6
ATOM
1372
N
PRO
A
176
35.590
7.430
−13.068
1.00
23.97
7
ATOM
1373
CA
PRO
A
176
35.714
8.344
−14.172
1.00
26.00
6
ATOM
1374
C
PRO
A
176
34.750
9.485
−14.090
1.00
23.25
6
ATOM
1375
O
PRO
A
176
33.689
9.357
−13.462
1.00
23.13
8
ATOM
1376
CB
PRO
A
176
35.429
7.464
−15.401
1.00
26.90
6
ATOM
1377
CG
PRO
A
176
35.554
6.062
−14.946
1.00
30.42
6
ATOM
1378
CD
PRO
A
176
35.214
6.053
−13.467
1.00
26.21
6
ATOM
1379
N
ILE
A
177
35.026
10.601
−14.706
1.00
25.15
7
ATOM
1380
CA
ILE
A
177
34.220
11.792
−14.882
1.00
25.60
6
ATOM
1381
C
ILE
A
177
32.858
11.452
−15.470
1.00
26.15
6
ATOM
1382
O
ILE
A
177
32.823
10.610
−16.392
1.00
25.13
8
ATOM
1383
CB
ILE
A
177
35.002
12.755
−15.816
1.00
27.16
6
ATOM
1384
CG1
ILE
A
177
36.095
13.432
−14.910
1.00
32.12
6
ATOM
1385
CG2
ILE
A
177
34.203
13.794
−16.565
1.00
27.48
6
ATOM
1386
CD1
ILE
A
177
37.253
13.907
−15.774
1.00
33.86
6
ATOM
1387
N
MET
A
178
31.789
11.892
−14.839
1.00
23.56
7
ATOM
1388
CA
MET
A
178
30.439
11.695
−15.338
1.00
22.41
6
ATOM
1389
C
MET
A
178
30.253
12.624
−16.564
1.00
19.13
6
ATOM
1390
O
MET
A
178
30.623
13.780
−16.493
1.00
19.54
8
ATOM
1391
CB
MET
A
178
29.352
12.079
−14.359
1.00
28.06
6
ATOM
1392
CG
MET
A
178
29.443
11.331
−13.018
1.00
34.50
6
ATOM
1393
SD
MET
A
178
28.135
11.774
−11.868
1.00
41.82
16
ATOM
1394
CE
MET
A
178
28.027
13.573
−11.994
1.00
44.07
6
ATOM
1395
N
ARG
A
179
29.559
12.130
−17.573
1.00
19.57
7
ATOM
1396
CA
ARG
A
179
29.384
12.934
−18.776
1.00
18.81
6
ATOM
1397
C
ARG
A
179
27.950
12.914
−19.257
1.00
19.43
6
ATOM
1398
O
ARG
A
179
27.182
12.014
−18.938
1.00
19.78
8
ATOM
1399
CB
ARG
A
179
30.252
12.380
−19.936
1.00
20.44
6
ATOM
1400
CG
ARG
A
179
31.757
12.403
−19.680
1.00
21.94
6
ATOM
1401
CD
ARG
A
179
32.547
11.665
−20.791
1.00
22.96
6
ATOM
1402
NE
ARG
A
179
33.928
11.849
−20.377
1.00
24.17
7
ATOM
1403
CZ
ARG
A
179
34.636
12.995
−20.379
1.00
23.08
6
ATOM
1404
NH1
ARG
A
179
34.146
14.147
−20.883
1.00
22.58
7
ATOM
1405
NH2
ARG
A
179
35.872
12.925
−19.895
1.00
25.87
7
ATOM
1406
N
ALA
A
180
27.526
13.954
−19.931
1.00
19.29
7
ATOM
1407
CA
ALA
A
180
26.247
14.023
−20.609
1.00
20.57
6
ATOM
1408
C
ALA
A
180
26.269
13.017
−21.785
1.00
20.46
6
ATOM
1409
O
ALA
A
180
27.305
12.438
−22.089
1.00
20.53
8
ATOM
1410
CB
ALA
A
180
26.009
15.430
−21.100
1.00
20.95
6
ATOM
1411
N
LYS
A
181
25.065
12.823
−22.355
1.00
23.00
7
ATOM
1412
CA
LYS
A
181
24.978
11.807
−23.436
1.00
25.24
6
ATOM
1413
C
LYS
A
181
25.745
12.150
−24.672
1.00
23.73
6
ATOM
1414
O
LYS
A
181
26.108
11.238
−25.439
1.00
25.08
8
ATOM
1415
CB
LYS
A
181
23.496
11.637
−23.802
1.00
25.36
6
ATOM
1416
CG
LYS
A
181
22.670
10.939
−22.755
1.00
29.60
6
ATOM
1417
CD
LYS
A
181
23.217
9.642
−22.291
1.00
31.75
6
ATOM
1418
N
ASP
A
182
26.027
13.427
−24.854
1.00
22.41
7
ATOM
1419
CA
ASP
A
182
26.844
13.896
−25.958
1.00
23.30
6
ATOM
1420
C
ASP
A
182
28.319
13.944
−25.618
1.00
24.01
6
ATOM
1421
O
ASP
A
182
29.102
14.328
−26.481
1.00
23.06
8
ATOM
1422
CB
ASP
A
182
26.269
15.241
−26.435
1.00
23.96
6
ATOM
1423
CG
ASP
A
182
26.307
16.365
−25.427
1.00
25.62
6
ATOM
1424
OD1
ASP
A
182
26.954
16.241
−24.359
1.00
24.83
8
ATOM
1425
OD2
ASP
A
182
25.690
17.397
−25.755
1.00
27.42
8
ATOM
1426
N
GLY
A
183
28.808
13.557
−24.413
1.00
19.95
7
ATOM
1427
CA
GLY
A
183
30.201
13.464
−24.071
1.00
23.13
6
ATOM
1428
C
GLY
A
1B3
30.666
14.607
−23.127
1.00
19.95
6
ATOM
1429
O
GLY
A
183
31.799
14.532
−22.661
1.00
21.39
8
ATOM
1430
N
LEU
A
184
29.882
15.681
−23.119
1.00
19.14
7
ATOM
1431
CA
LEU
A
184
30.339
16.847
−22.301
1.00
18.16
6
ATOM
1432
C
LEU
A
184
30.494
16.470
−20.832
1.00
18.40
6
ATOM
1433
O
LEU
A
184
29.587
15.913
−20.225
1.00
19.97
8
ATOM
1434
CB
LEU
A
184
29.377
18.028
−22.486
1.00
18.63
6
ATOM
1435
CG
LEU
A
184
29.738
19.280
−21.652
1.00
17.34
6
ATOM
1436
CD1
LEU
A
184
31.065
19.909
−22.111
1.00
19.12
6
ATOM
1437
CD2
LEU
A
184
28.615
20.311
−21.740
1.00
19.88
6
ATOM
1438
N
ALA
A
185
31.607
16.870
−20.184
1.00
16.12
7
ATOM
1439
CA
ALA
A
185
31.782
16.555
−18.761
1.00
18.63
6
ATOM
1440
C
ALA
A
185
30.744
17.337
−17.942
1.00
17.79
6
ATOM
1441
O
ALA
A
185
30.537
18.511
−18.196
1.00
18.57
8
ATOM
1442
CB
ALA
A
185
33.237
16.872
−18.396
1.00
20.34
6
ATOM
1443
N
LEU
A
186
30.024
16.634
−17.065
1.00
16.87
7
ATOM
1444
CA
LEU
A
186
29.020
17.352
−16.271
1.00
16.99
6
ATOM
1445
C
LEU
A
186
29.790
18.284
−15.327
1.00
17.67
6
ATOM
1446
O
LEU
A
186
30.768
17.866
−14.658
1.00
20.34
8
ATOM
1447
CB
LEU
A
186
28.117
16.384
−15.513
1.00
16.87
6
ATOM
1448
CG
LEU
A
186
27.300
15.408
−16.358
1.00
18.67
6
ATOM
1449
CD1
LEU
A
186
26.353
14.626
−15.456
1.00
20.67
6
ATOM
1450
CD2
LEU
A
186
26.520
16.166
−17.415
1.00
17.31
6
ATOM
1451
N
SER
A
187
29.252
19.481
−15.220
1.00
18.83
7
ATOM
1452
CA
SER
A
187
29.915
20.486
−14.382
1.00
17.18
6
ATOM
1453
C
SER
A
187
29.000
21.631
−14.105
1.00
17.64
6
ATOM
1454
O
SER
A
187
28.216
22.057
−14.964
1.00
18.63
8
ATOM
1455
CB
SER
A
187
31.153
21.021
−15.151
1.00
20.23
6
ATOM
1456
OG
SER
A
187
31.730
22.134
−14.430
1.00
20.91
8
ATOM
1457
N
SER
A
188
29.176
22.275
−12.905
1.00
17.55
7
ATOM
1458
CA
SER
A
188
28.463
23.548
−12.722
1.00
17.70
6
ATOM
1459
C
SER
A
188
28.806
24.605
−13.755
1.00
17.74
6
ATOM
1460
O
SER
A
188
28.014
25.522
−14.095
1.00
18.92
8
ATOM
1461
CB
SER
A
188
28.799
24.124
−11.327
1.00
19.73
6
ATOM
1462
OG
SER
A
188
30.220
24.296
−11.200
1.00
20.84
8
ATOM
1463
N
ARG
A
189
29.969
24.554
−14.393
1.00
18.16
7
ATOM
1464
CA
ARG
A
189
30.424
25.497
−15.393
1.00
19.85
6
ATOM
1465
C
ARG
A
189
29.538
25.498
−16.634
1.00
20.33
6
ATOM
1466
O
ARG
A
189
29.484
26.473
−17.348
1.00
21.91
8
ATOM
1467
CB
ARG
A
189
31.879
25.201
−15.823
1.00
20.55
6
ATOM
1468
CG
ARG
A
189
32.801
25.314
−14.605
1.00
22.89
6
ATOM
1469
CD
ARG
A
189
34.254
25.061
−15.042
1.00
23.21
6
ATOM
1470
NE
ARG
A
189
35.037
25.170
−13.785
1.00
25.97
7
ATOM
1471
CZ
ARG
A
189
36.121
25.924
−13.683
1.00
28.29
6
ATOM
1472
NH1
ARG
A
189
36.608
26.564
−14.711
1.00
26.60
7
ATOM
1473
NH2
ARG
A
189
36.744
25.966
−12.487
1.00
28.41
7
ATOM
1474
N
ASN
A
190
28.914
24.324
−16.956
1.00
19.42
7
ATOM
1475
CA
ASN
A
190
28.105
24.261
−18.156
1.00
19.64
6
ATOM
1476
C
ASN
A
190
26.963
25.235
−18.114
1.00
22.61
6
ATOM
1477
O
ASN
A
190
26.271
25.606
−19.109
1.00
23.27
8
ATOM
1478
CB
ASN
A
190
27.544
22.841
−18.332
1.00
19.54
6
ATOM
1479
CG
ASN
A
190
28.675
21.842
−18.530
1.00
21.41
6
ATOM
1480
OD1
ASN
A
190
28.471
20.621
−18.265
1.00
21.40
8
ATOM
1481
ND2
ASN
A
190
29.819
22.309
−18.997
1.00
19.16
7
ATOM
1497
N
GLY
A
191
26.554
25.616
−16.760
1.00
27.44
7
ATOM
1498
CA
GLY
A
191
25.459
26.574
−16.600
1.00
28.04
6
ATOM
1499
C
GLY
A
191
25.750
27.966
−17.117
1.00
29.70
6
ATOM
1500
O
GLY
A
191
24.790
28.715
−17.294
1.00
31.47
8
ATOM
1482
N
TYR
A
192
26.966
28.311
−17.457
1.00
26.92
7
ATOM
1483
CA
TYR
A
192
27.272
29.642
−17.970
1.00
29.88
6
ATOM
1484
C
TYR
A
192
27.308
29.633
−19.479
1.00
29.91
6
ATOM
1485
O
TYR
A
192
27.538
30.724
−20.046
1.00
34.28
8
ATOM
1486
CB
TYR
A
192
28.611
30.173
−17.427
1.00
30.32
6
ATOM
1487
CG
TYR
A
192
28.459
30.366
−15.928
1.00
32.17
6
ATOM
1488
CD1
TYR
A
192
28.608
29.256
−15.102
1.00
32.38
6
ATOM
1489
CD2
TYR
A
192
28.097
31.585
−15.362
1.00
34.00
6
ATOM
1490
CE1
TYR
A
192
28.438
29.352
−13.751
1.00
35.21
6
ATOM
1491
CE2
TYR
A
192
27.927
31.687
−13.985
1.00
34.55
6
ATOM
1492
CZ
TYR
A
192
28.106
30.589
−13.195
1.00
36.66
6
ATOM
1493
OH
TYR
A
192
27.942
30.636
−11.819
1.00
38.33
8
ATOM
1494
N
LEU
A
193
27.090
28.487
−20.135
1.00
28.20
7
ATOM
1495
CA
LEU
A
193
27.054
28.479
−21.575
1.00
26.63
6
ATOM
1496
C
LEU
A
193
25.718
28.903
−22.154
1.00
27.15
6
ATOM
1497
O
LEU
A
193
24.697
28.434
−21.647
1.00
28.28
8
ATOM
1498
CB
LEU
A
193
27.315
27.057
−22.112
1.00
26.20
6
ATOM
1499
CG
LEU
A
193
28.613
26.402
−21.654
1.00
25.58
6
ATOM
1500
CD1
LEU
A
193
28.593
24.905
−21.877
1.00
24.08
6
ATOM
1501
CD2
LEU
A
193
29.827
27.005
−22.390
1.00
27.77
6
ATOM
1502
N
THR
A
194
25.679
29.616
−23.303
1.00
28.42
7
ATOM
1503
CA
THR
A
194
24.376
29.825
−23.934
1.00
27.62
6
ATOM
1504
C
THR
A
194
23.892
28.531
−24.561
1.00
25.74
6
ATOM
1505
O
THR
A
194
24.735
27.621
−24.723
1.00
26.48
8
ATOM
1506
CB
THR
A
194
24.463
30.922
−25.011
1.00
29.34
6
ATOM
1507
OG1
THR
A
194
25.465
30.535
−25.956
1.00
30.55
8
ATOM
1508
CG2
THR
A
194
24.862
32.238
−24.353
1.00
32.65
6
ATOM
1509
N
ALA
A
195
22.663
28.446
−25.043
1.00
25.15
7
ATOM
1510
CA
ALA
A
195
22.211
27.253
−25.755
1.00
25.73
6
ATOM
1511
C
ALA
A
195
23.105
26.994
−26.972
1.00
28.33
6
ATOM
1512
O
ALA
A
195
23.460
25.834
−27.241
1.00
28.09
8
ATOM
1513
CB
ALA
A
195
20.768
27.315
−26.209
1.00
25.63
6
ATOM
1514
N
GLU
A
196
23.486
28.068
−27.703
1.00
27.21
7
ATOM
1515
CA
GLU
A
196
24.366
27.886
−28.843
1.00
28.84
6
ATOM
1516
C
GLU
A
196
25.718
27.351
−28.424
1.00
25.77
6
ATOM
1517
O
GLU
A
196
26.282
26.445
−29.054
1.00
30.10
8
ATOM
1518
CB
GLU
A
196
24.534
29.239
−29.570
1.00
31.35
6
ATOM
1519
N
GLN
A
197
26.278
27.889
−27.328
1.00
26.45
7
ATOM
1520
CA
GLN
A
197
27.567
27.412
−26.855
1.00
25.85
6
ATOM
1521
C
GLN
A
197
27.489
25.961
−26.330
1.00
25.97
6
ATOM
1522
O
GLN
A
197
28.406
25.210
−26.618
1.00
25.79
8
ATOM
1523
CB
GLN
A
197
28.157
28.273
−25.717
1.00
27.14
6
ATOM
1524
CG
GLN
A
197
28.452
29.662
−26.408
1.00
29.94
6
ATOM
1525
CD
GLN
A
197
28.544
30.739
−25.358
1.00
31.03
6
ATOM
1526
OE1
GLN
A
197
28.249
30.597
−24.174
1.00
31.48
8
ATOM
1527
NE2
GLN
A
197
28.949
31.963
−25.739
1.00
30.58
7
ATOM
1528
N
ARG
A
198
26.335
25.639
−25.736
1.00
23.62
7
ATOM
1529
CA
ARG
A
198
26.151
24.282
−25.209
1.00
23.58
6
ATOM
1530
C
ARG
A
198
26.204
23.282
−26.345
1.00
24.98
6
ATOM
1531
O
ARG
A
198
26.761
22.214
−26.214
1.00
25.17
8
ATOM
1532
CB
ARG
A
198
24.831
24.133
−24.454
1.00
22.16
6
ATOM
1533
CG
ARG
A
198
24.576
22.689
−23.946
1.00
21.81
6
ATOM
1534
CD
ARG
A
198
25.656
22.194
−23.010
1.00
22.56
6
ATOM
1535
NE
ARG
A
198
25.386
20.830
−22.532
1.00
21.88
7
ATOM
1536
CZ
ARG
A
198
25.614
19.724
−23.247
1.00
24.32
6
ATOM
1537
NH1
ARG
A
198
25.384
18.481
−22.824
1.00
23.45
7
ATOM
1538
NH2
ARG
A
198
26.118
19.830
−24.477
1.00
25.14
7
ATOM
1539
N
LYS
A
199
25.707
23.649
−27.549
1.00
23.80
7
ATOM
1540
CA
LYS
A
199
25.820
22.710
−28.684
1.00
22.66
6
ATOM
1541
C
LYS
A
199
27.221
22.558
−29.202
1.00
22.59
6
ATOM
1542
O
LYS
A
199
27.608
21.508
−29.753
1.00
24.00
8
ATOM
1543
CB
LYS
A
199
24.855
23.272
−29.743
1.00
25.23
6
ATOM
1544
CG
LYS
A
199
24.661
22.284
−30.903
1.00
27.40
6
ATOM
1545
CD
LYS
A
199
23.602
22.991
−31.802
1.00
32.35
6
ATOM
1546
CE
LYS
A
199
23.336
22.059
−32.983
1.00
36.02
6
ATOM
1547
NZ
LYS
A
199
22.311
22.674
−33.894
1.00
38.59
7
ATOM
1548
N
ILE
A
200
28.111
23.556
−29.074
1.00
22.04
7
ATOM
1549
CA
ILE
A
200
29.513
23.458
−29.440
1.00
25.05
6
ATOM
1550
C
ILE
A
200
30.415
22.725
−28.438
1.00
23.70
6
ATOM
1551
O
ILE
A
200
31.347
21.980
−28.775
1.00
22.15
8
ATOM
1552
CB
ILE
A
200
30.128
24.863
−29.575
1.00
25.43
6
ATOM
1553
CG1
ILE
A
200
29.457
25.528
−30.809
1.00
26.99
6
ATOM
1554
CG2
ILE
A
200
31.644
24.911
−29.704
1.00
26.61
6
ATOM
1555
CD1
ILE
A
200
29.746
27.029
−30.827
1.00
28.65
6
ATOM
1556
N
ALA
A
201
29.987
22.836
−27.170
1.00
22.88
7
ATOM
1557
CA
ALA
A
201
30.773
22.278
−26.053
1.00
24.80
6
ATOM
1558
C
ALA
A
201
31.217
20.829
−26.110
1.00
23.52
6
ATOM
1559
O
ALA
A
201
32.363
20.607
−25.709
1.00
21.96
8
ATOM
1560
CB
ALA
A
201
29.913
22.499
−24.781
1.00
24.70
6
ATOM
1561
N
PRO
A
202
30.498
19.846
−26.659
1.00
24.18
7
ATOM
1562
CA
PRO
A
202
30.946
18.473
−26.796
1.00
24.19
6
ATOM
1563
C
PRO
A
202
32.191
18.288
−27.649
1.00
26.04
6
ATOM
1564
O
PRO
A
202
32.900
17.282
−27.556
1.00
25.77
8
ATOM
1565
CB
PRO
A
202
29.759
17.693
−27.382
1.00
24.31
6
ATOM
1566
CG
PRO
A
202
28.579
18.572
−27.068
1.00
23.02
6
ATOM
1567
CD
PRO
A
202
29.073
19.991
−27.051
1.00
22.33
6
ATOM
1568
N
GLY
A
203
32.559
19.351
−28.406
1.00
25.61
7
ATOM
1569
CA
GLY
A
203
33.779
19.327
−29.179
1.00
26.22
6
ATOM
1570
C
GLY
A
203
35.012
19.196
−28.324
1.00
24.81
6
ATOM
1571
O
GLY
A
203
36.061
18.750
−28.817
1.00
24.88
8
ATOM
1572
N
LEU
A
204
34.999
19.724
−27.082
1.00
23.90
7
ATOM
1573
CA
LEU
A
204
36.199
19.561
−26.254
1.00
23.72
6
ATOM
1574
C
LEU
A
204
36.550
18.119
−26.035
1.00
23.32
6
ATOM
1575
O
LEU
A
204
37.689
17.689
−26.239
1.00
24.33
8
ATOM
1576
CB
LEU
A
204
35.957
20.361
−24.936
1.00
24.53
6
ATOM
1577
CG
LEU
A
204
37.111
20.290
−23.972
1.00
25.84
6
ATOM
1578
CD1
LEU
A
204
38.425
20.791
−24.586
1.00
26.75
6
ATOM
1579
CD2
LEU
A
204
36.806
21.156
−22.742
1.00
26.68
6
ATOM
1580
N
TYR
A
205
35.580
17.243
−25.663
1.00
21.57
7
ATOM
1581
CA
TYR
A
205
35.804
15.836
−25.435
1.00
22.36
6
ATOM
1582
C
TYR
A
205
36.200
15.116
−26.748
1.00
21.69
6
ATOM
1583
O
TYR
A
205
37.041
14.212
−26.762
1.00
23.95
8
ATOM
1584
CB
TYR
A
205
34.533
15.211
−24.809
1.00
21.96
6
ATOM
1585
CG
TYR
A
205
34.766
13.758
−24.505
1.00
25.55
6
ATOM
1586
CD1
TYR
A
205
35.727
13.322
−23.619
1.00
27.86
6
ATOM
1587
CD2
TYR
A
205
34.059
12.802
−25.253
1.00
29.16
6
ATOM
1588
CE1
TYR
A
205
35.901
11.979
−23.364
1.00
30.07
6
ATOM
1589
CE2
TYR
A
205
34.261
11.448
−25.003
1.00
30.89
6
ATOM
1590
CZ
TYR
A
205
35.158
11.053
−24.064
1.00
32.67
6
ATOM
1591
OH
TYR
A
205
35.373
9.702
−23.839
1.00
36.20
8
ATOM
1592
N
LYS
A
206
35.652
15.679
−27.833
1.00
23.35
7
ATOM
1593
CA
LYS
A
206
36.040
15.114
−29.149
1.00
24.75
6
ATOM
1594
C
LYS
A
206
37.530
15.306
−29.401
1.00
24.74
6
ATOM
1595
O
LYS
A
206
38.252
14.359
−29.757
1.00
26.16
8
ATOM
1596
CB
LYS
A
206
35.223
15.740
−30.293
1.00
25.21
6
ATOM
1597
CG
LYS
A
206
33.784
15.236
−30.295
1.00
30.61
6
ATOM
1598
CD
LYS
A
206
33.118
15.648
−31.621
1.00
34.58
6
ATOM
1599
CE
LYS
A
206
31.600
15.547
−31.489
1.00
37.70
6
ATOM
1600
NZ
LYS
A
206
30.951
15.934
−32.794
1.00
40.74
7
ATOM
1601
N
VAL
A
207
37.995
16.518
−29.128
1.00
25.56
7
ATOM
1602
CA
VAL
A
207
39.432
16.818
−29.324
1.00
26.41
6
ATOM
1603
C
VAL
A
207
40.240
16.016
−28.333
1.00
26.75
6
ATOM
1604
O
VAL
A
207
41.246
15.351
−28.662
1.00
26.06
8
ATOM
1605
CB
VAL
A
207
39.714
18.318
−29.266
1.00
26.88
6
ATOM
1606
CG1
VAL
A
207
41.212
18.590
−29.172
1.00
27.69
6
ATOM
1607
CG2
VAL
A
207
39.062
18.967
−30.489
1.00
27.15
6
ATOM
1608
N
LEU
A
208
39.793
15.917
−27.065
1.00
26.81
7
ATOM
1609
CA
LEU
A
208
40.472
15.110
−26.079
1.00
26.80
6
ATOM
1610
C
LEU
A
208
40.555
13.645
−26.462
1.00
27.53
6
ATOM
1611
O
LEU
A
208
41.616
13.017
−26.276
1.00
27.79
8
ATOM
1612
CB
LEU
A
208
39.736
15.325
−24.732
1.00
28.31
6
ATOM
1613
CG
LEU
A
208
40.248
14.531
−23.535
1.00
31.14
6
ATOM
1614
CD1
LEU
A
208
41.649
14.906
−23.142
1.00
31.37
6
ATOM
1615
CD2
LEU
A
208
39.288
14.741
−22.347
1.00
33.29
6
ATOM
1616
N
SER
A
209
39.539
13.042
−27.028
1.00
26.96
7
ATOM
1617
CA
SER
A
209
39.536
11.655
−27.442
1.00
28.65
6
ATOM
1618
C
SER
A
209
40.427
11.463
−28.696
1.00
30.30
6
ATOM
1619
O
SER
A
209
41.021
10.401
−28.829
1.00
29.86
8
ATOM
1620
CB
SER
A
209
38.141
11.126
−27.751
1.00
32.08
6
ATOM
1621
OG
SER
A
209
37.320
11.455
−26.630
1.00
36.96
8
ATOM
1622
N
SER
A
210
40.502
12.521
−29.507
1.00
31.09
7
ATOM
1623
CA
SEP
A
210
41.372
12.426
−30.703
1.00
33.89
6
ATOM
1624
C
SER
A
210
42.826
12.447
−30.297
1.00
33.77
6
ATOM
1625
O
SER
A
210
43.687
11.734
−30.842
1.00
34.87
8
ATOM
1626
CB
SER
A
210
41.024
13.563
−31.655
1.00
36.51
6
ATOM
1627
OG
SER
A
210
42.171
13.743
−32.490
1.00
42.40
8
ATOM
1628
N
ILE
A
211
43.172
13.190
−29.230
1.00
31.25
7
ATOM
1629
CA
ILE
A
211
44.530
13.129
−28.705
1.00
30.79
6
ATOM
1630
C
ILE
A
211
44.815
11.731
−28.188
1.00
31.65
6
ATOM
1631
O
ILE
A
211
45.878
11.124
−28.405
1.00
31.20
8
ATOM
1632
CB
ILE
A
211
44.710
14.154
−27.580
1.00
30.45
6
ATOM
1633
CG1
ILE
A
211
44.646
15.580
−28.137
1.00
29.16
6
ATOM
1634
CG2
ILE
A
211
46.009
13.912
−26.797
1.00
28.20
6
ATOM
1635
CD1
ILE
A
211
44.501
16.613
−27.014
1.00
28.78
6
ATOM
1636
N
ALA
A
212
43.882
11.162
−27.426
1.00
31.19
7
ATOM
1637
CA
ALA
A
212
44.069
9.828
−26.852
1.00
31.19
6
ATOM
1638
C
ALA
A
212
44.251
8.789
−27.955
1.00
33.70
6
ATOM
1639
O
ALA
A
212
45.100
7.892
−27.832
1.00
34.72
8
ATOM
1640
CB
ALA
A
212
42.879
9.427
−25.995
1.00
31.27
6
ATOM
1641
N
ASP
A
213
43.478
8.916
−29.045
1.00
32.83
7
ATOM
1642
CA
ASP
A
213
43.576
7.982
−30.167
1.00
34.55
6
ATOM
1643
C
ASP
A
213
45.008
7.998
−30.723
1.00
34.80
6
ATOM
1644
O
ASP
A
213
45.616
6.938
−30.847
1.00
36.87
8
ATOM
1645
CB
ASP
A
213
42.567
8.322
−31.256
1.00
33.87
6
ATOM
1646
CG
ASP
A
213
41.145
7.900
−30.886
1.00
36.07
6
ATOM
1647
OD1
ASP
A
213
40.932
7.091
−29.951
1.00
36.03
8
ATOM
1648
OD2
ASP
A
213
40.224
8.400
−31.585
1.00
36.99
8
ATOM
1649
N
LYS
A
214
45.527
9.193
−30.994
1.00
34.39
7
ATOM
1650
CA
LYS
A
214
46.892
9.357
−31.506
1.00
35.31
6
ATOM
1651
C
LYS
A
214
47.904
8.782
−30.536
1.00
37.91
6
ATOM
1652
O
LYS
A
214
48.900
8.106
−30.920
1.00
39.73
8
ATOM
1653
CB
LYS
A
214
47.196
10.833
−31.789
1.00
33.06
6
ATOM
1654
CG
LYS
A
214
46.295
11.525
−32.774
1.00
33.68
6
ATOM
1655
CD
LYS
A
214
46.733
12.968
−33.079
1.00
32.27
6
ATOM
1656
CE
LYS
A
214
45.891
13.544
−34.215
1.00
33.88
6
ATOM
1657
NZ
LYS
A
214
46.243
14.978
−34.497
1.00
35.57
7
ATOM
1658
N
LEU
A
215
47.726
9.056
−29.227
1.00
38.37
7
ATOM
1659
CA
LEU
A
215
48.742
8.507
−28.299
1.00
41.26
6
ATOM
1660
C
LEU
A
215
48.676
6.988
−28.267
1.00
42.76
6
ATOM
1661
O
LEU
A
215
49.717
6.311
−28.250
1.00
43.43
8
ATOM
1662
CB
LEU
A
215
48.615
9.016
−26.871
1.00
38.15
6
ATOM
1663
CG
LEU
A
215
48.941
10.483
−26.658
1.00
39.14
6
ATOM
1664
CD1
LEU
A
215
48.406
10.973
−25.306
1.00
39.20
6
ATOM
1665
CD2
LEU
A
215
50.441
10.749
−26.718
1.00
39.00
6
ATOM
1666
N
GLN
A
216
47.493
6.407
−28.253
1.00
44.37
7
ATOM
1667
CA
GLN
A
216
47.328
4.952
−28.225
1.00
47.10
6
ATOM
1668
C
GLN
A
216
47.833
4.272
−29.499
1.00
47.76
6
ATOM
1669
O
GLN
A
216
48.153
3.081
−29.469
1.00
48.80
8
ATOM
1670
CD
GLN
A
216
45.859
4.643
−27.991
1.00
48.55
6
ATOM
1671
CG
GLN
A
216
45.452
3.303
−27.435
1.00
50.81
6
ATOM
1672
CD
GLN
A
216
44.259
3.444
−26.493
1.00
53.17
6
ATOM
1673
OE1
GLN
A
216
43.252
4.063
−26.856
1.00
54.69
8
ATOM
1674
NE2
GLN
A
216
44.354
2.898
−25.279
1.00
53.81
7
ATOM
1675
N
ALA
A
217
47.944
4.977
−30.617
1.00
47.64
7
ATOM
1676
CA
ALA
A
217
48.431
4.433
−31.869
1.00
48.49
6
ATOM
1677
C
ALA
A
217
49.948
4.569
−31.997
1.00
48.68
6
ATOM
1678
O
ALA
A
217
50.517
4.182
−33.024
1.00
51.00
8
ATOM
1679
CB
ALA
A
217
47.789
5.138
−33.060
1.00
47.71
6
ATOM
1680
N
GLY
A
218
50.612
5.211
−31.056
1.00
47.70
7
ATOM
1681
CA
GLY
A
218
52.037
5.390
−31.027
1.00
46.44
6
ATOM
1682
C
GLY
A
218
52.539
6.780
−31.316
1.00
47.59
6
ATOM
1683
O
GLY
A
218
53.771
6.979
−31.285
1.00
47.50
8
ATOM
1684
N
GLU
A
219
51.677
7.755
−31.607
1.00
45.89
7
ATOM
1685
CA
GLU
A
219
52.216
9.086
−31.891
1.00
46.96
6
ATOM
1686
C
GLU
A
219
52.912
9.624
−30.651
1.00
48.26
6
ATOM
1687
O
GLU
A
219
52.403
9.484
−29.530
1.00
48.86
8
ATOM
1688
CB
GLU
A
219
51.146
10.071
−32.380
1.00
47.88
6
ATOM
1689
CG
GLU
A
219
50.460
9.695
−33.672
1.00
48.05
6
ATOM
1690
CD
GLU
A
219
49.744
10.817
−34.384
1.00
50.68
6
ATOM
1691
OE1
GLU
A
219
50.134
12.015
−34.408
1.00
51.01
8
ATOM
1692
OE2
GLU
A
219
48.702
10.497
−35.025
1.00
52.09
8
ATOM
1693
N
ARG
A
220
54.135
10.154
−30.831
1.00
47.68
7
ATOM
1694
CA
ARG
A
220
54.868
10.698
−29.694
1.00
47.37
6
ATOM
1695
C
ARG
A
220
55.402
12.091
−29.989
1.00
47.62
6
ATOM
1696
O
ARG
A
220
56.106
12.622
−29.125
1.00
49.49
8
ATOM
1697
CB
ARG
A
220
56.014
9.790
−29.239
1.00
46.78
6
ATOM
1698
CG
ARG
A
220
55.570
8.463
−28.643
1.00
46.54
6
ATOM
1699
CD
ARG
A
220
54.878
8.628
−27.293
1.00
45.80
6
ATOM
1700
NE
ARG
A
220
54.371
7.359
−26.801
1.00
45.04
7
ATOM
1701
CZ
ARG
A
220
53.281
6.683
−27.074
1.00
44.93
6
ATOM
1702
NH1
ARG
A
220
52.341
7.093
−27.930
1.00
45.42
7
ATOM
1703
NH2
ARG
A
220
53.080
5.516
−26.476
1.00
44.28
7
ATOM
1704
N
ASP
A
221
54.976
12.756
−31.052
1.00
48.60
7
ATOM
1705
CA
ASP
A
221
55.381
14.161
−31.242
1.00
48.15
6
ATOM
1706
C
ASP
A
221
54.296
15.005
−30.557
1.00
46.06
6
ATOM
1707
O
ASP
A
221
53.379
15.515
−31.197
1.00
44.76
8
ATOM
1708
CB
ASP
A
221
55.576
14.527
−32.691
1.00
50.20
6
ATOM
1709
CG
ASP
A
221
56.053
15.928
−32.988
1.00
53.21
6
ATOM
1710
OD1
ASP
A
221
56.188
16.801
−32.101
1.00
53.81
8
ATOM
1711
OD2
ASP
A
221
56.309
16.204
−34.191
1.00
55.09
8
ATOM
1712
N
LEU
A
222
54.465
15.167
−29.249
1.00
43.92
7
ATOM
1713
CA
LEU
A
222
53.451
15.829
−28.427
1.00
42.81
6
ATOM
1714
C
LEU
A
222
53.215
17.271
−28.774
1.00
43.64
6
ATOM
1715
O
LEU
A
222
52.066
17.762
−28.789
1.00
41.82
8
ATOM
1716
CB
LEU
A
222
53.894
15.652
−26.952
1.00
43.09
6
ATOM
1717
CG
LEU
A
222
54.196
14.191
−26.578
1.00
41.83
6
ATOM
1718
CD1
LEU
A
222
54.442
14.033
−25.081
1.00
42.53
6
ATOM
1719
CD2
LEU
A
222
53.086
13.237
−26.991
1.00
41.15
6
ATOM
1720
N
ASP
A
223
54.285
18.012
−29.105
1.00
43.23
7
ATOM
1721
CA
ASP
A
223
54.124
19.416
−29.472
1.00
44.33
6
ATOM
1722
C
ASP
A
223
53.223
19.562
−30.688
1.00
44.26
6
ATOM
1723
O
ASP
A
223
52.401
20.490
−30.770
1.00
45.10
8
ATOM
1724
CB
ASP
A
223
55.508
20.042
−29.717
1.00
45.77
6
ATOM
1725
N
GLU
A
224
53.398
18.654
−31.651
1.00
44.43
7
ATOM
1726
CA
GLU
A
224
52.583
18.676
−32.863
1.00
45.57
6
ATOM
1727
C
GLU
A
224
51.126
18.332
−32.533
1.00
41.13
6
ATOM
1728
O
GLU
A
224
50.187
18.995
−32.967
1.00
40.57
8
ATOM
1729
CB
GLU
A
224
53.146
17.723
−33.915
1.00
49.14
6
ATOM
1730
CG
GLU
A
224
52.327
17.645
−35.186
1.00
53.71
6
ATOM
1731
CD
GLU
A
224
52.241
18.926
−35.991
1.00
57.27
6
ATOM
1732
OE1
GLU
A
224
52.627
20.028
−35.530
1.00
58.34
8
ATOM
1733
OE2
GLU
A
224
51.738
18.792
−37.141
1.00
59.44
8
ATOM
1734
N
ILE
A
225
50.928
17.234
−31.837
1.00
38.07
7
ATOM
1735
CA
ILE
A
225
49.602
16.821
−31.360
1.00
36.44
6
ATOM
1736
C
ILE
A
225
48.838
17.929
−30.641
1.00
35.31
6
ATOM
1737
O
ILE
A
225
47.630
18.075
−30.873
1.00
34.79
8
ATOM
1738
CB
ILE
A
225
49.745
15.630
−30.401
1.00
36.23
6
ATOM
1739
CG1
ILE
A
225
50.310
14.449
−31.200
1.00
36.60
6
ATOM
1740
CG2
ILE
A
225
48.432
15.233
−29.722
1.00
36.18
6
ATOM
1741
CD1
ILE
A
225
50.515
13.174
−30.428
1.00
37.76
6
ATOM
1742
N
ILE
A
226
49.522
18.680
−29.780
1.00
33.53
7
ATOM
1743
CA
ILE
A
226
48.922
19.759
−29.025
1.00
33.52
6
ATOM
1744
C
ILE
A
226
48.614
20.969
−29.881
1.00
33.80
6
ATOM
1745
O
ILE
A
226
47.581
21.655
−29.737
1.00
32.30
8
ATOM
1746
CB
ILE
A
226
49.877
20.107
−27.843
1.00
34.98
6
ATOM
1747
CG1
ILE
A
226
49.847
18.937
−26.874
1.00
34.99
6
ATOM
1748
CG2
ILE
A
226
49.490
21.417
−27.159
1.00
34.94
6
ATOM
1749
CD1
ILE
A
226
50.657
19.117
−25.611
1.00
36.97
6
ATOM
1750
N
THR
A
227
49.527
21.261
−30.830
1.00
33.69
7
ATOM
1751
CA
THR
A
227
49.287
22.418
−31.697
1.00
34.02
6
ATOM
1752
C
THR
A
227
48.040
22.160
−32.526
1.00
32.93
6
ATOM
1753
O
THR
A
227
47.183
23.034
−32.604
1.00
33.21
8
ATOM
1754
CB
THR
A
227
50.469
22.754
−32.630
1.00
36.23
6
ATOM
1755
OG1
THR
A
227
51.656
22.905
−31.839
1.00
38.63
8
ATOM
1756
CG2
THR
A
227
50.229
24.059
−33.378
1.00
37.54
6
ATOM
1757
N
ILE
A
228
47.887
20.967
−33.060
1.00
33.57
7
ATOM
1758
CA
ILE
A
228
46.742
20.647
−33.899
1.00
33.85
6
ATOM
1759
C
ILE
A
228
45.453
20.703
−33.074
1.00
33.32
6
ATOM
1760
O
ILE
A
228
44.417
21.205
−33.482
1.00
31.47
8
ATOM
1761
CB
ILE
A
228
46.908
19.275
−34.533
1.00
36.08
6
ATOM
1762
CG1
ILE
A
228
48.002
19.323
−35.634
1.00
39.34
6
ATOM
1763
CG2
ILE
A
228
45.610
18.758
−35.136
1.00
35.68
6
ATOM
1764
CD1
ILE
A
228
48.385
17.919
−36.092
1.00
39.59
6
ATOM
1765
N
ALA
A
229
45.597
20.146
−31.859
1.00
33.09
7
ATOM
1766
CA
ALA
A
229
44.441
20.114
−30.930
1.00
31.53
6
ATOM
1767
C
ALA
A
229
43.948
21.497
−30.607
1.00
28.89
6
ATOM
1768
O
ALA
A
229
42.733
21.771
−30.644
1.00
28.46
8
ATOM
1769
CB
ALA
A
229
44.898
19.315
−29.707
1.00
31.42
6
ATOM
1770
N
GLY
A
230
44.836
22.471
−30.407
1.00
29.20
7
ATOM
1771
CA
GLY
A
230
44.485
23.857
−30.166
1.00
30.51
6
ATOM
1772
C
GLY
A
230
43.797
24.472
−31.372
1.00
31.48
6
ATOM
1773
O
GLY
A
230
42.759
25.155
−31.288
1.00
33.24
8
ATOM
1774
N
GLN
A
231
44.374
24.217
−32.569
1.00
33.19
7
ATOM
1775
CA
GLN
A
231
43.812
24.700
−33.823
1.00
33.48
6
ATOM
1776
C
GLN
A
231
42.396
24.206
−34.027
1.00
32.96
6
ATOM
1777
O
GLN
A
231
41.476
24.995
−34.324
1.00
34.21
8
ATOM
1778
CB
GLN
A
231
44.704
24.245
−35.003
1.00
34.34
6
ATOM
1779
CG
GLN
A
231
46.007
25.041
−35.007
1.00
36.14
6
ATOM
1780
CD
GLN
A
231
47.002
24.556
−36.052
1.00
38.53
6
ATOM
1781
OE1
GLN
A
231
46.812
23.541
−36.732
1.00
39.14
8
ATOM
1782
NE2
GLN
A
231
48.085
25.312
−36.189
1.00
39.12
7
ATOM
1783
N
GLU
A
232
42.214
22.900
−33.801
1.00
31.08
7
ATOM
1784
CA
GLU
A
232
40.897
22.280
−33.907
1.00
33.90
6
ATOM
1785
C
GLU
A
232
39.897
22.898
−32.923
1.00
32.79
6
ATOM
1786
O
GLU
A
232
38.785
23.235
−33.345
1.00
30.71
8
ATOM
1787
CB
GLU
A
232
40.956
20.772
−33.659
1.00
36.16
6
ATOM
1788
CG
GLU
A
232
41.681
19.963
−34.705
1.00
40.99
6
ATOM
1789
CD
GLU
A
232
41.956
18.526
−34.336
1.00
43.88
6
ATOM
1790
OE1
GLU
A
232
42.231
18.222
−33.162
1.00
46.75
8
ATOM
1791
OE2
GLU
A
232
41.978
17.624
−35.213
1.00
46.96
8
ATOM
1792
N
LEU
A
233
40.279
23.075
−31.654
1.00
31.79
7
ATOM
1793
CA
LEU
A
233
39.390
23.738
−30.717
1.00
31.75
6
ATOM
1794
C
LEU
A
233
39.053
25.159
−31.151
1.00
30.93
6
ATOM
1795
O
LEU
A
233
37.914
25.617
−31.117
1.00
29.58
8
ATOM
1796
CB
LEU
A
233
40.002
23.804
−29.306
1.00
28.67
6
ATOM
1797
CG
LEU
A
233
40.122
22.439
−28.598
1.00
29.48
6
ATOM
1798
CD1
LEU
A
233
41.084
22.505
−27.425
1.00
29.09
6
ATOM
1799
CD2
LEU
A
233
38.712
21.976
−28.189
1.00
30.10
6
ATOM
1800
N
ASN
A
234
40.083
25.889
−31.615
1.00
32.79
7
ATOM
1801
CA
ASN
A
234
39.861
27.288
−32.011
1.00
33.77
6
ATOM
1802
C
ASN
A
234
38.946
27.388
−33.220
1.00
31.44
6
ATOM
1803
O
ASN
A
234
38.071
28.254
−33.258
1.00
32.82
8
ATOM
1804
CB
ASN
A
234
41.220
27.972
−32.243
1.00
36.16
6
ATOM
1805
CG
ASN
A
234
41.890
28.295
−30.919
1.00
39.98
6
ATOM
1806
OD1
ASN
A
234
41.296
28.257
−29.838
1.00
40.76
8
ATOM
1807
ND2
ASN
A
234
43.185
28.592
−30.922
1.00
39.55
7
ATOM
1808
N
GLU
A
235
39.068
26.440
−34.127
1.00
31.44
7
ATOM
1809
CA
GLU
A
235
38.223
26.392
−35.306
1.00
34.68
6
ATOM
1810
C
GLU
A
235
36.779
26.082
−34.971
1.00
34.35
6
ATOM
1811
O
GLU
A
235
35.878
26.565
−35.629
1.00
35.56
8
ATOM
1812
CB
GLU
A
235
38.763
25.314
−36.244
1.00
36.35
6
ATOM
1813
N
LYS
A
236
36.532
25.307
−33.908
1.00
36.15
7
ATOM
1814
CA
LYS
A
236
35.169
24.977
−33.488
1.00
35.47
6
ATOM
1815
C
LYS
A
236
34.483
26.106
−32.738
1.00
34.87
6
ATOM
1816
O
LYS
A
236
33.253
26.085
−32.561
1.00
36.38
8
ATOM
1817
CB
LYS
A
236
35.213
23.748
−32.577
1.00
37.47
6
ATOM
1818
CG
LYS
A
236
35.609
22.450
−33.245
1.00
38.51
6
ATOM
1819
CD
LYS
A
236
35.643
21.345
−32.192
1.00
40.94
6
ATOM
1820
CE
LYS
A
236
36.184
20.083
−32.827
1.00
42.93
6
ATOM
1821
NZ
LYS
A
236
36.231
18.973
−31.850
1.00
45.15
7
ATOM
1822
N
GLY
A
237
35.225
27.094
−32.274
1.00
33.61
7
ATOM
1823
CA
GLY
A
237
34.660
28.241
−31.576
1.00
33.28
6
ATOM
1824
C
GLY
A
237
35.127
28.401
−30.157
1.00
32.89
6
ATOM
1825
O
GLY
A
237
34.644
29.291
−29.429
1.00
36.87
8
ATOM
1826
N
PHE
A
238
36.017
27.546
−29.668
1.00
30.90
7
ATOM
1827
CA
PHE
A
238
36.629
27.664
−28.380
1.00
31.61
6
ATOM
1828
C
PHE
A
238
37.817
28.641
−28.417
1.00
35.03
6
ATOM
1829
O
PHE
A
238
38.191
29.022
−29.528
1.00
37.95
8
ATOM
1830
CB
PHE
A
238
37.201
26.338
−27.875
1.00
29.76
6
ATOM
1831
CG
PHE
A
238
36.165
25.258
−27.686
1.00
30.50
6
ATOM
1832
CD1
PHE
A
238
35.712
24.500
−28.727
1.00
29.47
6
ATOM
1833
CD2
PHE
A
238
35.679
24.979
−26.414
1.00
31.42
6
ATOM
1834
CE1
PHE
A
238
34.752
23.501
−28.555
1.00
31.11
6
ATOM
1835
CE2
PHE
A
238
34.731
23.986
−26.233
1.00
29.77
6
ATOM
1836
CZ
PHE
A
238
34.284
23.235
−27.279
1.00
29.29
6
ATOM
1837
N
ARG
A
239
38.388
28.963
−27.268
1.00
34.76
7
ATOM
1838
CA
ARG
A
239
39.674
29.645
−27.216
1.00
35.49
6
ATOM
1839
C
ARG
A
239
40.472
28.742
−26.270
1.00
35.32
6
ATOM
1840
O
ARG
A
239
40.308
28.724
−25.057
1.00
32.89
8
ATOM
1841
CB
ARG
A
239
39.721
31.088
−26.754
1.00
37.36
6
ATOM
1842
CG
ARG
A
239
39.226
32.068
−27.822
1.00
39.64
6
ATOM
1843
N
ALA
A
240
41.233
27.877
−26.931
1.00
36.31
7
ATOM
1844
CA
ALA
A
240
42.124
26.921
−26.293
1.00
36.79
6
ATOM
1845
C
ALA
A
240
42.906
27.617
−25.203
1.00
38.54
6
ATOM
1846
O
ALA
A
240
43.360
28.735
−25.495
1.00
39.25
8
ATOM
1847
CB
ALA
A
240
43.087
26.347
−27.333
1.00
36.86
6
ATOM
1848
N
ASP
A
241
43.035
27.053
−24.024
1.00
39.01
7
ATOM
1849
CA
ASP
A
241
43.689
27.789
−22.947
1.00
42.42
6
ATOM
1850
C
ASP
A
241
44.867
27.010
−22.396
1.00
43.73
6
ATOM
1851
O
ASP
A
241
45.894
27.608
−22.061
1.00
46.19
8
ATOM
1852
CB
ASP
A
241
42.686
28.105
−21.828
1.00
43.72
6
ATOM
1853
CG
ASP
A
241
43.319
28.991
−20.771
1.00
46.29
6
ATOM
1854
OD1
ASP
A
241
43.712
30.124
−21.130
1.00
47.38
8
ATOM
1855
OD2
ASP
A
241
43.433
28.560
−19.610
1.00
46.21
8
ATOM
1856
N
ASP
A
242
44.733
25.690
−22.292
1.00
41.53
7
ATOM
1857
CA
ASP
A
242
45.828
24.876
−21.764
1.00
39.46
6
ATOM
1858
C
ASP
A
242
45.607
23.442
−22.177
1.00
37.10
6
ATOM
1859
O
ASP
A
242
44.496
22.895
−22.059
1.00
34.02
8
ATOM
1860
CB
ASP
A
242
45.908
25.001
−20.242
1.00
43.32
6
ATOM
1861
CG
ASP
A
242
47.103
24.275
−19.661
1.00
47.37
6
ATOM
1862
OD1
ASP
A
242
46.980
23.437
−18.736
1.00
49.59
8
ATOM
1863
OD2
ASP
A
242
48.231
24.530
−20.158
1.00
50.50
8
ATOM
1864
N
ILE
A
243
46.597
22.785
−22.750
1.00
33.48
7
ATOM
1865
CA
ILE
A
243
46.550
21.419
−23.193
1.00
32.08
6
ATOM
1866
C
ILE
A
243
47.853
20.812
−22.718
1.00
33.41
6
ATOM
1867
O
ILE
A
243
48.895
21.390
−23.062
1.00
32.28
8
ATOM
1868
CB
ILE
A
243
46.424
21.205
−24.719
1.00
33.19
6
ATOM
1869
CG1
ILE
A
243
45.141
21.847
−25.222
1.00
33.31
6
ATOM
1870
CG2
ILE
A
243
46.504
19.703
−24.995
1.00
32.88
6
ATOM
1871
CD1
ILE
A
243
44.892
21.792
−26.713
1.00
33.52
6
ATOM
1872
N
GLN
A
244
47.829
19.735
−21.975
1.00
33.31
7
ATOM
1873
CA
GLN
A
244
49.003
19.097
−21.436
1.00
35.24
6
ATOM
1874
C
GLN
A
244
48.849
17.592
−21.483
1.00
34.74
6
ATOM
1875
O
GLN
A
244
47.741
17.056
−21.422
1.00
33.25
8
ATOM
1876
CB
GLN
A
244
49.300
19.528
−19.967
1.00
39.02
6
ATOM
1877
CG
GLN
A
244
49.773
20.962
−19.905
1.00
43.89
6
ATOM
1878
CD
GLN
A
244
50.076
21.564
−18.569
1.00
47.28
6
ATOM
1879
OE1
GLN
A
244
50.148
20.870
−17.548
1.00
48.52
8
ATOM
1880
NE2
GLN
A
244
50.259
22.895
−18.597
1.00
49.46
7
ATOM
1881
N
ILE
A
245
49.943
16.870
−21.716
1.00
31.86
7
ATOM
1882
CA
ILE
A
245
50.000
15.439
−21.801
1.00
31.75
6
ATOM
1883
C
ILE
A
245
51.110
14.967
−20.852
1.00
33.59
6
ATOM
1884
O
ILE
A
245
52.183
15.586
−20.888
1.00
36.14
8
ATOM
1885
CB
ILE
A
245
50.299
14.888
−23.213
1.00
33.28
6
ATOM
1886
CG1
ILE
A
245
49.188
15.324
−24.177
1.00
32.78
6
ATOM
1887
CG2
ILE
A
245
50.470
13.387
−23.164
1.00
33.13
6
ATOM
1888
CD1
ILE
A
245
49.424
15.049
−25.648
1.00
33.13
6
ATOM
1889
N
ARG
A
246
50.827
14.054
−19.946
1.00
34.84
7
ATOM
1890
CA
ARG
A
246
51.816
13.609
−18.982
1.00
35.92
6
ATOM
1891
C
ARG
A
246
51.687
12.122
−18.690
1.00
35.36
6
ATOM
1892
O
ARG
A
246
50.697
11.461
−18.911
1.00
35.88
8
ATOM
1893
CB
ARG
A
246
51.713
14.251
−17.589
1.00
36.79
6
ATOM
1894
CG
ARG
A
246
51.674
15.747
−17.458
1.00
41.24
6
ATOM
1895
CD
ARG
A
246
53.032
16.284
−17.914
1.00
46.18
6
ATOM
1896
NE
ARG
A
246
53.251
17.654
−17.502
1.00
49.48
7
ATOM
1897
CZ
ARG
A
246
53.913
18.040
−16.420
1.00
51.58
6
ATOM
1898
NH1
ARG
A
246
54.466
17.155
−15.603
1.00
51.91
7
ATOM
1899
NH2
ARG
A
246
54.006
19.352
−16.229
1.00
53.89
7
ATOM
1900
N
ASP
A
247
52.730
11.616
−18.003
1.00
35.81
7
ATOM
1901
CA
ASP
A
247
52.753
10.248
−17.537
1.00
34.88
6
ATOM
1902
C
ASP
A
247
51.652
10.087
−16.495
1.00
31.75
6
ATOM
1903
O
ASP
A
247
51.690
10.908
−15.584
1.00
32.95
8
ATOM
1904
CB
ASP
A
247
54.146
9.952
−16.954
1.00
37.68
6
ATOM
1905
CG
ASP
A
247
54.195
8.479
−16.611
1.00
39.66
6
ATOM
1906
OD1
ASP
A
247
53.482
8.015
−15.710
1.00
41.79
8
ATOM
1907
OD2
ASP
A
247
54.924
7.748
−17.284
1.00
42.94
8
ATOM
1908
N
ALA
A
248
50.712
9.185
−16.600
1.00
33.81
7
ATOM
1909
CA
ALA
A
248
49.616
9.156
−15.609
1.00
32.51
6
ATOM
1910
C
ALA
A
248
50.041
8.675
−14.232
1.00
34.35
6
ATOM
1911
O
ALA
A
248
49.399
9.063
−13.249
1.00
33.85
8
ATOM
1912
CB
ALA
A
248
48.499
8.253
−16.070
1.00
33.01
6
ATOM
1913
N
ASP
A
249
51.057
7.825
−14.103
1.00
36.10
7
ATOM
1914
CA
ASP
A
249
51.462
7.281
−12.822
1.00
35.70
6
ATOM
1915
C
ASP
A
249
52.421
8.185
−12.073
1.00
33.40
6
ATOM
1916
O
ASP
A
249
52.399
8.230
−10.818
1.00
31.30
8
ATOM
1917
CB
ASP
A
249
52.152
5.916
−13.031
1.00
39.11
6
ATOM
1918
CG
ASP
A
249
51.137
5.007
−13.715
1.00
43.20
6
ATOM
1919
OD1
ASP
A
249
50.028
4.826
−13.134
1.00
45.31
8
ATOM
1920
OD2
ASP
A
249
51.423
4.514
−14.817
1.00
43.99
8
ATOM
1921
N
THR
A
250
53.275
8.844
−12.857
1.00
31.16
7
ATOM
1922
CA
THR
A
250
54.301
9.667
−12.240
1.00
32.87
6
ATOM
1923
C
THR
A
250
54.087
11.144
−12.416
1.00
32.81
6
ATOM
1924
O
THR
A
250
54.760
11.935
−11.789
1.00
30.56
8
ATOM
1925
CB
THR
A
250
55.740
9.378
−12.792
1.00
34.12
6
ATOM
1926
OG1
THR
A
250
55.779
9.795
−14.158
1.00
34.42
8
ATOM
1927
CG2
THR
A
250
56.080
7.911
−12.637
1.00
34.28
6
ATOM
1928
N
LEU
A
251
53.281
11.587
−13.365
1.00
32.56
7
ATOM
1929
CA
LEU
A
251
52.972
12.978
−13.672
1.00
34.35
6
ATOM
1930
C
LEU
A
251
54.124
13.689
−14.360
1.00
35.41
6
ATOM
1931
O
LEU
A
251
54.093
14.893
−14.592
1.00
35.99
8
ATOM
1932
CB
LEU
A
251
52.494
13.758
−12.418
1.00
33.68
6
ATOM
1933
CG
LEU
A
251
51.220
13.147
−11.792
1.00
34.55
6
ATOM
1934
CD1
LEU
A
251
50.797
13.969
−10.573
1.00
35.91
6
ATOM
1935
CD2
LEU
A
251
50.101
13.012
−12.821
1.00
35.43
6
ATOM
1936
N
LEU
A
252
55.194
12.962
−14.695
1.00
39.58
7
ATOM
1937
CA
LEU
A
252
56.323
13.587
−15.418
1.00
40.96
6
ATOM
1938
C
LEU
A
252
55.945
13.614
−16.874
1.00
43.27
6
ATOM
1939
O
LEU
A
252
54.906
13.129
−17.318
1.00
40.97
8
ATOM
1940
CB
LEU
A
252
57.550
12.584
−15.264
1.00
42.55
6
ATOM
1941
CG
LEU
A
252
58.072
12.496
−13.823
1.00
43.46
6
ATOM
1942
CD1
LEU
A
252
59.196
11.476
−13.685
1.00
44.26
6
ATOM
1943
CD2
LEU
A
252
58.546
13.868
−13.341
1.00
43.34
6
ATOM
1944
N
GLU
A
253
56.855
14.189
−17.659
1.00
46.27
7
ATOM
1945
CA
GLU
A
253
56.716
14.144
−19.109
1.00
48.94
6
ATOM
1946
C
GLU
A
253
56.642
12.706
−19.612
1.00
48.01
6
ATOM
1947
O
GLU
A
253
57.291
11.928
−18.871
1.00
48.08
8
ATOM
1948
CB
GLU
A
253
57.877
14.878
−19.783
1.00
52.86
6
ATOM
1949
CG
GLU
A
253
57.914
16.371
−19.500
1.00
57.25
6
ATOM
1950
CD
GLU
A
253
56.720
17.104
−20.077
1.00
60.45
6
ATOM
1951
OE1
GLU
A
253
56.308
16.771
−21.207
1.00
61.73
8
ATOM
1952
OE2
GLU
A
253
56.194
18.011
−19.397
1.00
61.77
8
ATOM
1953
N
VAL
A
254
55.835
12.324
−20.596
1.00
48.66
7
ATOM
1954
CA
VAL
A
254
55.849
10.887
−20.872
1.00
49.85
6
ATOM
1955
C
VAL
A
254
57.149
10.638
−21.614
1.00
51.30
6
ATOM
1956
O
VAL
A
254
57.658
11.494
−22.340
1.00
49.27
8
ATOM
1957
CB
VAL
A
254
54.576
10.399
−21.614
1.00
51.06
6
ATOM
1958
CG1
VAL
A
254
53.600
11.541
−21.825
1.00
50.21
6
ATOM
1959
CG2
VAL
A
254
54.935
9.757
−22.940
1.00
51.39
6
ATOM
1960
N
SER
A
255
57.636
9.432
−21.398
1.00
50.78
7
ATOM
1961
CA
SER
A
255
58.878
8.951
−21.946
1.00
52.29
6
ATOM
1962
C
SER
A
255
58.718
7.516
−22.423
1.00
53.07
6
ATOM
1963
O
SER
A
255
57.625
6.965
−22.444
1.00
53.08
8
ATOM
1964
CB
SER
A
255
59.978
8.985
−20.878
1.00
51.99
6
ATOM
1965
OG
SER
A
255
59.761
7.859
−20.013
1.00
51.83
8
ATOM
1966
N
GLU
A
256
59.844
6.858
−22.692
1.00
55.01
7
ATOM
1967
CA
GLU
A
256
59.903
5.485
−23.155
1.00
55.63
6
ATOM
1968
C
GLU
A
256
59.251
4.493
−22.207
1.00
55.82
6
ATOM
1969
O
GLU
A
256
58.566
3.543
−22.591
1.00
55.91
8
ATOM
1970
CB
GLU
A
256
61.380
5.091
−23.350
1.00
56.43
6
ATOM
1971
N
THR
A
257
59.458
4.732
−20.919
1.00
55.14
7
ATOM
1972
CA
THR
A
257
58.921
3.928
−19.846
1.00
54.05
6
ATOM
1973
C
THR
A
257
57.443
4.151
−19.554
1.00
51.69
6
ATOM
1974
O
THR
A
257
56.836
3.301
−18.887
1.00
51.58
8
ATOM
1975
CB
THR
A
257
59.723
4.223
−18.554
1.00
55.07
6
ATOM
1976
OG1
THR
A
257
59.404
5.533
−18.065
1.00
56.77
8
ATOM
1977
CG2
THR
A
257
61.215
4.150
−18.828
1.00
55.65
6
ATOM
1978
N
SER
A
258
56.834
5.252
−20.000
1.00
49.85
7
ATOM
1979
CA
SER
A
258
55.426
5.481
−19.663
1.00
46.23
6
ATOM
1980
C
SER
A
258
54.484
4.382
−20.104
1.00
46.46
6
ATOM
1981
O
SER
A
258
54.511
3.984
−21.269
1.00
47.83
8
ATOM
1982
CB
SER
A
258
54.950
6.783
−20.306
1.00
44.06
6
ATOM
1983
OG
SER
A
258
55.742
7.841
−19.839
1.00
40.94
8
ATOM
1984
N
LYS
A
259
53.626
3.905
−19.221
1.00
46.05
7
ATOM
1985
CA
LYS
A
259
52.624
2.902
−19.512
1.00
46.69
6
ATOM
1986
C
LYS
A
259
51.252
3.551
−19.739
1.00
45.85
6
ATOM
1987
O
LYS
A
259
50.329
3.046
−20.369
1.00
45.29
8
ATOM
1988
CB
LYS
A
259
52.455
1.886
−18.382
1.00
46.44
6
ATOM
1989
CG
LYS
A
259
53.726
1.200
−17.920
1.00
47.93
6
ATOM
1990
N
ARG
A
260
51.088
4.696
−19.069
1.00
46.77
7
ATOM
1991
CA
ARG
A
260
49.800
5.397
−19.104
1.00
45.39
6
ATOM
1992
C
ARG
A
260
49.991
6.882
−19.278
1.00
41.75
6
ATOM
1993
O
ARG
A
260
50.970
7.421
−18.763
1.00
41.96
8
ATOM
1994
CB
ARG
A
260
49.004
5.146
−17.814
1.00
48.72
6
ATOM
1995
CG
ARG
A
260
48.340
3.797
−17.715
1.00
52.78
6
ATOM
1996
CD
ARG
A
260
47.783
3.490
−16.342
1.00
56.11
6
ATOM
1997
NE
ARG
A
260
48.800
3.016
−15.423
1.00
60.02
7
ATOM
1998
CZ
ARG
A
260
49.366
1.817
−15.362
1.00
61.86
6
ATOM
1999
NH1
ARG
A
260
49.066
0.806
−16.179
1.00
62.97
7
ATOM
2000
NH2
ARG
A
260
50.275
1.615
−14.410
1.00
62.19
7
ATOM
2001
N
ALA
A
261
49.079
7.547
−20.024
1.00
39.42
7
ATOM
2002
CA
ALA
A
261
49.232
8.993
−20.107
1.00
35.31
6
ATOM
2003
C
ALA
A
261
47.928
9.630
−19.612
1.00
32.26
6
ATOM
2004
O
ALA
A
261
46.872
9.005
−19.790
1.00
34.66
8
ATOM
2005
CB
ALA
A
261
49.538
9.504
−21.504
1.00
34.95
6
ATOM
2006
N
VAL
A
262
48.060
10.831
−19.087
1.00
29.67
7
ATOM
2007
CA
VAL
A
262
46.852
11.578
−18.705
1.00
27.51
6
ATOM
2008
C
VAL
A
262
46.916
12.796
−19.608
1.00
27.97
6
ATOM
2009
O
VAL
A
262
47.977
13.414
−19.791
1.00
26.28
8
ATOM
2010
CB
VAL
A
262
46.750
11.979
−17.233
1.00
29.25
6
ATOM
2011
CG1
VAL
A
262
47.995
12.725
−16.785
1.00
30.58
6
ATOM
2012
CG2
VAL
A
262
45.527
12.884
−16.976
1.00
30.36
6
ATOM
2013
N
ILE
A
263
45.801
13.185
−20.185
1.00
26.21
7
ATOM
2014
CA
ILE
A
263
45.639
14.343
−21.031
1.00
26.33
6
ATOM
2015
C
ILE
A
263
44.738
15.341
−20.300
1.00
28.09
6
ATOM
2016
O
ILE
A
263
43.635
14.903
−19.935
1.00
26.14
8
ATOM
2017
CB
ILE
A
263
44.977
13.970
−22.357
1.00
27.18
6
ATOM
2018
CG1
ILE
A
263
45.701
12.767
−22.999
1.00
30.42
6
ATOM
2019
CG2
ILE
A
263
44.931
15.184
−23.302
1.00
26.41
6
ATOM
2020
CD1
ILE
A
263
44.751
11.943
−23.867
1.00
32.55
6
ATOM
2021
N
LEU
A
264
45.198
16.564
−20.149
1.00
28.73
7
ATOM
2022
CA
LEU
A
264
44.453
17.626
−19.514
1.00
30.58
6
ATOM
2023
C
LEU
A
264
44.108
18.698
−20.530
1.00
29.44
6
ATOM
2024
O
LEU
A
264
45.005
19.177
−21.235
1.00
30.50
8
ATOM
2025
CB
LEU
A
264
45.273
18.264
−18.392
1.00
33.45
6
ATOM
2026
CG
LEU
A
264
46.310
17.397
−17.677
1.00
35.36
6
ATOM
2027
CD1
LEU
A
264
47.287
18.261
−16.855
1.00
38.43
6
ATOM
2028
CD2
LEU
A
264
45.634
16.357
−16.800
1.00
36.22
6
ATOM
2029
N
VAL
A
265
42.875
19.166
−20.643
1.00
28.12
7
ATOM
2030
CA
VAL
A
265
42.516
20.228
−21.586
1.00
30.77
6
ATOM
2031
C
VAL
A
265
41.662
21.288
−20.868
1.00
30.38
6
ATOM
2032
O
VAL
A
265
40.888
20.946
−19.964
1.00
33.23
8
ATOM
2033
CB
VAL
A
265
41.740
19.716
−22.798
1.00
30.45
6
ATOM
2034
CG1
VAL
A
265
42.546
18.732
−23.649
1.00
31.64
6
ATOM
2035
CG2
VAL
A
265
40.456
18.962
−22.415
1.00
30.65
6
ATOM
2036
N
ALA
A
266
41.822
22.538
−21.233
1.00
30.29
7
ATOM
2037
CA
ALA
A
266
40.992
23.628
−20.697
1.00
27.93
6
ATOM
2038
C
ALA
A
266
40.722
24.514
−21.890
1.00
28.75
6
ATOM
2039
O
ALA
A
266
41.687
24.771
−22.653
1.00
31.65
8
ATOM
2040
CB
ALA
A
266
41.637
24.388
−19.574
1.00
28.93
6
ATOM
2041
N
ALA
A
267
39.535
25.012
−22.069
1.00
27.14
7
ATOM
2042
CA
ALA
A
267
39.237
25.880
−23.189
1.00
28.13
6
ATOM
2043
C
ALA
A
267
38.051
26.744
−22.796
1.00
29.67
6
ATOM
2044
O
ALA
A
267
37.054
26.257
−22.261
1.00
27.60
8
ATOM
2045
CB
ALA
A
267
38.861
25.167
−24.478
1.00
26.05
6
ATOM
2046
N
TRP
A
268
38.151
28.007
−23.166
1.00
29.63
7
ATOM
2047
CA
TRP
A
268
37.074
28.951
−22.969
1.00
28.26
6
ATOM
2048
C
TRP
A
268
36.049
28.766
−24.072
1.00
29.88
6
ATOM
2049
O
TRP
A
268
36.407
28.609
−25.245
1.00
30.20
8
ATOM
2050
CB
TRP
A
268
37.599
30.394
−22.996
1.00
30.40
6
ATOM
2051
CG
TRP
A
268
38.406
30.735
−21.778
1.00
31.50
6
ATOM
2052
CD1
TRP
A
268
39.756
30.638
−21.572
1.00
32.04
6
ATOM
2053
CD2
TRP
A
268
37.850
31.336
−20.602
1.00
29.94
6
ATOM
2054
NE1
TRP
A
268
40.071
31.097
−20.307
1.00
32.09
7
ATOM
2055
CE2
TRP
A
268
38.905
31.521
−19.699
1.00
32.20
6
ATOM
2056
CE3
TRP
A
268
36.543
31.660
−20.214
1.00
29.41
6
ATOM
2057
CZ2
TRP
A
268
38.729
32.062
−18.420
1.00
30.97
6
ATOM
2058
CZ3
TRP
A
268
36.362
32.188
−18.965
1.00
30.37
6
ATOM
2059
CH2
TRP
A
268
37.448
32.390
−18.097
1.00
29.74
6
ATOM
2060
N
LEU
A
269
34.789
28.947
−23.715
1.00
28.17
7
ATOM
2061
CA
LEU
A
269
33.648
28.954
−24.579
1.00
29.03
6
ATOM
2062
C
LEU
A
269
32.680
29.913
−23.885
1.00
29.91
6
ATOM
2063
O
LEU
A
269
32.201
29.674
−22.758
1.00
25.57
8
ATOM
2064
CB
LEU
A
269
33.139
27.528
−24.786
1.00
30.48
6
ATOM
2065
CG
LEU
A
269
31.952
27.443
−25.719
1.00
31.96
6
ATOM
2066
CD1
LEU
A
269
32.337
27.993
−27.103
1.00
30.89
6
ATOM
2067
CD2
LEU
A
269
31.423
26.003
−25.790
1.00
31.19
6
ATOM
2068
N
GLY
A
270
32.559
31.132
−24.446
1.00
29.19
7
ATOM
2069
CA
GLY
A
270
31.738
32.156
−23.798
1.00
29.83
6
ATOM
2070
C
GLY
A
270
32.341
32.563
−22.463
1.00
32.39
6
ATOM
2071
O
GLY
A
270
33.549
32.829
−22.369
1.00
32.69
8
ATOM
2072
N
ASP
A
271
31.552
32.562
−21.390
1.00
30.56
7
ATOM
2073
CA
ASP
A
271
32.088
32.888
−20.075
1.00
31.93
6
ATOM
2074
C
ASP
A
271
32.450
31.649
−19.271
1.00
31.25
6
ATOM
2075
O
ASP
A
271
32.749
31.710
−18.079
1.00
30.60
8
ATOM
2076
CB
ASP
A
271
31.087
33.758
−19.289
1.00
33.98
6
ATOM
2077
CG
ASP
A
271
31.073
35.165
−19.921
1.00
37.85
6
ATOM
2078
OD1
ASP
A
271
32.103
35.682
−20.401
1.00
38.52
8
ATOM
2079
OD2
ASP
A
271
29.996
35.770
−19.944
1.00
39.53
8
ATOM
2080
N
ALA
A
272
32.462
30.482
−19.903
1.00
29.77
7
ATOM
2081
CA
ALA
A
272
32.828
29.254
−19.228
1.00
27.77
6
ATOM
2082
C
ALA
A
272
34.256
28.826
−19.557
1.00
26.45
6
ATOM
2083
O
ALA
A
272
34.545
28.837
−20.745
1.00
26.44
8
ATOM
2084
CB
ALA
A
272
31.977
28.068
−19.666
1.00
27.56
6
ATOM
2085
N
ARG
A
273
35.053
28.448
−18.602
1.00
25.11
7
ATOM
2086
CA
ARG
A
273
36.354
27.839
−18.859
1.00
25.96
6
ATOM
2087
C
ARG
A
273
36.194
26.346
−18.606
1.00
23.79
6
ATOM
2088
O
ARG
A
273
36.292
25.868
−17.465
1.00
25.36
8
ATOM
2089
CB
ARG
A
273
37.467
28.400
−17.962
1.00
27.51
6
ATOM
2090
CG
ARG
A
273
38.864
27.853
−18.355
1.00
27.52
6
ATOM
2091
CD
ARG
A
273
39.848
28.605
−17.421
1.00
28.40
6
ATOM
2092
NE
ARG
A
273
41.215
28.212
−17.720
0.50
26.25
7
ATOM
2093
CZ
ARG
A
273
41.850
27.144
−17.306
0.50
26.10
6
ATOM
2094
NH1
ARG
A
273
41.229
26.281
−16.517
0.50
28.04
7
ATOM
2095
NH2
ARG
A
273
43.107
26.909
−17.691
0.50
25.33
7
ATOM
2096
N
LEU
A
274
35.918
25.587
−19.693
1.00
25.09
7
ATOM
2097
CA
LEU
A
274
35.608
24.173
−19.545
1.00
23.10
6
ATOM
2098
C
LEU
A
274
36.845
23.385
−19.359
1.00
23.02
6
ATOM
2099
O
LEU
A
274
37.846
23.706
−20.001
1.00
24.38
8
ATOM
2100
CB
LEU
A
274
34.863
23.714
−20.847
1.00
22.40
6
ATOM
2101
CG
LEU
A
274
33.548
24.488
−21.045
1.00
22.92
6
ATOM
2102
CD1
LEU
A
274
32.953
24.119
−22.368
1.00
25.59
6
ATOM
2103
CD2
LEU
A
274
32.619
24.185
−19.846
1.00
24.66
6
ATOM
2104
N
ILE
A
275
36.844
22.342
−18.576
1.00
22.01
7
ATOM
2105
CA
ILE
A
275
37.965
21.529
−18.235
1.00
24.38
6
ATOM
2106
C
ILE
A
275
37.640
20.072
−18.439
1.00
24.31
6
ATOM
2107
O
ILE
A
275
36.504
19.675
−18.126
1.00
23.32
8
ATOM
2108
CB
ILE
A
275
38.290
21.785
−16.743
1.00
27.33
6
ATOM
2109
CG1
ILE
A
275
38.853
23.233
−16.577
1.00
30.12
6
ATOM
2110
CG2
ILE
A
275
39.295
20.826
−16.161
1.00
32.15
6
ATOM
2111
CD1
ILE
A
275
38.634
23.632
−15.112
1.00
33.95
6
ATOM
2112
N
ASP
A
276
38.611
19.282
−18.865
1.00
23.56
7
ATOM
2113
CA
ASP
A
276
38.347
17.845
−19.005
1.00
24.73
6
ATOM
2114
C
ASP
A
276
39.702
17.125
−18.966
1.00
24.26
6
ATOM
2115
O
ASP
A
276
40.768
17.741
−19.153
1.00
24.98
8
ATOM
2116
CB
ASP
A
276
37.551
17.545
−20.271
1.00
24.30
6
ATOM
2117
CG
ASP
A
276
36.730
16.276
−20.290
1.00
26.28
6
ATOM
2118
OD1
ASP
A
276
36.927
15.468
−19.324
1.00
27.91
8
ATOM
2119
OD2
ASP
A
276
35.946
16.119
−21.251
1.00
25.73
8
ATOM
2120
N
ASN
A
277
39.671
15.855
−18.697
1.00
22.14
7
ATOM
2121
CA
ASN
A
277
40.857
15.020
−18.682
1.00
25.69
6
ATOM
2122
C
ASN
A
277
40.473
13.587
−19.027
1.00
24.93
6
ATOM
2123
O
ASN
A
277
39.335
13.139
−18.920
1.00
25.86
8
ATOM
2124
CB
ASN
A
277
41.608
15.073
−17.350
1.00
28.42
6
ATOM
2125
CG
ASN
A
277
41.077
14.298
−16.164
1.00
32.43
6
ATOM
2126
OD1
ASN
A
277
40.715
13.140
−16.247
1.00
37.45
8
ATOM
2127
ND2
ASN
A
277
41.023
14.889
−14.994
1.00
35.65
7
ATOM
2128
N
LYS
A
278
41.517
12.825
−19.428
1.00
28.31
7
ATOM
2129
CA
LYS
A
278
41.338
11.429
−19.765
1.00
31.78
6
ATOM
2130
C
LYS
A
278
42.655
10.677
−19.634
1.00
33.11
6
ATOM
2131
O
LYS
A
278
43.692
11.227
−19.991
1.00
33.12
8
ATOM
2132
CB
LYS
A
278
40.814
11.323
−21.189
1.00
32.53
6
ATOM
2133
CG
LYS
A
278
40.748
10.008
−21.905
1.00
35.09
6
ATOM
2134
CD
LYS
A
278
39.814
10.144
−23.124
1.00
38.06
6
ATOM
2135
CE
LYS
A
278
39.115
8.808
−23.384
1.00
39.45
6
ATOM
2136
NZ
LYS
A
278
37.984
9.018
−24.354
1.00
40.81
7
ATOM
2137
N
MET
A
279
42.594
9.455
−19.139
1.00
35.39
7
ATOM
2138
CA
MET
A
279
43.799
8.636
−19.046
1.00
39.07
6
ATOM
2139
C
MET
A
279
43.777
7.645
−20.201
1.00
40.75
6
ATOM
2140
O
MET
A
279
42.688
7.224
−20.590
1.00
39.38
8
ATOM
2141
CB
MET
A
279
43.895
7.997
−17.641
1.00
42.09
6
ATOM
2142
CG
MET
A
279
44.366
9.076
−16.657
1.00
45.36
6
ATOM
2143
SD
MET
A
279
44.591
8.656
−14.926
1.00
51.28
16
ATOM
2144
CE
MET
A
279
42.948
8.136
−14.428
1.00
49.74
6
ATOM
2145
N
VAL
A
280
44.953
7.391
−20.786
1.00
41.33
7
ATOM
2146
CA
VAL
A
280
44.994
6.466
−21.917
1.00
44.04
6
ATOM
2147
C
VAL
A
280
46.138
5.483
−21.692
1.00
45.91
6
ATOM
2148
O
VAL
A
280
47.232
5.881
−21.274
1.00
44.69
8
ATOM
2149
CB
VAL
A
280
45.126
7.195
−23.265
1.00
43.07
6
ATOM
2150
CG1
VAL
A
280
46.430
7.978
−23.326
1.00
43.41
6
ATOM
2151
CG2
VAL
A
280
45.060
6.239
−24.439
1.00
43.94
6
ATOM
2152
N
GLU
A
281
45.787
4.211
−21.867
1.00
51.13
7
ATOM
2153
CA
GLU
A
281
46.797
3.151
−21.712
1.00
54.78
6
ATOM
2154
C
GLU
A
281
47.658
3.176
−22.971
1.00
55.75
6
ATOM
2155
O
GLU
A
281
47.155
3.235
−24.094
1.00
55.40
8
ATOM
2156
CB
GLU
A
281
46.186
1.784
−21.469
1.00
56.82
6
ATOM
2157
CG
GLU
A
281
45.244
1.658
−20.296
1.00
59.30
6
ATOM
2158
CD
GLU
A
281
45.898
1.424
−18.957
1.00
61.75
6
ATOM
2159
OE1
GLU
A
281
47.135
1.218
−18.919
1.00
62.80
S
ATOM
2160
OE2
GLU
A
281
45.187
1.411
−17.923
1.00
62.74
8
ATOM
2161
N
LEU
A
282
48.958
3.235
−22.781
1.00
57.94
7
ATOM
2162
CA
LEU
A
282
49.944
3.334
−23.844
1.00
60.20
6
ATOM
2163
C
LEU
A
282
50.394
1.966
−24.343
1.00
62.75
6
ATOM
2164
O
LEU
A
282
50.792
1.813
−25.501
1.00
63.61
8
ATOM
2165
CB
LEU
A
282
51.132
4.160
−23.353
1.00
60.14
6
ATOM
2166
CG
LEU
A
282
51.250
5.643
−23.655
1.00
59.64
6
ATOM
2167
CD1
LEU
A
282
49.954
6.281
−24.103
1.00
59.72
6
ATOM
2168
CD2
LEU
A
282
51.880
6.386
−22.494
1.00
58.92
6
ATOM
2169
N
ALA
A
283
50.285
0.961
−23.484
1.00
64.72
7
ATOM
2170
CA
ALA
A
283
50.637
−0.410
−23.818
1.00
66.41
6
ATOM
2171
C
ALA
A
283
49.397
−1.291
−23.933
1.00
67.10
6
ATOM
2172
O
ALA
A
283
48.394
−0.879
−24.563
1.00
68.25
8
ATOM
2173
CB
ALA
A
283
51.563
−1.007
−22.764
1.00
66.62
6
Monomer B
ATOM
2174
N
MET
B
1
58.003
−23.593
11.263
1.00
36.48
7
ATOM
2175
CA
MET
B
1
58.132
−22.126
11.083
1.00
33.40
6
ATOM
2176
C
MET
B
1
58.194
−21.749
9.627
1.00
33.88
6
ATOM
2177
O
MET
B
1
59.003
−22.271
8.843
1.00
34.96
8
ATOM
2178
CB
MET
B
1
59.383
−21.686
11.860
1.00
32.85
6
ATOM
2179
CG
MET
B
1
59.602
−20.178
11.711
1.00
32.05
6
ATOM
2180
SD
MET
B
1
61.001
−19.706
12.738
1.00
32.48
16
ATOM
2181
CE
MET
B
1
62.316
−19.795
11.507
1.00
33.02
6
ATOM
2182
N
LEU
B
2
57.366
−20.850
9.145
1.00
30.67
7
ATOM
2183
CA
LEU
B
2
57.332
−20.400
7.790
1.00
31.35
6
ATOM
2184
C
LEU
B
2
58.315
−19.246
7.576
1.00
32.39
6
ATOM
2185
O
LEU
B
2
58.367
−18.394
8.491
1.00
31.76
8
ATOM
2186
CB
LEU
B
2
55.926
−19.896
7.473
1.00
35.48
6
ATOM
2187
CG
LEU
B
2
54.773
−20.875
7.670
1.00
38.24
6
ATOM
2188
CD1
LEU
B
2
53.410
−20.187
7.668
1.00
37.95
6
ATOM
2189
CD2
LEU
B
2
54.803
−21.930
6.560
1.00
38.99
6
ATOM
2190
N
ILE
B
3
58.980
−19.217
6.439
1.00
28.48
7
ATOM
2191
CA
ILE
B
3
59.916
−18.162
6.099
1.00
29.00
6
ATOM
2192
C
ILE
B
3
59.442
−17.553
4.806
1.00
30.65
6
ATOM
2193
O
ILE
B
3
59.350
−18.257
3.778
1.00
31.80
8
ATOM
2194
CB
ILE
B
3
61.380
−18.634
5.938
1.00
31.56
6
ATOM
2195
CG1
ILE
B
3
61.859
−19.222
7.261
1.00
31.29
6
ATOM
2196
CG2
ILE
B
3
62.257
−17.481
5.477
1.00
32.77
6
ATOM
2197
CD1
ILE
B
3
63.283
−19.769
7.266
1.00
37.37
6
ATOM
2198
N
ILE
B
4
58.918
−16.333
4.826
1.00
24.55
7
ATOM
2199
CA
ILE
B
4
58.284
−15.663
3.748
1.00
26.13
6
ATOM
2200
C
ILE
B
4
59.159
−14.534
3.279
1.00
28.00
6
ATOM
2201
O
ILE
B
4
59.649
−13.738
4.079
1.00
28.39
8
ATOM
2202
CB
ILE
B
4
56.926
−15.034
4.179
1.00
26.38
6
ATOM
2203
CG1
ILE
B
4
56.042
−16.103
4.827
1.00
30.33
6
ATOM
2204
CG2
ILE
B
4
56.248
−14.318
3.013
1.00
28.07
6
ATOM
2205
CD1
ILE
B
4
55.611
−17.272
3.955
1.00
30.56
6
ATOM
2206
N
GLU
B
5
59.374
−14.485
1.987
1.00
29.37
7
ATOM
2207
CA
GLU
B
5
60.209
−13.449
1.380
1.00
31.10
6
ATOM
2208
C
GLU
B
5
59.387
−12.614
0.487
1.00
30.29
6
ATOM
2209
O
GLU
B
5
59.982
−11.574
0.059
1.00
32.17
8
ATOM
2210
CB
GLU
B
5
61.292
−14.267
0.655
1.00
35.81
6
ATOM
2211
CG
GLU
B
5
62.267
−15.017
1.547
1.00
40.51
6
ATOM
2212
CD
GLU
B
5
63.167
−15.907
0.709
1.00
45.93
6
ATOM
2213
OE1
GLU
B
5
63.562
−16.994
1.195
1.00
48.88
8
ATOM
2214
OE2
GLU
B
5
63.451
−15.521
−0.447
1.00
46.38
8
ATOM
2215
N
THR
B
6
58.142
−12.721
0.076
1.00
26.13
7
ATOM
2216
CA
THR
B
6
57.578
−11.758
−0.836
1.00
27.91
6
ATOM
2217
C
THR
B
6
56.298
−11.128
−0.207
1.00
24.93
6
ATOM
2218
O
THR
B
6
55.656
−11.788
0.619
1.00
27.98
8
ATOM
2219
CB
THR
B
6
57.229
−12.351
−2.205
1.00
31.04
6
ATOM
2220
OG1
THR
B
6
56.159
−13.300
−2.052
1.00
30.86
8
ATOM
2221
CG2
THR
B
6
58.425
−13.076
−2.851
1.00
31.94
6
ATOM
2222
N
LEU
B
7
55.927
−10.037
−0.790
1.00
27.39
7
ATOM
2223
CA
LEU
B
7
54.715
−9.308
−0.367
1.00
28.55
6
ATOM
2224
C
LEU
B
7
53.455
−10.153
−0.636
1.00
27.46
6
ATOM
2225
O
LEU
B
7
52.669
−10.343
0.308
1.00
26.58
8
ATOM
2226
CB
LEU
B
7
54.583
−7.921
−0.986
1.00
29.88
6
ATOM
2227
CG
LEU
B
7
55.750
−6.939
−0.729
1.00
31.25
6
ATOM
2228
CD1
LEU
B
7
55.361
−5.499
−1.043
1.00
31.80
6
ATOM
2229
CD2
LEU
B
7
56.271
−7.052
0.703
1.00
30.25
6
ATOM
2230
N
PRO
B
8
53.288
−10.697
−1.811
1.00
28.20
7
ATOM
2231
CA
PRO
B
8
52.092
−11.501
−2.092
1.00
28.01
6
ATOM
2232
C
PRO
B
8
51.973
−12.671
−1.172
1.00
27.27
6
ATOM
2233
O
PRO
B
8
50.869
−12.943
−0.641
1.00
26.76
8
ATOM
2234
CB
PRO
B
8
52.264
−11.941
−3.550
1.00
30.16
6
ATOM
2235
CG
PRO
B
8
53.126
−10.877
−4.147
1.00
30.87
6
ATOM
2236
CD
PRO
B
8
54.088
−10.500
−3.047
1.00
28.88
6
ATOM
2237
N
LEU
B
9
53.045
−13.427
−0.954
1.00
25.43
7
ATOM
2238
CA
LEU
B
9
53.054
−14.599
−0.088
1.00
25.93
6
ATOM
2239
C
LEU
B
9
52.839
−14.206
1.363
1.00
27.59
6
ATOM
2240
O
LEU
B
9
52.069
−14.843
2.081
1.00
25.94
8
ATOM
2241
CB
LEU
B
9
54.355
−15.416
−0.317
1.00
27.71
6
ATOM
2242
CG
LEU
B
9
54.311
−16.200
−1.656
1.00
31.97
6
ATOM
2243
CD1
LEU
B
9
55.671
−16.790
−1.961
1.00
30.14
6
ATOM
2244
CD2
LEU
B
9
53.236
−17.279
−1.607
1.00
32.64
6
ATOM
2245
N
LEU
B
10
53.323
−13.028
1.819
1.00
25.26
7
ATOM
2246
CA
LEU
B
10
53.068
−12.583
3.182
1.00
23.45
6
ATOM
2247
C
LEU
B
10
51.581
−12.234
3.362
1.00
22.04
6
ATOM
2248
O
LEU
B
10
50.941
−12.683
4.336
1.00
22.46
8
ATOM
2249
CB
LEU
B
10
53.963
−11.368
3.535
1.00
25.32
6
ATOM
2250
CG
LEU
B
10
53.618
−10.738
4.917
1.00
23.24
6
ATOM
2251
CD1
LEU
B
10
53.904
−11.665
6.068
1.00
21.41
6
ATOM
2252
CD2
LEU
B
10
54.376
−9.417
5.105
1.00
22.97
6
ATOM
2253
N
ARG
B
11
50.992
−11.537
2.407
1.00
23.80
7
ATOM
2254
CA
ARG
B
11
49.591
−11.130
2.459
1.00
26.88
6
ATOM
2255
C
ARG
B
11
48.681
−12.350
2.583
1.00
26.18
6
ATOM
2256
O
ARG
B
11
47.707
−12.322
3.328
1.00
23.87
8
ATOM
2257
CB
ARG
B
11
49.208
−10.303
1.232
1.00
26.73
6
ATOM
2258
CG
ARG
B
11
49.968
−8.984
1.209
1.00
29.98
6
ATOM
2259
CD
ARG
B
11
49.306
−7.986
0.278
1.00
35.78
6
ATOM
2260
NE
ARG
B
11
49.673
−6.602
0.492
1.00
38.73
7
ATOM
2261
CZ
ARG
B
11
50.447
−5.830
−0.254
1.00
39.79
6
ATOM
2262
NH1
ARG
B
11
51.031
−6.255
−1.376
1.00
41.64
7
ATOM
2263
NH2
ARG
B
11
50.651
−4.546
0.070
1.00
40.26
7
ATOM
2264
N
GLN
B
12
48.992
−13.409
1.864
1.00
24.75
7
ATOM
2265
CA
GLN
B
12
48.289
−14.712
1.885
1.00
23.93
6
ATOM
2266
C
GLN
B
12
48.282
−15.281
3.285
1.00
23.24
6
ATOM
2267
O
GLN
B
12
47.231
−15.711
3.804
1.00
23.11
8
ATOM
2268
CB
GLN
B
12
48.919
−15.669
0.879
1.00
25.20
6
ATOM
2269
CG
GLN
B
12
48.494
−17.114
0.983
1.00
31.10
6
ATOM
2270
CD
GLN
B
12
48.983
−18.004
−0.160
1.00
33.85
6
ATOM
2271
OE1
GLN
B
12
50.160
−18.359
−0.226
1.00
34.46
8
ATOM
2272
NE2
GLN
B
12
48.024
−18.373
−1.035
1.00
37.05
7
ATOM
2273
N
GLN
B
13
49.406
−15.241
4.018
1.00
20.76
7
ATOM
2274
CA
GLN
B
13
49.531
−15.725
5.367
1.00
21.58
6
ATOM
2275
C
GLN
B
13
48.755
−14.802
6.342
1.00
19.88
6
ATOM
2276
O
GLN
B
13
48.070
−15.312
7.250
1.00
20.12
8
ATOM
2277
CB
GLN
B
13
51.005
−15.852
5.844
1.00
22.55
6
ATOM
2278
CG
GLN
B
13
51.779
−16.951
5.087
1.00
25.94
6
ATOM
2279
CD
GLN
B
13
51.107
−18.297
5.150
1.00
27.86
6
ATOM
2280
OE1
GLN
B
13
50.677
−18.693
6.225
1.00
28.91
8
ATOM
2281
NE2
GLN
B
13
50.985
−18.937
3.993
1.00
32.63
7
ATOM
2282
N
ILE
B
14
48.738
−13.510
6.042
1.00
21.05
7
ATOM
2283
CA
ILE
B
14
48.035
−12.575
6.947
1.00
20.18
6
ATOM
2284
C
ILE
B
14
46.501
−12.822
6.819
1.00
21.51
6
ATOM
2285
O
ILE
B
14
45.800
−12.838
7.850
1.00
21.76
8
ATOM
2286
CB
ILE
B
14
48.438
−11.133
6.718
1.00
21.52
6
ATOM
2287
CG1
ILE
B
14
49.931
−10.873
7.014
1.00
21.53
6
ATOM
2288
CG2
ILE
B
14
47.609
−10.137
7.572
1.00
20.30
6
ATOM
2289
CD1
ILE
B
14
50.448
−11.493
8.287
1.00
20.36
6
ATOM
2290
N
ARG
B
15
46.060
−13.042
5.580
1.00
21.97
7
ATOM
2291
CA
ARG
B
15
44.640
−13.407
5.403
1.00
21.03
6
ATOM
2292
C
ARG
B
15
44.328
−14.704
6.120
1.00
20.84
6
ATOM
2293
O
ARG
B
15
43.231
−14.819
6.693
1.00
21.21
8
ATOM
2294
CB
ARG
B
15
44.362
−13.468
3.903
1.00
23.95
6
ATOM
2295
CG
ARG
B
15
44.439
−12.110
3.182
1.00
28.33
6
ATOM
2296
CD
ARG
B
15
43.633
−12.304
1.885
1.00
35.29
6
ATOM
2297
NE
ARG
B
15
44.463
−13.095
0.938
1.00
39.61
7
ATOM
2298
CZ
ARG
B
15
45.378
−12.352
0.272
1.00
43.48
6
ATOM
2299
NH1
ARG
B
15
45.533
−11.036
0.426
1.00
44.40
7
ATOM
2300
NH2
ARG
B
15
46.158
−12.973
−0.594
1.00
43.72
7
ATOM
2301
N
ARG
B
16
45.189
−15.724
6.069
1.00
18.66
7
ATOM
2302
CA
ARG
B
16
44.923
−16.986
6.717
1.00
19.99
6
ATOM
2303
C
ARG
B
16
44.816
−16.743
8.234
1.00
20.42
6
ATOM
2304
O
ARG
B
16
43.855
−17.229
8.824
1.00
19.70
8
ATOM
2305
CB
ARG
B
16
45.959
−18.073
6.435
1.00
22.24
6
ATOM
2306
CG
ARG
B
16
45.869
−19.264
7.352
1.00
23.29
6
ATOM
2307
CD
ARG
B
16
46.986
−20.277
7.132
1.00
25.24
6
ATOM
2308
NE
ARG
B
16
48.309
−19.702
7.470
1.00
27.88
7
ATOM
2309
CZ
ARG
B
16
48.797
−19.716
8.706
1.00
28.92
6
ATOM
2310
NH1
ARG
B
16
50.016
−19.215
8.961
1.00
28.52
7
ATOM
2311
NH2
ARG
B
16
48.126
−20.327
9.679
1.00
24.92
7
ATOM
2312
N
LEU
B
17
45.716
−15.933
8.815
1.00
19.27
7
ATOM
2313
CA
LEU
B
17
45.626
−15.699
10.270
1.00
20.77
6
ATOM
2314
C
LEU
B
17
44.352
−14.990
10.702
1.00
20.30
6
ATOM
2315
O
LEU
B
17
43.778
−15.286
11.759
1.00
19.03
8
ATOM
2316
CB
LEU
B
17
46.900
−14.923
10.697
1.00
22.28
6
ATOM
2317
CG
LEU
B
17
48.154
−15.834
10.589
1.00
20.91
6
ATOM
2318
CD1
LEU
B
17
49.346
−14.854
10.747
1.00
23.26
6
ATOM
2319
CD2
LEU
B
17
48.210
−16.976
11.546
1.00
23.26
6
ATOM
2320
N
ARG
B
18
43.880
−14.084
9.852
1.00
20.08
7
ATOM
2321
CA
ARG
B
18
42.616
−13.394
10.085
1.00
20.19
6
ATOM
2322
C
ARG
B
18
41.443
−14.367
10.053
1.00
20.24
6
ATOM
2323
O
ARG
B
18
40.595
−14.419
10.938
1.00
19.77
8
ATOM
2324
CB
ARG
B
18
42.410
−12.287
9.049
1.00
19.52
6
ATOM
2325
CG
ARG
B
18
41.388
−11.239
9.456
1.00
25.28
6
ATOM
2326
CD
ARG
B
18
40.953
−10.402
8.264
1.00
30.78
6
ATOM
2327
NE
ARG
B
18
42.033
−9.556
7.766
1.00
37.79
7
ATOM
2328
CZ
ARG
B
18
42.285
−9.348
6.478
1.00
41.34
6
ATOM
2329
NH1
ARG
B
18
41.532
−9.927
5.553
1.00
41.84
7
ATOM
2330
NH2
ARG
B
18
43.290
−8.562
6.119
1.00
42.14
7
ATOM
2331
N
MET
B
19
41.447
−15.266
9.053
1.00
19.56
7
ATOM
2332
CA
MET
B
19
40.384
−16.272
8.983
1.00
21.07
6
ATOM
2333
C
MET
B
19
40.376
−17.192
10.199
1.00
19.93
6
ATOM
2334
O
MET
B
19
39.291
−17.611
10.629
1.00
18.95
8
ATOM
2335
CB
MET
B
19
40.507
−17.047
7.683
1.00
21.11
6
ATOM
2336
CG
MET
B
19
39.650
−18.307
7.449
1.00
22.70
6
ATOM
2337
SD
MET
B
19
40.253
−19.824
8.206
1.00
21.29
16
ATOM
2338
CE
MET
B
19
41.816
−20.143
7.368
1.00
22.90
6
ATOM
2339
N
GLU
B
20
41.516
−17.512
10.731
1.00
18.16
7
ATOM
2340
CA
GLU
B
20
41.687
−18.429
11.858
1.00
20.12
6
ATOM
2341
C
GLU
B
20
41.280
−17.732
13.182
1.00
20.85
6
ATOM
2342
O
GLU
B
20
41.156
−18.387
14.243
1.00
24.28
8
ATOM
2343
CB
GLU
B
20
43.113
−18.960
11.945
1.00
18.82
6
ATOM
2344
CG
GLU
B
20
43.467
−19.977
10.846
1.00
21.83
6
ATOM
2345
CD
GLU
B
20
44.911
−20.433
10.890
1.00
26.79
6
ATOM
2346
OE1
GLU
B
20
45.611
−20.063
11.869
1.00
28.93
8
ATOM
2347
OE2
GLU
B
20
45.312
−21.210
9.985
1.00
26.44
8
ATOM
2348
N
GLY
B
21
41.236
−16.424
13.172
1.00
21.16
7
ATOM
2349
CA
GLY
B
21
40.877
−15.568
14.299
1.00
20.08
6
ATOM
2350
C
GLY
B
21
42.055
−15.540
15.311
1.00
21.45
6
ATOM
2351
O
GLY
B
21
41.856
−15.580
16.546
1.00
20.95
8
ATOM
2352
N
LYS
B
22
43.279
−15.515
14.815
1.00
17.96
7
ATOM
2353
CA
LYS
B
22
44.458
−15.503
15.668
1.00
21.37
6
ATOM
2354
C
LYS
B
22
44.924
−14.091
15.953
1.00
23.78
6
ATOM
2355
O
LYS
B
22
44.942
−13.267
15.041
1.00
24.76
8
ATOM
2356
CB
LYS
B
22
45.638
−16.191
14.984
1.00
22.71
6
ATOM
2357
CG
LYS
B
22
45.420
−17.662
14.646
1.00
25.81
6
ATOM
2358
CD
LYS
B
22
45.337
−18.553
15.836
1.00
28.29
6
ATOM
2359
CE
LYS
B
22
44.963
−19.997
15.550
1.00
33.33
6
ATOM
2360
NZ
LYS
B
22
45.832
−20.715
14.575
1.00
29.69
7
ATOM
2361
N
ARG
B
23
45.285
−13.775
17.175
1.00
19.63
7
ATOM
2362
CA
ARG
B
23
45.917
−12.467
17.446
1.00
22.19
6
ATOM
2363
C
ARG
B
23
47.415
−12.521
17.203
1.00
20.99
6
ATOM
2364
O
ARG
B
23
48.014
−13.529
17.533
1.00
22.27
8
ATOM
2365
CB
ARG
B
23
45.620
−12.042
18.877
1.00
23.98
6
ATOM
2366
CG
ARG
B
23
44.149
−11.748
19.161
1.00
33.05
6
ATOM
2367
CD
ARG
B
23
43.965
−11.207
20.600
1.00
35.95
6
ATOM
2368
NE
ARG
B
23
44.774
−11.865
21.560
1.00
39.00
7
ATOM
2369
CZ
ARG
B
23
45.045
−12.903
22.319
1.00
38.30
6
ATOM
2370
NH1
ARG
B
23
44.343
−14.060
22.457
1.00
34.37
7
ATOM
2371
NH2
ARG
B
23
46.204
−12.653
22.881
1.00
33.10
7
ATOM
2372
N
VAL
B
24
47.873
−11.534
16.444
1.00
19.44
7
ATOM
2373
CA
VAL
B
24
49.260
−11.534
15.984
1.00
19.87
6
ATOM
2374
C
VAL
B
24
50.133
−10.493
16.615
1.00
20.77
6
ATOM
2375
O
VAL
B
24
49.724
−9.356
16.770
1.00
20.17
8
ATOM
2376
CB
VAL
B
24
49.220
−11.301
14.473
1.00
20.82
6
ATOM
2377
CG1
VAL
B
24
50.587
−11.071
13.856
1.00
21.58
6
ATOM
2378
CG2
VAL
B
24
48.493
−12.516
13.838
1.00
22.44
6
ATOM
2379
N
ALA
B
25
51.327
−10.950
17.072
1.00
18.32
7
ATOM
2380
CA
ALA
B
25
52.294
−9.989
17.591
1.00
18.65
6
ATOM
2381
C
ALA
B
25
53.431
−9.885
16.600
1.00
22.09
6
ATOM
2382
O
ALA
B
25
53.908
−10.915
16.053
1.00
26.60
8
ATOM
2383
CB
ALA
B
25
52.871
−10.371
18.953
1.00
20.06
6
ATOM
2384
N
LEU
B
26
53.922
−8.705
16.329
1.00
18.28
7
ATOM
2385
CA
LEU
B
26
54.997
−8.468
15.410
1.00
16.76
6
ATOM
2386
C
LEU
B
26
56.273
−8.010
16.156
1.00
20.96
6
ATOM
2387
O
LEU
B
26
56.139
−7.157
17.020
1.00
21.27
8
ATOM
2388
CB
LEU
B
26
54.673
−7.425
14.340
1.00
19.09
6
ATOM
2389
CG
LEU
B
26
55.816
−6.890
13.487
1.00
19.40
6
ATOM
2390
CD1
LEU
B
26
56.464
−7.969
12.603
1.00
21.45
6
ATOM
2391
CD2
LEU
B
26
55.320
−5.738
12.604
1.00
22.40
6
ATOM
2392
N
VAL
B
27
57.396
−8.642
15.874
1.00
20.49
7
ATOM
2393
CA
VAL
B
27
58.684
−8.136
16.430
1.00
19.53
6
ATOM
2394
C
VAL
B
27
59.576
−7.694
15.308
1.00
21.55
6
ATOM
2395
O
VAL
B
27
60.170
−8.516
14.520
1.00
22.20
8
ATOM
2396
CB
VAL
B
27
59.378
−9.239
17.253
1.00
21.88
6
ATOM
2397
CG1
VAL
B
27
60.658
−8.617
17.884
1.00
21.20
6
ATOM
2398
CG2
VAL
B
27
58.513
−9.837
18.318
1.00
20.54
6
ATOM
2399
N
PRO
B
28
59.761
−6.435
14.910
1.00
20.58
7
ATOM
2400
CA
PRO
B
28
60.557
−5.881
13.878
1.00
21.31
6
ATOM
2401
C
PRO
B
28
62.068
−5.886
14.202
1.00
24.78
6
ATOM
2402
O
PRO
B
28
62.428
−5.538
15.336
1.00
26.50
8
ATOM
2403
CB
PRO
B
28
60.112
−4.424
13.720
1.00
22.66
6
ATOM
2404
CG
PRO
B
28
58.741
−4.426
14.395
1.00
20.85
6
ATOM
2405
CD
PRO
B
28
58.946
−5.327
15.578
1.00
20.40
6
ATOM
2406
N
THR
B
29
62.875
−6.483
13.317
1.00
26.26
7
ATOM
2407
CA
THR
B
29
64.329
−6.556
13.614
1.00
25.08
6
ATOM
2408
C
THR
B
29
65.126
−6.328
12.359
1.00
25.98
6
ATOM
2409
O
THR
B
29
64.643
−6.415
11.228
1.00
23.47
8
ATOM
2410
CB
THR
B
29
64.820
−7.900
14.201
1.00
26.97
6
ATOM
2411
OG1
THR
B
29
65.022
−8.817
13.088
1.00
26.74
8
ATOM
2412
CG2
THR
B
29
63.914
−8.579
15.219
1.00
25.95
6
ATOM
2413
N
MET
B
30
66.471
−6.078
12.560
1.00
25.32
7
ATOM
2414
CA
MET
B
30
67.357
−5.995
11.415
1.00
26.82
6
ATOM
2415
C
MET
B
30
68.261
−7.249
11.384
1.00
28.96
6
ATOM
2416
O
MET
B
30
69.347
−7.183
10.815
1.00
30.56
8
ATOM
2417
CB
MET
B
30
68.229
−4.738
11.416
1.00
26.43
6
ATOM
2418
CG
MET
B
30
67.252
−3.504
11.203
1.00
27.24
6
ATOM
2419
SD
MET
B
30
67.969
−2.187
10.263
1.00
28.19
16
ATOM
2420
CE
MET
B
30
69.323
−1.713
11.388
1.00
33.08
6
ATOM
2421
N
GLY
B
31
67.793
−8.340
11.934
1.00
27.82
7
ATOM
2422
CA
GLY
B
31
68.599
−9.593
11.926
1.00
29.40
6
ATOM
2423
C
GLY
B
31
69.833
−9.495
12.829
1.00
31.29
6
ATOM
2424
O
GLY
B
31
69.934
−8.645
13.713
1.00
28.83
8
ATOM
2425
N
ASN
B
32
70.728
−10.486
12.690
1.00
31.40
7
ATOM
2426
CA
ASN
B
32
71.923
−10.565
13.552
1.00
33.60
6
ATOM
2427
C
ASN
B
32
71.454
−10.664
14.982
1.00
30.00
6
ATOM
2428
O
ASN
B
32
71.870
−9.961
15.906
1.00
32.23
8
ATOM
2429
CB
ASN
B
32
72.857
−9.379
13.347
1.00
35.71
6
ATOM
2430
CG
ASN
B
32
74.231
−9.610
13.979
1.00
39.99
6
ATOM
2431
OD1
ASN
B
32
74.920
−8.633
14.294
1.00
42.85
8
ATOM
2432
ND2
ASN
B
32
74.607
−10.864
14.228
1.00
40.08
7
ATOM
2433
N
LEU
B
33
70.506
−11.572
15.191
1.00
30.19
7
ATOM
2434
CA
LEU
B
33
69.833
−11.774
16.449
1.00
29.02
6
ATOM
2435
C
LEU
B
33
70.684
−12.343
17.566
1.00
35.03
6
ATOM
2436
O
LEU
B
33
71.521
−13.207
17.312
1.00
36.34
8
ATOM
2437
CB
LEU
B
33
68.616
−12.717
16.279
1.00
30.07
6
ATOM
2438
CG
LEU
B
33
67.670
−12.217
15.191
1.00
29.98
6
ATOM
2439
CD1
LEU
B
33
66.434
−13.121
15.083
1.00
31.08
6
ATOM
2440
CD2
LEU
B
33
67.221
−10.777
15.431
1.00
28.84
6
ATOM
2441
N
HIS
B
34
70.295
−11.945
18.774
1.00
35.85
7
ATOM
2442
CA
HIS
B
34
71.004
−12.381
19.965
1.00
39.05
6
ATOM
2443
C
HIS
B
34
69.976
−12.567
21.067
1.00
37.94
6
ATOM
2444
O
HIS
B
34
68.762
−12.451
20.791
1.00
37.26
8
ATOM
2445
CB
HIS
B
34
72.097
−11.404
20.404
1.00
40.15
6
ATOM
2446
CG
HIS
B
34
71.668
−10.006
20.714
1.00
42.43
6
ATOM
2447
ND1
HIS
B
34
70.876
−9.671
21.799
1.00
44.12
7
ATOM
2448
CD2
HIS
B
34
71.953
−8.848
20.062
1.00
43.13
6
ATOM
2449
CE1
HIS
B
34
70.689
−8.360
21.808
1.00
44.28
6
ATOM
2450
NE2
HIS
B
34
71.323
−7.840
20.763
1.00
44.67
7
ATOM
2451
N
ASP
B
35
70.439
−12.874
22.263
1.00
36.30
7
ATOM
2452
CA
ASP
B
35
69.531
−13.176
23.352
1.00
38.71
6
ATOM
2453
C
ASP
B
35
68.539
−12.055
23.649
1.00
38.11
6
ATOM
2454
O
ASP
B
35
67.448
−12.373
24.116
1.00
38.15
8
ATOM
2455
CB
ASP
B
35
70.309
−13.480
24.637
1.00
43.89
6
ATOM
2456
CG
ASP
B
35
71.071
−14.776
24.631
1.00
48.19
6
ATOM
2457
OD1
ASP
B
35
71.046
−15.496
23.603
1.00
50.75
8
ATOM
2458
OD2
ASP
B
35
71.701
−15.074
25.689
1.00
51.91
8
ATOM
2459
N
GLY
B
36
68.919
−10.788
23.499
1.00
35.59
7
ATOM
2460
CA
GLY
B
36
68.007
−9.688
23.778
1.00
33.96
6
ATOM
2461
C
GLY
B
36
66.844
−9.774
22.751
1.00
32.11
6
ATOM
2462
O
GLY
B
36
65.738
−9.524
23.235
1.00
30.98
8
ATOM
2463
N
HIS
B
37
67.149
−10.177
21.521
1.00
31.48
7
ATOM
2464
CA
HIS
B
37
66.086
−10.322
20.581
1.00
31.68
6
ATOM
2465
C
HIS
B
37
65.118
−11.479
20.969
1.00
33.06
6
ATOM
2466
O
HIS
B
37
63.861
−11.440
20.850
1.00
30.99
8
ATOM
2467
CB
HIS
B
37
66.507
−10.514
19.175
1.00
31.96
6
ATOM
2468
CG
HIS
B
37
67.366
−9.425
18.643
1.00
34.37
6
ATOM
2469
ND1
HIS
B
37
66.888
−8.299
18.005
1.00
37.43
7
ATOM
2470
CD2
HIS
B
37
68.714
−9.330
18.624
1.00
34.96
6
ATOM
2471
CE1
HIS
B
37
67.890
−7.535
17.580
1.00
35.54
6
ATOM
2472
NE2
HIS
B
37
69.003
−8.153
17.962
1.00
39.23
7
ATOM
2473
N
MET
B
38
65.704
−12.577
21.486
1.00
31.32
7
ATOM
2474
CA
MET
B
38
64.880
−13.668
22.001
1.00
31.44
6
ATOM
2475
C
MET
B
38
63.959
−13.252
23.115
1.00
29.66
6
ATOM
2476
O
MET
B
38
62.851
−13.809
23.253
1.00
28.40
8
ATOM
2477
CB
MET
B
38
65.799
−14.827
22.487
1.00
34.21
6
ATOM
2478
CG
MET
B
38
66.423
−15.620
21.375
1.00
35.15
6
ATOM
2479
SD
MET
B
38
65.631
−15.970
19.832
1.00
35.12
16
ATOM
2480
CE
MET
B
38
66.123
−14.628
18.770
1.00
36.33
6
ATOM
2481
N
LYS
B
39
64.228
−12.308
23.996
1.00
29.09
7
ATOM
2482
CA
LYS
B
39
63.368
−11.857
25.065
1.00
26.18
6
ATOM
2483
C
LYS
B
39
62.142
−11.078
24.470
1.00
25.41
6
ATOM
2484
O
LYS
B
39
61.042
−11.228
24.964
1.00
26.08
8
ATOM
2485
CB
LYS
B
39
64.048
−10.935
26.076
1.00
27.75
6
ATOM
2486
CG
LYS
B
39
63.195
−10.551
27.262
1.00
27.45
6
ATOM
2487
CD
LYS
B
39
64.031
−9.643
28.216
1.00
30.13
6
ATOM
2488
CE
LYS
B
39
63.142
−9.261
29.377
1.00
29.21
6
ATOM
2489
NZ
LYS
B
39
63.883
−8.413
30.361
1.00
32.36
7
ATOM
2490
N
LEU
B
40
62.394
−10.379
23.402
1.00
26.07
7
ATOM
2491
CA
LEU
B
40
61.256
−9.741
22.709
1.00
25.52
6
ATOM
2492
C
LEU
B
40
60.254
−10.805
22.220
1.00
25.72
6
ATOM
2493
O
LEU
B
40
59.855
−10.609
22.293
1.00
23.50
8
ATOM
2494
CB
LEU
B
40
61.702
−8.954
21.497
1.00
26.47
6
ATOM
2495
CG
LEU
B
40
62.739
−7.859
21.758
1.00
30.07
6
ATOM
2496
CD1
LEU
B
40
63.073
−7.128
20.474
1.00
31.00
6
ATOM
2497
CD2
LEU
B
40
62.237
−6.905
22.832
1.00
30.41
6
ATOM
2498
N
VAL
B
41
60.844
−11.842
21.611
1.00
25.04
7
ATOM
2499
CA
VAL
B
41
59.995
−12.936
21.065
1.00
24.43
6
ATOM
2500
C
VAL
B
41
59.235
−13.579
22.162
1.00
23.84
6
ATOM
2501
O
VAL
B
41
58.037
−13.868
22.103
1.00
23.75
8
ATOM
2502
CB
VAL
B
41
60.893
−13.922
20.289
1.00
24.40
6
ATOM
2503
CG1
VAL
B
41
60.057
−15.140
19.914
1.00
24.57
6
ATOM
2504
CG2
VAL
B
41
61.496
−13.337
19.819
1.00
25.66
6
ATOM
2505
N
ASP
B
42
59.826
−13.850
23.376
1.00
25.85
7
ATOM
2506
CA
ASP
B
42
59.130
−14.426
24.480
1.00
26.19
6
ATOM
2507
C
ASP
B
42
57.994
−13.543
24.981
1.00
28.20
6
ATOM
2508
O
ASP
B
42
56.910
−14.030
25.341
1.00
27.55
8
ATOM
2509
CB
ASP
8
42
60.131
−14.709
25.659
1.00
29.50
6
ATOM
2510
CG
ASP
B
42
61.118
−15.822
25.377
1.00
32.71
6
ATOM
2511
OD1
ASP
B
42
61.051
−16.616
24.419
1.00
33.03
8
ATOM
2512
OD2
ASP
B
42
62.135
−15.893
26.160
1.00
33.67
8
ATOM
2513
N
GLU
B
43
58.205
−12.216
24.957
1.00
26.23
7
ATOM
2514
CA
GLU
B
43
57.130
−11.321
25.355
1.00
27.21
6
ATOM
2515
C
GLU
B
43
55.973
−11.339
24.327
1.00
24.30
6
ATOM
2516
O
GLU
B
43
54.809
−11.340
24.709
1.00
24.66
8
ATOM
2517
CB
GLU
B
43
57.676
−9.912
25.475
1.00
30.67
6
ATOM
2518
CG
GLU
B
43
56.740
−8.904
26.130
1.00
36.81
6
ATOM
2519
CD
GLU
B
43
56.445
−9.257
27.585
1.00
40.25
6
ATOM
2520
OE1
GLU
B
43
57.347
−9.847
28.236
1.00
44.07
8
ATOM
2521
OE2
GLU
B
43
55.348
−8.999
28.121
1.00
40.92
8
ATOM
2522
N
ALA
B
44
56.324
−11.466
23.083
1.00
26.35
7
ATOM
2523
CA
ALA
B
44
55.321
−11.474
21.969
1.00
23.41
6
ATOM
2524
C
ALA
B
44
54.526
−12.754
22.879
1.00
26.63
6
ATOM
2525
O
ALA
B
44
53.287
−12.728
22.074
1.00
26.61
8
ATOM
2526
CB
ALA
B
44
56.007
−11.299
20.651
1.00
25.41
6
ATOM
2527
N
LYS
B
45
55.209
−13.882
22.329
1.00
27.34
7
ATOM
2528
CA
LYS
B
45
54.542
−15.169
22.501
1.00
29.71
6
ATOM
2529
C
LYS
B
45
53.589
−15.160
23.659
1.00
28.45
6
ATOM
2530
O
LYS
B
45
52.559
−15.805
23.717
1.00
28.18
8
ATOM
2531
CB
LYS
B
45
55.537
−16.322
22.783
1.00
32.90
6
ATOM
2532
CG
LYS
B
45
56.368
−16.726
21.588
1.00
38.80
6
ATOM
2533
CD
LYS
B
45
57.724
−17.301
21.961
1.00
43.49
6
ATOM
2534
CE
LYS
B
45
57.757
−18.398
23.004
1.00
46.00
6
ATOM
2535
NZ
LYS
B
45
59.077
−18.396
23.727
1.00
47.62
7
ATOM
2536
N
ALA
B
46
53.935
−14.446
24.748
1.00
27.58
7
ATOM
2537
CA
ALA
B
46
53.076
−14.389
25.900
1.00
27.60
6
ATOM
2538
C
ALA
B
46
51.831
−13.527
25.751
1.00
28.91
6
ATOM
2539
O
ALA
B
46
50.905
−13.633
26.549
1.00
30.19
8
ATOM
2540
CB
ALA
B
46
53.882
−13.818
27.097
1.00
28.29
6
ATOM
2541
N
ARG
B
47
51.754
−12.657
24.741
1.00
26.88
7
ATOM
2542
CA
ARG
B
47
50.691
−11.719
24.586
1.00
25.76
6
ATOM
2543
C
ARG
B
47
49.781
−11.972
23.373
1.00
23.01
6
ATOM
2544
O
ARG
B
47
48.813
−11.243
23.291
1.00
23.89
8
ATOM
2545
CB
ARG
B
47
51.345
−10.312
24.433
1.00
24.92
6
ATOM
2546
CG
ARG
B
47
51.975
−9.858
25.800
1.00
27.22
6
ATOM
2547
CD
ARG
B
47
52.755
−8.575
25.491
1.00
29.69
6
ATOM
2548
NE
ARG
B
47
53.415
−7.966
26.670
1.00
34.33
7
ATOM
2549
CZ
ARG
B
47
52.861
−6.966
27.358
1.00
35.85
6
ATOM
2550
NH1
ARG
B
47
51.688
−6.442
27.073
1.00
35.22
7
ATOM
2551
NH2
ARG
B
47
53.555
−6.467
28.392
1.00
37.54
7
ATOM
2552
N
ALA
B
48
50.203
−12.899
22.529
1.00
23.33
7
ATOM
2553
CA
ALA
B
48
49.413
−13.114
21.284
1.00
23.32
6
ATOM
2554
C
ALA
B
48
49.405
−14.574
20.933
1.00
26.45
6
ATOM
2555
O
ALA
B
48
50.224
−15.356
21.466
1.00
24.59
8
ATOM
2556
CB
ALA
B
48
50.059
−12.332
20.168
1.00
23.24
6
ATOM
2557
N
ASP
B
49
48.547
−15.010
20.004
1.00
24.54
7
ATOM
2558
CA
ASP
B
49
48.537
−16.394
19.594
1.00
24.90
6
ATOM
2559
C
ASP
B
49
49.677
−16.770
18.689
1.00
24.42
6
ATOM
2560
O
ASP
B
49
50.254
−17.869
18.668
1.00
26.07
8
ATOM
2561
CB
ASP
B
49
47.237
−16.656
18.803
1.00
26.28
6
ATOM
2562
CG
ASP
B
49
45.979
−16.417
19.627
1.00
30.04
6
ATOM
2563
OD1
ASP
B
49
45.977
−16.990
20.754
1.00
32.57
8
ATOM
2564
OD2
ASP
B
49
45.038
−15.712
19.183
1.00
30.75
8
ATOM
2565
N
VAL
B
50
50.004
−15.842
17.792
1.00
20.95
7
ATOM
2566
CA
VAL
B
50
50.980
−15.998
16.747
1.00
20.87
6
ATOM
2567
C
VAL
B
50
52.014
−14.905
16.734
1.00
20.83
6
ATOM
2568
O
VAL
B
50
51.742
−13.704
16.973
1.00
20.70
8
ATOM
2569
CB
VAL
B
50
50.241
−16.031
15.369
1.00
22.53
6
ATOM
2570
CG1
VAL
B
50
51.112
−15.780
14.170
1.00
26.09
6
ATOM
2571
CG2
VAL
B
50
49.536
−17.393
15.199
1.00
25.40
6
ATOM
2572
N
VAL
B
51
53.286
−15.325
16.567
1.00
19.42
7
ATOM
2573
CA
VAL
B
51
54.373
−14.336
16.498
1.80
22.20
6
ATOM
2574
C
VAL
B
51
54.975
−14.279
15.113
1.00
22.35
6
ATOM
2575
O
VAL
B
51
55.400
−15.274
14.488
1.00
23.37
8
ATOM
2576
CB
VAL
B
51
55.498
−14.618
17.516
1.00
23.80
6
ATOM
2577
CG1
VAL
B
51
56.616
−13.574
17.449
1.00
24.48
6
ATOM
2578
CG2
VAL
B
51
54.855
−14.682
18.910
1.00
28.00
6
ATOM
2579
N
VAL
B
52
55.108
−13.080
14.590
1.00
18.68
7
ATOM
2580
CA
VAL
B
52
55.734
−12.772
13.322
1.00
17.55
6
ATOM
2581
C
VAL
B
52
57.014
−11.980
13.623
1.00
21.15
6
ATOM
2582
O
VAL
B
52
56.930
−10.957
14.319
1.00
19.41
8
ATOM
2583
CB
VAL
B
52
54.885
−11.936
12.341
1.00
19.87
6
ATOM
2584
CG1
VAL
B
52
55.613
−11.467
11.107
1.00
19.90
6
ATOM
2585
CG2
VAL
B
52
53.651
−12.759
11.943
1.00
20.31
6
ATOM
2586
N
VAL
B
53
58.150
−12.469
13.104
1.00
20.72
7
ATOM
2587
CA
VAL
B
53
59.396
−11.698
13.267
1.00
20.35
6
ATOM
2588
C
VAL
B
53
59.854
−11.261
11.925
1.00
22.26
6
ATOM
2589
O
VAL
B
53
59.933
−12.026
10.948
1.00
23.47
8
ATOM
2590
CB
VAL
B
53
60.505
−12.545
13.977
1.00
20.44
6
ATOM
2591
CG1
VAL
B
53
61.791
−11.700
14.053
1.00
22.35
6
ATOM
2592
CG2
VAL
B
53
60.059
−13.004
15.346
1.00
22.26
6
ATOM
2593
N
SER
B
54
60.144
−9.957
11.694
1.00
20.14
7
ATOM
2594
CA
SER
B
54
60.629
−9.453
10.425
1.00
20.53
6
ATOM
2595
C
SER
B
54
62.157
−9.208
10.601
1.00
23.03
6
ATOM
2596
O
SER
B
54
62.594
−8.867
11.697
1.00
23.22
8
ATOM
2597
CB
SER
B
54
59.973
−8.182
9.883
1.00
24.56
6
ATOM
2598
OG
SER
B
54
60.079
−7.161
10.861
1.00
24.52
8
ATOM
2599
N
ILE
B
55
62.804
−9.615
9.537
1.00
25.11
7
ATOM
2600
CA
ILE
B
55
64.289
−9.443
9.508
1.00
23.93
6
ATOM
2601
C
ILE
B
55
64.589
−8.756
8.220
1.00
22.42
6
ATOM
2602
O
ILE
B
55
64.333
−9.214
7.082
1.00
23.75
8
ATOM
2603
CB
ILE
B
55
65.017
−10.788
9.599
1.00
25.95
6
ATOM
2604
CG1
ILE
B
55
64.888
−11.494
10.920
1.00
25.74
6
ATOM
2605
CG2
ILE
B
55
66.512
−10.480
9.307
1.00
26.43
6
ATOM
2606
CD1
ILE
B
55
65.315
−12.955
10.805
1.00
29.38
6
ATOM
2607
N
PHE
B
56
65.039
−7.469
8.273
1.00
23.82
7
ATOM
2608
CA
PHE
B
56
65.225
−6.624
7.153
1.00
24.66
6
ATOM
2609
C
PHE
B
56
66.202
−5.465
7.454
1.00
26.79
6
ATOM
2610
O
PHE
B
56
65.937
−4.712
8.392
1.00
26.50
8
ATOM
2611
CB
PHE
B
56
63.878
−6.011
6.668
1.00
22.93
6
ATOM
2612
CG
PHE
B
56
64.081
−5.130
5.476
1.00
24.37
6
ATOM
2613
CD1
PHE
B
56
64.570
−5.602
4.262
1.00
25.67
6
ATOM
2614
CD2
PHE
B
56
63.711
−3.781
5.549
1.00
23.80
6
ATOM
2615
CE1
PHE
B
56
64.765
−4.758
3.193
1.00
25.30
6
ATOM
2616
CE2
PHE
B
56
63.882
−2.969
4.441
1.00
25.84
6
ATOM
2617
CZ
PHE
B
56
64.399
−3.429
3.249
1.00
27.27
6
ATOM
2618
N
VAL
B
57
67.330
−5.512
6.717
1.00
28.13
7
ATOM
2619
CA
VAL
B
57
68.347
−4.471
7.001
1.00
27.59
6
ATOM
2620
C
VAL
B
57
67.968
−3.357
6.089
1.00
26.50
6
ATOM
2621
O
VAL
B
57
68.047
−3.404
4.871
1.00
28.47
8
ATOM
2622
CB
VAL
B
57
69.787
−5.034
6.846
1.00
28.54
6
ATOM
2623
CG1
VAL
B
57
70.795
−3.915
7.235
1.00
30.14
6
ATOM
2624
CG2
VAL
B
57
70.028
−6.232
7.674
1.00
27.80
6
ATOM
2625
N
ASN
B
58
67.280
−2.367
6.723
1.00
27.33
7
ATOM
2626
CA
ASN
B
58
66.643
−1.277
5.989
1.00
28.47
6
ATOM
2627
C
ASN
B
58
67.589
−0.208
5.529
1.00
28.30
6
ATOM
2628
O
ASN
B
58
68.068
0.587
6.350
1.00
29.87
8
ATOM
2629
CB
ASN
B
58
65.608
−0.711
7.004
1.00
27.68
6
ATOM
2630
CG
ASN
B
58
64.919
0.542
6.507
1.00
24.26
6
ATOM
2631
OD1
ASN
B
58
64.739
0.717
5.381
1.00
26.55
8
ATOM
2632
ND2
ASN
B
58
64.487
1.392
7.445
1.00
24.78
7
ATOM
2633
N
PRO
B
59
67.828
−0.063
4.251
1.00
32.20
7
ATOM
2634
CA
PRO
B
59
68.766
0.929
3.749
1.00
32.85
6
ATOM
2635
C
PRO
B
59
68.415
2.336
4.177
1.00
35.54
6
ATOM
2636
C
PRO
B
59
69.298
3.191
4.360
1.00
33.70
8
ATOM
2637
CB
PRO
B
59
68.703
0.729
2.239
1.00
36.08
6
ATOM
2638
CG
PRO
B
59
68.404
−0.761
2.113
1.00
35.06
6
ATOM
2639
CD
PRO
B
59
67.336
−0.957
3.170
1.00
34.20
6
ATOM
2640
N
MET
B
60
67.111
2.642
4.360
1.00
34.39
7
ATOM
2641
CA
MET
B
60
66.683
3.994
4.699
1.00
36.32
6
ATOM
2642
C
MET
B
60
67.197
4.523
6.022
1.00
37.35
6
ATOM
2643
O
MET
B
60
67.169
5.772
6.239
1.00
38.05
8
ATOM
2644
CB
MET
B
60
65.148
4.088
4.790
1.00
37.91
6
ATOM
2645
CG
MET
B
60
64.450
4.720
3.624
1.00
39.92
6
ATOM
2646
SD
MET
B
60
62.934
5.666
4.060
1.00
39.02
16
ATOM
2647
CE
MET
B
60
61.890
5.076
2.719
1.00
40.24
6
ATOM
2648
N
GLN
B
61
67.520
3.632
6.950
1.00
36.15
7
ATOM
2649
CA
GLN
B
61
67.973
4.079
8.262
1.00
37.72
6
ATOM
2650
C
GLN
B
61
69.493
3.884
8.375
1.00
39.87
6
ATOM
2651
O
GLN
B
61
70.042
3.727
9.476
1.00
42.79
8
ATOM
2652
CB
GLN
B
61
67.179
3.390
9.361
1.00
35.80
6
ATOM
2653
CG
GLN
B
61
67.540
1.949
9.681
1.00
32.41
6
ATOM
2654
CD
GLN
B
61
66.514
1.303
10.572
1.00
29.81
6
ATOM
2655
OE1
GLN
B
61
65.349
0.972
10.194
1.00
28.50
8
ATOM
2656
NE2
GLN
B
61
66.860
0.939
11.787
1.00
27.42
7
ATOM
2657
N
PHE
B
62
70.210
3.961
7.244
1.00
39.42
7
ATOM
2658
CA
PHE
B
62
71.665
3.901
7.241
1.00
40.52
6
ATOM
2659
C
PHE
B
62
72.216
5.205
6.643
1.00
43.48
6
ATOM
2660
O
PHE
B
62
71.742
5.679
5.613
1.00
41.80
8
ATOM
2661
CB
PHE
B
62
72.285
2.727
6.462
1.00
39.44
6
ATOM
2662
CG
PHE
B
62
72.261
1.476
7.310
1.00
38.25
6
ATOM
2663
CD1
PHE
B
62
71.094
0.697
7.350
1.00
37.73
6
ATOM
2664
CD2
PHE
B
62
73.329
1.085
8.076
1.00
37.32
6
ATOM
2665
CE1
PHE
B
62
71.053
−0.422
8.157
1.00
37.14
6
ATOM
2666
CE2
PHE
B
62
73.294
−0.044
8.870
1.00
36.89
6
ATOM
2667
CZ
PHE
B
62
72.145
−0.825
B.902
1.00
37.49
6
ATOM
2668
N
ASP
B
63
73.267
5.723
7.257
1.00
48.37
7
ATOM
2669
CA
ASP
B
63
73.887
6.980
6.816
1.00
51.97
6
ATOM
2670
C
ASP
B
63
74.709
6.872
5.539
1.00
53.02
6
ATOM
2671
O
ASP
B
63
74.642
7.765
4.679
1.00
53.58
8
ATOM
2672
CB
ASP
B
63
74.800
7.511
7.922
1.00
53.54
6
ATOM
2673
CG
ASP
B
63
74.087
7.668
9.251
1.00
55.47
6
ATOM
2674
OD1
ASP
B
63
72.832
7.712
9.265
1.00
57.99
8
ATOM
2675
OD2
ASP
B
63
74.767
7.751
10.294
1.00
56.33
8
ATOM
2676
N
ARG
B
64
75.521
5.830
5.420
1.00
52.77
7
ATOM
2677
CA
ARG
B
64
76.344
5.697
4.211
1.00
54.08
6
ATOM
2678
C
ARG
B
64
76.323
4.250
3.759
1.00
54.41
6
ATOM
2679
O
ARG
B
64
76.037
3.392
4.582
1.00
53.32
8
ATOM
2680
CB
ARG
B
64
77.758
6.205
4.486
1.00
53.78
6
ATOM
2681
N
PRO
B
65
76.658
3.987
2.505
1.00
56.79
7
ATOM
2682
CA
PRO
B
65
76.654
2.637
1.974
1.00
57.90
6
ATOM
2683
C
PRO
B
65
77.533
1.632
2.682
1.00
59.54
6
ATOM
2684
O
PRO
B
65
77.159
0.456
2.659
1.00
59.29
8
ATOM
2685
CB
PRO
B
65
77.123
2.790
0.528
1.00
58.01
6
ATOM
2686
CG
PRO
B
65
77.017
4.235
0.201
1.00
58.02
6
ATOM
2687
CD
PRO
B
65
77.011
5.007
1.489
1.00
57.36
6
ATOM
2688
N
GLU
B
66
78.651
1.990
3.291
1.00
60.73
7
ATOM
2689
CA
GLU
B
66
79.545
1.029
3.926
1.00
60.74
6
ATOM
2690
C
GLU
B
66
78.996
0.590
5.268
1.00
58.41
6
ATOM
2691
O
GLU
B
66
79.184
−0.554
5.672
1.00
59.32
8
ATOM
2692
CB
GLU
B
66
80.949
1.612
4.114
1.00
63.95
6
ATOM
2693
CG
GLU
B
66
81.554
2.085
2.807
1.00
67.09
6
ATOM
2694
CD
GLU
B
66
81.129
3.469
2.387
1.00
69.60
6
ATOM
2695
OE1
GLU
B
66
80.077
4.027
2.774
1.00
71.11
8
ATOM
2696
OE2
GLU
B
66
81.873
4.122
1.612
1.00
71.37
8
ATOM
2697
N
ASP
B
67
78.271
1.521
5.890
1.00
55.22
7
ATOM
2698
CA
ASP
B
67
77.618
1.142
7.151
1.00
53.44
6
ATOM
2699
C
ASP
B
67
76.586
0.068
6.773
1.00
49.67
6
ATOM
2700
O
ASP
B
67
76.505
−0.978
7.418
1.00
47.57
8
ATOM
2701
CB
ASP
B
67
77.109
2.400
7.818
1.00
55.45
6
ATOM
2702
CG
ASP
B
67
78.226
3.389
8.134
1.00
58.05
6
ATOM
2703
OD1
ASP
B
67
79.352
3.283
7.602
1.00
58.16
8
ATOM
2704
OD2
ASP
B
67
77.993
4.307
8.954
1.00
58.74
8
ATOM
2705
N
LEU
B
68
75.906
0.243
5.640
1.00
47.47
7
ATOM
2706
CA
LEU
B
68
74.908
−0.706
5.170
1.00
45.94
6
ATOM
2707
C
LEU
B
68
75.575
−2.002
4.715
1.00
46.59
6
ATOM
2708
O
LEU
B
68
75.241
−3.082
5.201
1.00
47.70
8
ATOM
2709
CB
LEU
B
68
74.066
−0.198
4.001
1.00
44.25
6
ATOM
2710
CG
LEU
B
68
72.989
−1.184
3.489
1.00
42.50
6
ATOM
2711
CD1
LEU
B
68
72.064
−1.563
4.634
1.00
40.69
6
ATOM
2712
CD2
LEU
B
68
72.214
−0.620
2.317
1.00
42.43
6
ATOM
2713
N
ALA
B
69
76.513
−1.866
3.793
1.00
46.99
7
ATOM
2714
CA
ALA
B
69
77.238
−3.024
3.259
1.00
47.49
6
ATOM
2715
C
ALA
B
69
77.930
−3.829
4.337
1.00
46.64
6
ATOM
2716
O
ALA
B
69
77.913
−5.072
4.256
1.00
48.02
8
ATOM
2717
CB
ALA
B
69
78.258
−2.532
2.235
1.00
48.47
6
ATOM
2718
N
ARG
B
70
78.475
−3.201
5.370
1.00
45.74
7
ATOM
2719
CA
ARG
B
70
79.158
−3.961
6.411
1.00
44.24
6
ATOM
2720
C
ARG
B
70
78.246
−4.487
7.495
1.00
44.00
6
ATOM
2721
O
ARG
B
70
78.700
−5.308
8.281
1.00
41.15
8
ATOM
2722
CB
ARG
B
70
80.247
−3.071
7.038
1.00
46.62
6
ATOM
2723
N
TYR
B
71
76.966
−4.108
7.573
1.00
41.84
7
ATOM
2724
CA
TYR
B
71
76.076
−4.624
8.609
1.00
39.35
6
ATOM
2725
C
TYR
B
71
75.935
−6.141
8.508
1.00
37.54
6
ATOM
2726
O
TYR
B
71
75.788
−6.673
7.410
1.00
37.39
8
ATOM
2727
CB
TYR
B
71
74.712
−3.919
8.487
1.00
38.73
6
ATOM
2728
CG
TYR
B
71
73.927
−4.054
9.778
1.00
36.95
6
ATOM
2729
CD1
TYR
B
71
74.099
−3.155
10.806
1.00
34.97
6
ATOM
2730
CD2
TYR
B
71
72.993
−5.079
9.946
1.00
35.71
6
ATOM
2731
CE1
TYR
B
71
73.405
−3.260
12.004
1.00
35.01
6
ATOM
2732
CE2
TYR
B
71
72.287
−5.192
11.109
1.00
33.37
6
ATOM
2733
CZ
TYR
B
71
72.462
−4.292
12.119
1.00
34.69
6
ATOM
2734
OH
TYR
B
71
71.765
−4.407
13.290
1.00
34.77
8
ATOM
2735
N
PRO
B
72
75.985
−6.835
9.625
1.00
37.73
7
ATOM
2736
CA
PRO
B
72
76.030
−8.293
9.644
1.00
40.09
6
ATOM
2737
C
PRO
B
72
74.756
−8.966
9.194
1.00
42.74
6
ATOM
2738
O
PRO
B
72
73.697
−8.753
9.783
1.00
42.94
8
ATOM
2739
CB
PRO
B
72
76.369
−8.681
11.080
1.00
39.27
6
ATOM
2740
CG
PRO
B
72
76.366
−7.442
11.876
1.00
39.73
6
ATOM
2741
CD
PRO
B
72
76.222
−6.266
10.967
1.00
37.89
6
ATOM
2742
N
ARG
B
73
74.856
−9.773
8.147
1.00
42.53
7
ATOM
2743
CA
ARG
B
73
73.687
−10.492
7.639
1.00
43.36
6
ATOM
2744
C
ARG
B
73
73.881
−11.945
7.992
1.00
43.07
6
ATOM
2745
O
ARG
B
73
74.875
−12.526
7.534
1.00
42.68
8
ATOM
2746
CB
ARG
B
73
73.524
−10.225
6.143
1.00
45.53
6
ATOM
2747
CG
ARG
B
73
73.306
−8.700
5.962
1.00
48.13
6
ATOM
2748
CD
ARG
B
73
72.868
−8.393
4.559
1.00
49.65
6
ATOM
2749
NE
ARG
B
73
72.537
−7.021
4.268
1.00
51.16
7
ATOM
2750
CZ
ARG
B
73
73.255
−5.930
4.486
1.00
51.88
6
ATOM
2751
NH1
ARG
B
73
74.449
−5.968
5.071
1.00
53.24
7
ATOM
2752
NH2
ARG
B
73
72.779
−4.755
4.085
1.00
51.96
7
ATOM
2753
N
THR
B
74
73.054
−12.505
8.869
1.00
40.78
7
ATOM
2754
CA
THR
B
74
73.184
−13.870
9.338
1.00
38.76
6
ATOM
2755
C
THR
B
74
71.806
−14.564
9.373
1.00
36.02
6
ATOM
2756
O
THR
B
74
71.381
−15.074
10.395
1.00
35.74
8
ATOM
2757
CB
THR
B
74
73.825
−13.949
10.726
1.00
39.81
6
ATOM
2758
OG1
THR
B
74
72.965
−13.304
11.686
1.00
41.92
8
ATOM
2759
CG2
THR
B
74
75.176
−13.231
10.872
1.00
39.68
6
ATOM
2760
N
LEU
B
75
71.163
−14.648
8.241
1.00
38.12
7
ATOM
2761
CA
LEU
B
75
69.795
−15.148
8.140
1.00
38.95
6
ATOM
2762
C
LEU
B
75
69.657
−16.574
8.644
1.00
39.45
6
ATOM
2763
O
LEU
B
75
68.791
−16.843
9.478
1.00
37.24
8
ATOM
2764
CB
LEU
B
75
69.269
−15.024
6.693
1.00
41.95
6
ATOM
2765
CG
LEU
B
75
67.785
−15.355
6.505
1.00
42.42
6
ATOM
2766
CD1
LEU
B
75
66.907
−14.527
7.453
1.00
43.76
6
ATOM
2767
CD2
LEU
B
75
67.332
−15.146
5.070
1.00
42.41
6
ATOM
2768
N
GLN
B
76
70.525
−17.509
8.187
1.00
39.28
7
ATOM
2769
CA
GLN
B
76
70.400
−18.884
8.667
1.00
39.73
6
ATOM
2770
C
GLN
B
76
70.476
−18.965
10.181
1.00
36.54
6
ATOM
2771
O
GLN
B
76
69.671
−19.700
10.759
1.00
35.73
8
ATOM
2772
CB
GLN
B
76
71.477
−19.872
8.150
1.00
42.75
6
ATOM
2773
CG
GLN
B
76
71.375
−21.209
8.897
1.00
45.19
6
ATOM
2774
CD
GLN
B
76
72.464
−22.227
8.683
1.00
48.00
6
ATOM
2775
OE1
GLN
B
76
72.386
−23.355
9.236
1.00
51.20
8
ATOM
2776
NE2
GLN
B
76
73.482
−21.896
7.921
1.00
46.67
7
ATOM
2777
N
GLU
B
77
71.442
−18.317
10.808
1.00
33.90
7
ATOM
2778
CA
GLU
B
77
71.585
−18.356
12.259
1.00
33.25
6
ATOM
2779
C
GLU
B
77
70.408
−17.708
13.013
1.00
32.48
6
ATOM
2780
O
GLU
B
77
69.960
−18.170
14.072
1.00
31.46
8
ATOM
2781
CB
GLU
B
77
72.885
−17.636
12.627
1.00
33.79
6
ATOM
2782
N
ASP
B
78
69.915
−16.625
12.388
1.00
32.55
7
ATOM
2783
CA
ASP
B
78
68.738
−15.937
12.973
1.00
30.24
6
ATOM
2784
C
ASP
B
78
67.576
−16.964
12.993
1.00
28.55
6
ATOM
2785
O
ASP
B
78
66.981
−17.174
14.032
1.00
29.32
8
ATOM
2786
CB
ASP
B
78
68.337
−14.697
12.209
1.00
31.00
6
ATOM
2787
CG
ASP
B
78
69.331
−13.551
12.195
1.00
34.64
6
ATOM
2788
OD1
ASP
B
78
70.144
−13.494
13.151
1.00
37.80
8
ATOM
2789
OD2
ASP
B
78
69.328
−12.744
11.228
1.00
36.82
8
ATOM
2790
N
CYS
B
79
67.355
−17.543
11.825
1.00
30.19
7
ATOM
2791
CA
CYS
B
79
66.231
−18.500
11.625
1.00
33.57
6
ATOM
2792
C
CYS
B
79
66.327
−19.720
12.495
1.00
35.51
6
ATOM
2793
O
CYS
B
79
65.350
−20.136
13.149
1.00
34.66
8
ATOM
2794
CB
CYS
B
79
66.184
−18.792
10.132
1.00
33.80
6
ATOM
2795
SG
CYS
B
79
65.381
−17.456
9.190
1.00
37.92
16
ATOM
2796
N
GLU
B
80
67.543
−20.281
12.707
1.00
36.68
7
ATOM
2797
CA
GLU
B
80
67.692
−21.347
13.691
1.00
35.97
6
ATOM
2798
C
GLU
B
80
67.370
−20.883
15.088
1.00
33.68
6
ATOM
2799
O
GLU
B
80
66.764
−21.625
15.883
1.00
34.88
8
ATOM
2800
CB
GLU
B
80
69.130
−21.906
13.660
1.00
36.66
6
ATOM
2801
N
LYS
B
81
67.668
−19.638
15.520
1.00
34.02
7
ATOM
2802
CA
LYS
B
81
67.277
−19.253
16.875
1.00
31.36
6
ATOM
2803
C
LYS
B
81
65.756
−19.047
17.017
1.00
30.38
6
ATOM
2804
O
LYS
B
81
65.183
−19.326
18.068
1.00
29.64
8
ATOM
2805
CB
LYS
B
81
67.967
−17.965
17.314
1.00
35.26
6
ATOM
2806
CG
LYS
B
81
69.451
−18.114
17.566
1.00
37.30
6
ATOM
2807
CD
LYS
B
81
70.118
−16.744
17.730
1.00
39.14
6
ATOM
2808
CE
LYS
B
81
71.635
−17.011
17.782
1.00
41.26
6
ATOM
2809
NZ
LYS
B
81
72.310
−15.733
18.142
1.00
43.00
7
ATOM
2810
N
LEU
B
82
65.158
−18.495
15.965
1.00
30.34
7
ATOM
2811
CA
LEU
B
82
63.700
−18.248
16.019
1.00
30.06
6
ATOM
2812
C
LEU
B
82
62.914
−19.540
16.028
1.00
32.53
6
ATOM
2813
O
LEU
B
82
61.880
−19.695
16.694
1.00
32.69
8
ATOM
2814
CB
LEU
B
82
63.335
−17.328
14.845
1.00
30.48
6
ATOM
2815
CG
LEU
B
82
63.981
−15.924
14.936
1.00
28.69
6
ATOM
2816
CD1
LEU
B
82
63.820
−15.222
13.603
1.00
25.14
6
ATOM
2817
CD2
LEU
B
82
63.412
−15.105
16.103
1.00
28.77
6
ATOM
2818
N
ASN
B
83
63.438
−20.549
15.323
1.00
33.22
7
ATOM
2819
CA
ASN
B
83
62.748
−21.849
15.282
1.00
36.28
6
ATOM
2820
C
ASN
B
83
62.747
−22.507
16.648
1.00
36.28
6
ATOM
2821
O
ASN
B
83
61.735
−23.043
17.139
1.00
35.49
8
ATOM
2822
CB
ASN
B
83
63.419
−22.656
14.181
1.00
39.05
6
ATOM
2823
CG
ASN
B
83
62.717
−23.983
13.943
1.00
42.41
6
ATOM
2824
OD1
ASN
B
83
63.382
−25.000
14.194
1.00
45.42
8
ATOM
2825
ND2
ASN
B
83
61.474
−23.962
13.533
1.00
41.68
7
ATOM
2826
N
LYS
B
84
63.820
−22.351
17.437
1.00
37.37
7
ATOM
2827
CA
LYS
B
84
63.850
−22.927
18.780
1.00
39.89
6
ATOM
2828
C
LYS
B
84
62.942
−22.200
19.747
1.00
40.11
6
ATOH
2829
O
LYS
B
84
62.533
−22.693
20.801
1.00
40.80
8
ATOM
2830
CB
LYS
B
84
65.305
−22.932
19.291
1.00
39.81
6
ATOM
2831
N
ARG
B
85
62.590
−20.942
19.425
1.00
40.09
7
ATOM
2832
CA
ARG
B
85
61.718
−20.125
20.235
1.00
39.63
6
ATOM
2833
C
ARG
B
85
60.260
−20.305
19.812
1.00
40.59
6
ATOM
2834
O
ARG
B
85
59.373
−19.647
20.334
1.00
42.54
8
ATOM
2835
CB
ARG
B
85
62.093
−18.647
20.134
1.00
40.48
6
ATOM
2836
CG
ARG
B
85
62.052
−17.972
21.510
1.00
41.38
6
ATOM
2837
CD
ARG
B
85
63.336
−18.317
22.253
1.00
42.99
6
ATOM
2838
NE
ARG
B
85
63.380
−17.724
23.588
1.00
42.49
7
ATOM
2839
CZ
ARG
B
85
64.475
−17.764
24.342
1.00
43.47
6
ATOM
2840
NH1
ARG
B
85
64.483
−17.233
25.553
1.00
42.44
7
ATOM
2841
NH2
ARG
B
85
65.570
−18.361
23.872
1.00
44.83
7
ATOM
2842
N
LYS
B
86
60.041
−21.151
18.827
1.00
39.06
7
ATOM
2843
CA
LYS
B
86
58.702
−21.492
18.348
1.00
38.48
6
ATOM
2844
C
LYS
B
86
57.996
−20.296
17.712
1.00
36.35
6
ATOM
2845
O
LYS
B
86
56.785
−20.127
17.808
1.00
34.81
8
ATOM
2846
CB
LYS
B
86
57.903
−22.087
19.511
1.00
39.68
6
ATOM
2847
N
VAL
B
87
58.751
−19.515
16.953
1.00
33.22
7
ATOM
2848
CA
VAL
B
87
58.133
−18.416
16.204
1.00
29.42
6
ATOM
2849
C
VAL
B
87
57.340
−18.986
15.051
1.00
30.11
6
ATOM
2850
O
VAL
B
87
57.704
−19.959
14.359
1.00
29.33
8
ATOM
2851
CB
VAL
B
87
59.267
−17.508
15.732
1.00
27.19
6
ATOM
2852
CG1
VAL
B
87
58.859
−16.637
14.581
1.00
28.11
6
ATOM
2853
CG2
VAL
B
87
59.756
−16.644
16.909
1.00
28.45
6
ATOM
2854
N
ASP
B
88
56.179
−18.408
14.740
1.00
27.32
7
ATOM
2855
CA
ASP
B
88
55.356
−18.963
13.667
1.00
26.78
6
ATOM
2856
C
ASP
B
88
55.780
−18.589
12.285
1.00
26.80
6
ATOM
2857
O
ASP
B
88
55.687
−19.415
11.342
1.00
26.44
8
ATOM
2858
CB
ASP
B
88
53.895
−18.488
13.889
1.00
29.04
6
ATOM
2859
CG
ASP
B
88
53.482
−18.856
15.298
1.00
30.71
6
ATOM
2860
OD1
ASP
B
88
52.991
−20.020
15.427
1.00
32.60
8
ATOM
2861
OD2
ASP
B
88
53.717
−18.147
16.323
1.00
30.59
8
ATOM
2862
N
LEU
B
89
56.204
−17.356
12.062
1.00
23.49
7
ATOM
2863
CA
LEU
B
89
56.498
−16.854
10.756
1.00
23.51
6
ATOM
2864
C
LEU
B
89
57.676
−15.880
10.729
1.00
23.91
6
ATOM
2865
O
LEU
B
89
57.609
−14.975
11.552
1.00
24.58
8
ATOM
2866
CB
LEU
B
89
55.236
−16.101
10.292
1.00
26.12
6
ATOM
2867
CG
LEU
B
89
55.179
−15.845
8.823
1.00
29.47
6
ATOM
2868
CD1
LEU
B
89
53.725
−15.783
8.333
1.00
31.30
6
ATOM
2869
CD2
LEU
B
89
55.883
−14.542
8.494
1.00
32.84
6
ATOM
2870
N
VAL
B
90
58.629
−15.971
9.842
1.00
23.43
7
ATOM
2871
CA
VAL
B
90
59.716
−15.006
9.714
1.00
23.35
6
ATOM
2872
C
VAL
B
90
59.553
−14.315
8.413
1.00
24.66
6
ATOM
2873
O
VAL
B
90
59.386
−14.905
7.324
1.00
24.98
8
ATOM
2874
CB
VAL
B
90
61.116
−15.722
9.862
1.00
23.84
6
ATOM
2875
CG1
VAL
B
90
62.212
−14.701
9.640
1.00
26.41
6
ATOM
2876
CG2
VAL
B
90
61.195
−16.379
11.217
1.00
23.75
6
ATOM
2877
N
PHE
B
91
59.462
−12.972
8.351
1.00
23.00
7
ATOM
2878
CA
PHE
B
91
59.363
−12.240
7.147
1.00
21.82
6
ATOM
2879
C
PHE
B
91
60.754
−11.693
6.787
1.00
24.30
6
ATOM
2880
O
PHE
B
91
61.258
−10.892
7.578
1.00
25.55
8
ATOM
2881
CB
PHE
B
91
58.346
−11.073
7.207
1.00
20.44
6
ATOM
2882
CG
PHE
B
91
58.180
−10.275
5.969
1.00
22.85
6
ATOM
2883
CD1
PHE
B
91
58.030
−10.779
4.676
1.00
21.26
6
ATOM
2884
CD2
PHE
B
91
58.164
−8.848
6.101
1.00
22.68
6
ATOM
2885
CE1
PHE
B
91
57.900
−9.976
3.571
1.00
22.13
6
ATOM
2886
CE2
PHE
B
91
58.006
−8.055
4.990
1.00
21.70
6
ATOM
2887
CZ
PHE
B
91
57.852
−8.587
3.703
1.00
23.17
6
ATOM
2888
N
ALA
B
92
61.345
−12.164
5.695
1.00
24.62
7
ATOM
2889
CA
ALA
B
92
62.738
−11.659
5.375
1.00
23.61
6
ATOM
2890
C
ALA
B
92
62.815
−11.216
3.975
1.00
25.99
6
ATOM
2891
O
ALA
B
92
63.216
−12.052
3.123
1.00
27.84
8
ATOM
2892
CB
ALA
B
92
63.656
−12.811
5.743
1.00
25.77
6
ATOM
2893
N
PRO
B
93
62.300
−10.088
3.518
1.00
25.21
7
ATOM
2894
CA
PRO
B
93
62.258
−9.655
2.170
1.00
26.28
6
ATOM
2895
C
PRO
B
93
63.583
−9.189
1.617
1.00
25.56
6
ATOM
2896
O
PRO
B
93
64.455
−8.761
2.381
1.00
27.95
8
ATOM
2897
CB
PRO
B
93
61.283
−8.471
2.238
1.00
26.93
6
ATOM
2898
CG
PRO
B
93
61.547
−7.888
3.586
1.00
26.11
6
ATOM
2899
CD
PRO
B
93
61.769
−9.060
4.516
1.00
24.38
6
ATOM
2900
N
SER
B
94
63.668
−9.114
0.292
1.00
28.86
7
ATOM
2901
CA
SER
B
94
64.891
−8.524
−0.309
1.00
30.21
6
ATOM
2902
C
SER
B
94
64.735
−7.010
−0.305
1.00
31.63
6
ATOM
2903
O
SER
B
94
63.635
−6.521
−0.100
1.00
27.09
8
ATOM
2904
CB
SER
B
94
65.138
−8.951
−1.719
1.00
28.52
6
ATOM
2905
OG
SER
B
94
64.254
−8.353
−2.673
1.00
29.83
8
ATOM
2906
N
VAL
B
95
65.802
−6.264
−0.628
1.00
32.49
7
ATOM
2907
CA
VAL
B
95
65.724
−4.840
−0.723
1.00
31.55
6
ATOM
2908
C
VAL
B
95
64.919
−4.487
−1.938
1.00
31.75
6
ATOM
2909
O
VAL
B
95
64.138
−3.540
−1.883
1.00
31.41
8
ATOM
2910
CB
VAL
B
95
67.144
−4.172
−0.780
1.00
32.74
6
ATOM
2911
CG1
VAL
B
95
67.050
−2.736
−1.221
1.00
34.17
6
ATOM
2912
CG2
VAL
B
95
67.813
−4.258
0.570
1.00
33.43
6
ATOM
2913
N
LYS
B
96
65.004
−5.262
−3.023
1.00
31.26
7
ATOM
2914
CA
LYS
B
96
64.226
−5.022
−4.212
1.00
31.62
6
ATOM
2915
C
LYS
B
96
62.744
−5.267
−3.889
1.00
29.22
6
ATOM
2916
O
LYS
B
96
61.905
−4.611
−4.487
1.00
32.48
8
ATOM
2917
CB
LYS
B
96
64.685
−5.913
−5.380
1.00
32.35
6
ATOM
2918
N
GLU
B
97
62.464
−6.172
−2.988
1.00
30.27
7
ATOM
2919
CA
GLU
B
97
61.056
−6.463
−2.667
1.00
31.03
6
ATOM
2920
C
GLU
B
97
60.375
−5.301
−1.936
1.00
30.11
6
ATOM
2921
O
GLU
B
97
59.235
−4.950
−2.211
1.00
31.04
8
ATOM
2922
CB
GLU
B
97
61.000
−7.749
−1.850
1.00
32.49
6
ATOM
2923
CG
GLU
B
97
59.570
−8.220
−1.623
1.00
33.54
6
ATOM
2924
CD
GLU
B
97
58.875
−8.792
−2.844
1.00
35.26
6
ATOM
2925
OE1
GLU
B
97
59.540
−9.132
−3.867
1.00
34.07
8
ATOM
2926
OE2
GLU
B
97
57.632
−8.980
−2.841
1.00
32.87
8
ATOM
2927
N
ILE
B
98
61.084
−4.723
−0.999
1.00
28.92
7
ATOM
2928
CA
ILE
B
98
60.582
−3.564
−0.235
1.00
28.98
6
ATOM
2929
C
ILE
B
98
60.727
−2.241
−0.955
1.00
30.40
6
ATOM
2930
O
ILE
B
98
59.849
−1.353
−0.964
1.00
25.83
8
ATOM
2931
CB
ILE
B
98
61.320
−3.544
1.123
1.00
26.40
6
ATOM
2932
CG1
ILE
B
98
60.992
−4.753
1.985
1.00
30.78
6
ATOM
2933
CG2
ILE
B
98
60.988
−2.241
1.865
1.00
26.02
6
ATOM
2934
CD1
ILE
B
98
59.551
−5.137
2.182
1.00
30.67
6
ATOM
2935
N
TYR
B
99
61.889
−2.036
−1.638
1.00
31.00
7
ATOM
2936
CA
TYR
B
99
62.170
−0.808
−2.356
1.00
32.52
6
ATOM
2937
C
TYR
B
99
62.505
−1.034
−3.812
1.00
34.54
6
ATOM
2938
O
TYR
B
99
63.655
−0.817
−4.255
1.00
35.45
8
ATOM
2939
CB
TYR
B
99
63.366
−0.108
−1.661
1.00
31.16
6
ATOM
2940
CG
TYR
B
99
63.179
0.250
−0.213
1.00
28.25
6
ATOM
2941
CD1
TYR
B
99
63.952
−0.243
0.825
1.00
28.01
6
ATOM
2942
CD2
TYR
B
99
62.202
1.193
0.117
1.00
28.98
6
ATOM
2943
CE1
TYR
B
99
63.754
0.159
2.135
1.00
27.92
6
ATOM
2944
CE2
TYR
B
99
62.006
1.609
1.427
1.00
28.86
6
ATOM
2945
CZ
TYR
B
99
62.774
1.073
2.446
1.00
27.90
6
ATOM
2946
OH
TYR
B
99
62.576
1.499
3.756
1.00
27.84
8
ATOM
2947
N
PRO
B
100
61.555
−1.416
−4.630
1.00
35.55
7
ATOM
2948
CA
PRO
B
100
61.774
−1.742
−6.033
1.00
37.21
6
ATOM
2949
C
PRO
B
100
62.327
−0.598
−6.843
1.00
38.72
6
ATOM
2950
O
PRO
B
100
63.107
−0.784
−7.787
1.00
39.39
8
ATOM
2951
CB
PRO
B
100
60.417
−2.189
−6.566
1.00
37.99
6
ATOM
2952
CG
PRO
B
100
59.412
−1.828
−5.543
1.00
35.50
6
ATOM
2953
CD
PRO
B
100
60.151
−1.710
−4.256
1.00
35.06
6
ATOM
2954
N
ASN
B
101
61.921
0.620
−6.487
1.00
38.14
7
ATOM
2955
CA
ASN
B
101
62.391
1.803
−7.192
1.00
38.05
6
ATOM
2956
C
ASN
B
101
63.459
2.537
−6.385
1.00
36.99
6
ATOM
2957
O
ASN
B
101
63.676
3.726
−6.653
1.00
39.29
8
ATOM
2958
CB
ASN
B
101
61.202
2.723
−7.451
1.00
39.89
6
ATOM
2959
CG
ASN
B
101
60.007
1.987
−8.013
1.00
41.77
6
ATOM
2960
OD1
ASN
B
101
58.930
1.884
−7.425
1.00
42.16
8
ATOM
2961
ND2
ASN
B
101
60.229
1.436
−9.197
1.00
42.54
7
ATOM
2962
N
GLY
B
102
64.028
1.920
−5.376
1.00
34.24
7
ATOM
2963
CA
GLY
B
102
64.956
2.603
−4.480
1.00
33.96
6
ATOM
2964
C
GLY
B
102
64.329
3.353
−3.324
1.00
34.73
6
ATOM
2965
O
GLY
B
102
63.091
3.507
−3.190
1.00
33.28
8
ATOM
2966
N
THR
B
103
65.153
3.914
−2.430
1.00
32.52
7
ATOM
2967
CA
THR
B
103
64.591
4.613
−1.279
1.00
32.04
6
ATOM
2968
C
THR
B
103
64.351
6.098
−1.472
1.00
33.64
6
ATOM
2969
O
THR
B
103
63.426
6.615
−0.800
1.00
32.63
8
ATOM
2970
CB
THR
B
103
65.544
4.405
−0.100
1.00
34.27
6
ATOM
2971
OG1
THR
B
103
66.808
4.981
−0.489
1.00
34.81
8
ATOM
2972
CG2
THR
B
103
65.762
2.948
0.225
1.00
34.11
6
ATOM
2973
N
GLU
B
104
65.063
6.775
−2.375
1.00
31.00
7
ATOM
2974
CA
GLU
B
104
64.919
8.220
−2.452
1.00
34.38
6
ATOM
2975
C
GLU
B
104
63.553
8.693
−2.915
1.00
35.05
6
ATOM
2976
O
GLU
B
104
63.205
9.837
−2.567
1.00
36.53
8
ATOM
2977
CB
GLU
B
104
66.012
8.810
−3.394
1.00
37.66
6
ATOM
2978
N
THR
B
105
62.883
7.955
−3.798
1.00
32.50
7
ATOM
2979
CA
THR
B
105
61.572
8.395
−4.264
1.00
33.06
6
ATOM
2980
C
THR
B
105
60.409
7.607
−3.633
1.00
30.67
6
ATOM
2981
O
THR
B
105
59.255
7.825
−4.025
1.00
30.32
8
ATOM
2982
CB
THR
B
105
61.469
8.256
−5.780
1.00
34.96
6
ATOM
2983
OG1
THR
B
105
61.702
6.883
−6.107
1.00
35.88
8
ATOM
2984
CG2
THR
B
105
62.498
9.147
−6.493
1.00
37.41
6
ATOM
2985
N
HIS
B
106
60.705
6.829
−2.610
1.00
28.38
7
ATOM
2986
CA
HIS
B
106
59.686
6.055
−1.897
1.00
26.95
6
ATOM
2987
C
HIS
B
106
58.943
6.945
−0.916
1.00
27.21
6
ATOM
2988
O
HIS
B
106
59.558
7.820
−0.286
1.00
25.40
8
ATOM
2989
CB
HIS
B
106
60.299
4.906
−1.129
1.00
26.76
6
ATOM
2990
CG
HIS
B
106
59.397
3.804
−0.619
1.00
26.50
6
ATOM
2991
ND1
HIS
B
106
58.822
3.908
0.632
1.00
26.30
7
ATOM
2992
CD2
HIS
B
106
59.017
2.642
−1.214
1.00
26.99
6
ATOM
2993
CE1
HIS
B
106
58.139
2.730
0.807
1.00
26.31
6
ATOM
2994
NE2
HIS
B
106
58.209
1.992
−0.276
1.00
27.12
7
ATOM
2995
N
THR
B
107
57.621
6.749
−0.815
1.00
24.60
7
ATOM
2996
CA
THR
B
107
56.852
7.517
0.177
1.00
22.48
6
ATOM
2997
C
THR
B
107
57.510
7.428
1.528
1.00
23.26
6
ATOM
2998
O
THR
B
107
58.100
6.378
1.812
1.00
24.71
8
ATOM
2999
CB
THR
B
107
55.425
6.933
0.229
1.00
22.11
6
ATOM
3000
OG1
THR
B
107
54.846
7.149
−1.052
1.00
21.94
8
ATOM
3001
CG2
THR
B
107
54.603
7.713
1.242
1.00
24.08
6
ATOM
3002
N
TYR
B
108
57.441
8.470
2.356
1.00
21.20
7
ATOM
3003
CA
TYR
B
108
58.037
8.298
3.677
1.00
22.80
6
ATOM
3004
C
TYR
B
108
57.170
8.870
4.799
1.00
23.19
6
ATOM
3005
O
TYR
B
108
56.257
9.711
4.564
1.00
20.67
8
ATOM
3006
CB
TYR
B
108
59.500
8.861
3.752
1.00
26.29
6
ATOM
3007
CG
TYR
B
108
59.581
10.367
3.586
1.00
27.43
6
ATOM
3008
CD1
TYR
B
108
59.350
11.243
4.641
1.00
30.64
6
ATOM
3009
CD2
TYR
B
108
59.795
10.914
2.331
1.00
31.95
6
ATOM
3010
CE1
TYR
B
108
59.352
12.617
4.478
1.00
31.91
6
ATOM
3011
CE2
TYR
B
108
59.821
12.272
2.159
1.00
34.14
6
ATOM
3012
CZ
TYR
B
108
59.609
13.130
3.235
1.00
34.42
6
ATOM
3013
OH
TYR
B
108
59.634
14.497
3.014
1.00
36.77
8
ATOM
3014
N
VAL
B
109
57.454
8.419
6.031
1.00
21.49
7
ATOM
3015
CA
VAL
B
109
56.734
8.809
7.224
1.00
21.55
6
ATOM
3016
C
VAL
B
109
57.707
9.552
8.149
1.00
23.45
6
ATOM
3017
O
VAL
B
109
58.712
8.918
8.447
1.00
22.21
8
ATOM
3018
CB
VAL
B
109
56.125
7.624
8.009
1.00
20.74
6
ATOM
3019
CG1
VAL
B
109
55.351
8.074
9.216
1.00
22.40
6
ATOM
3020
CG2
VAL
B
109
55.248
6.829
7.006
1.00
21.59
6
ATOM
3021
N
ASP
B
110
57.376
10.750
8.596
1.00
22.01
7
ATOM
3022
CA
ASP
B
110
58.343
11.465
9.478
1.00
24.43
6
ATOM
3023
C
ASP
B
110
57.632
11.952
10.711
1.00
23.59
6
ATOM
3024
O
ASP
B
110
56.504
12.458
10.672
1.00
21.44
8
ATOM
3025
CB
ASP
B
110
58.991
12.648
8.759
1.00
27.76
6
ATOM
3026
CG
ASP
B
110
60.461
12.751
9.239
1.00
36.19
6
ATOM
3027
OD1
ASP
B
110
61.056
12.013
10.077
1.00
37.59
8
ATOM
3028
OD2
ASP
B
110
61.173
13.585
8.645
1.00
39.38
8
ATOM
3029
N
VAL
B
111
58.257
11.795
11.892
1.00
23.56
7
ATOM
3030
CA
VAL
B
111
57.669
12.175
13.148
1.00
22.23
6
ATOM
3031
C
VAL
B
111
58.397
13.444
13.636
1.00
26.13
6
ATOM
3032
O
VAL
B
111
59.555
13.322
13.987
1.00
27.27
8
ATOM
3033
CB
VAL
B
111
57.822
11.100
14.216
1.00
23.73
6
ATOM
3034
CG1
VAL
B
111
57.213
11.440
15.574
1.00
23.64
6
ATOM
3035
CG2
VAL
B
111
57.143
9.759
13.858
1.00
24.27
6
ATOM
3036
N
PRO
B
112
57.801
14.619
13.564
1.00
24.70
7
ATOM
3037
CA
PRO
B
112
58.542
15.820
13.939
1.00
24.12
6
ATOM
3038
C
PRO
B
112
59.048
15.823
15.355
1.00
25.44
6
ATOM
3039
O
PRO
B
112
58.457
15.302
16.281
1.00
25.94
8
ATOM
3040
CB
PRO
B
112
57.517
16.950
13.719
1.00
26.49
6
ATOM
3041
CG
PRO
B
112
56.471
16.411
12.776
1.00
25.85
6
ATOM
3042
CD
PRO
B
112
56.449
14.912
13.005
1.00
25.31
6
ATOM
3043
N
GLY
B
113
60.180
16.517
15.580
1.00
27.49
7
ATOM
3044
CA
GLY
B
113
60.648
16.709
16.978
1.00
27.16
6
ATOM
3045
C
GLY
B
113
61.466
15.490
17.404
1.00
29.14
6
ATOM
3046
O
GLY
B
113
62.690
15.588
17.383
1.00
29.51
8
ATOM
3047
N
LEU
B
114
60.785
14.355
17.638
1.00
27.78
7
ATOM
3048
CA
LEU
B
114
61.512
13.141
18.019
1.00
28.34
6
ATOM
3049
C
LEU
B
114
62.545
12.685
17.019
1.00
29.38
6
ATOM
3050
O
LEU
B
114
63.611
12.122
17.362
1.00
28.08
8
ATOM
3051
CB
LEU
B
114
60.493
12.006
18.279
1.00
26.74
6
ATOM
3052
CG
LEU
B
114
59.539
12.250
19.424
1.00
28.28
6
ATOM
3053
CD1
LEU
B
114
58.565
11.088
19.594
1.00
26.02
6
ATOM
3054
CD2
LEU
B
114
60.295
12.476
20.742
1.00
28.90
6
ATOM
3055
N
SER
B
115
62.355
12.921
15.738
1.00
28.55
7
ATOM
3056
CA
SER
B
115
63.262
12.446
14.710
1.00
28.22
6
ATOM
3057
C
SER
B
115
64.540
13.284
14.611
1.00
30.73
6
ATOM
3058
O
SER
B
115
65.515
12.778
14.048
1.00
29.82
8
ATOM
3059
CB
SER
B
115
62.556
12.433
13.359
1.00
28.87
6
ATOM
3060
OG
SER
B
115
62.188
13.728
12.878
1.00
31.15
8
ATOM
3061
N
THR
B
116
64.480
14.501
15.168
1.00
30.45
7
ATOM
3062
CA
THR
B
116
65.625
15.383
14.934
1.00
32.38
6
ATOM
3063
C
THR
B
116
66.349
15.755
16.226
1.00
34.29
6
ATOM
3064
O
THR
B
116
67.346
16.447
16.085
1.00
38.91
8
ATOM
3065
CB
THR
B
116
65.213
16.700
14.232
1.00
32.70
6
ATOM
3066
OG1
THR
B
116
64.062
17.200
14.921
1.00
32.18
8
ATOM
3067
CG2
THR
B
116
64.868
16.509
12.776
1.00
33.85
6
ATOM
3068
N
MET
B
117
65.882
15.315
17.364
1.00
34.18
7
ATOM
3069
CA
MET
B
117
66.556
15.577
18.625
1.00
35.31
6
ATOM
3070
C
MET
B
117
67.520
14.454
18.990
1.00
37.27
6
ATOM
3071
O
MET
B
117
67.419
13.329
18.506
1.00
35.45
8
ATOM
3072
CB
MET
B
117
65.555
15.716
19.758
1.00
36.44
6
ATOM
3073
CG
MET
B
117
64.825
14.432
20.149
1.00
34.64
6
ATOM
3074
SD
MET
B
117
63.385
14.720
21.138
1.00
35.68
16
ATOM
3075
CE
MET
B
117
64.113
15.441
22.628
1.00
35.24
6
ATOM
3076
N
LEU
B
118
68.432
14.767
19.943
1.00
36.08
7
ATOM
3077
CA
LEU
B
118
69.384
13.776
20.444
1.00
35.32
6
ATOM
3078
C
LEU
B
118
70.141
13.060
19.370
1.00
36.49
6
ATOM
3079
O
LEU
B
118
70.769
13.672
18.490
1.00
38.03
8
ATOM
3080
CB
LEU
B
118
68.602
12.780
21.326
1.00
34.52
6
ATOM
3081
CG
LEU
B
118
67.955
13.401
22.550
1.00
34.53
6
ATOM
3082
CD1
LEU
B
118
67.125
12.422
23.336
1.00
33.90
6
ATOM
3083
CD2
LEU
B
118
69.054
13.987
23.492
1.00
36.09
6
ATOM
3084
N
GLU
B
119
70.061
11.719
19.302
1.00
39.19
7
ATOM
3085
CA
GLU
B
119
70.748
10.969
18.252
1.00
39.90
6
ATOM
3086
C
GLU
B
119
70.345
11.391
16.861
1.00
39.96
6
ATOM
3087
O
GLU
B
119
71.144
11.319
15.930
1.00
39.74
8
ATOM
3088
CB
GLU
B
119
70.439
9.477
18.447
1.00
42.37
6
ATOM
3089
CG
GLU
B
119
71.094
8.560
17.433
1.00
46.28
6
ATOM
3090
CD
GLU
B
119
70.981
7.080
17.777
1.00
47.62
6
ATOM
3091
OE1
GLU
B
119
70.337
6.733
18.805
1.00
48.65
8
ATOM
3092
OE2
GLU
B
119
71.561
6.302
16.970
1.00
49.17
8
ATOM
3093
N
GLY
B
120
69.102
11.892
16.668
1.00
38.75
7
ATOM
3094
CA
GLY
B
120
68.668
12.258
15.318
1.00
39.65
6
ATOM
3095
C
GLY
B
120
69.318
13.524
14.807
1.00
41.25
6
ATOM
3096
O
GLY
B
120
69.425
13.755
13.602
1.00
39.83
8
ATOM
3097
N
ALA
B
121
69.785
14.354
15.771
1.00
42.58
7
ATOM
3098
CA
ALA
B
121
70.410
15.623
15.404
1.00
44.15
6
ATOM
3099
C
ALA
B
121
71.647
15.421
14.552
1.00
44.51
6
ATOM
3100
O
ALA
B
121
71.836
16.162
13.587
1.00
46.30
8
ATOM
3101
CB
ALA
B
121
70.755
16.396
16.671
1.00
44.12
6
ATOM
3102
N
SER
B
122
72.464
14.428
14.839
1.00
46.51
7
ATOM
3103
CA
SER
B
122
73.663
14.179
14.040
1.00
48.95
6
ATOM
3104
C
SER
B
122
73.442
13.166
12.932
1.00
49.98
6
ATOM
3105
O
SER
B
122
74.351
12.912
12.125
1.00
49.74
8
ATOM
3106
CB
SER
B
122
74.790
13.675
14.943
1.00
49.52
6
ATOM
3107
OG
SER
B
122
74.248
12.758
15.879
1.00
51.88
8
ATOM
3108
N
ARG
B
123
72.222
12.591
12.854
1.00
48.32
7
ATOM
3109
CA
ARG
B
123
71.947
11.586
11.826
1.00
46.67
6
ATOM
3110
C
ARG
B
123
70.694
11.919
11.018
1.00
46.85
6
ATOM
3111
O
ARG
B
123
69.644
11.274
11.155
1.00
45.46
8
ATOM
3112
CB
ARG
B
123
71.789
10.202
12.467
1.00
46.37
6
ATOM
3113
CG
ARG
B
123
72.838
9.776
13.470
1.00
46.42
6
ATOM
3114
CD
ARG
B
123
72.773
8.316
13.871
1.00
46.50
6
ATOM
3115
NE
ARG
B
123
72.926
7.465
12.686
1.00
47.12
7
ATOM
3116
CZ
ARG
B
123
72.709
6.151
12.722
1.00
48.23
6
ATOM
3117
NH1
ARG
B
123
72.343
5.594
13.870
1.00
48.08
7
ATOM
3118
NH2
ARG
B
123
72.847
5.460
11.600
1.00
48.83
7
ATOM
3119
N
PRO
B
124
70.814
12.888
10.125
1.00
46.75
7
ATOM
3120
CA
PRO
B
124
69.724
13.307
9.272
1.00
45.09
6
ATOM
3121
C
PRO
B
124
69.159
12.130
8.501
1.00
43.72
6
ATOM
3122
O
PRO
B
124
69.907
11.332
7.919
1.00
42.42
8
ATOM
3123
CB
PRO
B
124
70.287
14.368
8.344
1.00
46.93
6
ATOM
3124
CG
PRO
B
124
71.771
14.278
8.490
1.00
47.37
6
ATOM
3125
CD
PRO
B
124
72.023
13.715
9.861
1.00
46.92
6
ATOM
3126
N
GLY
B
125
67.828
12.007
8.537
1.00
41.20
7
ATOM
3127
CA
GLY
B
125
67.230
10.900
7.774
1.00
39.29
6
ATOM
3128
C
GLY
B
125
67.135
9.577
8.510
1.00
37.20
6
ATOM
3129
O
GLY
B
125
66.420
8.699
7.989
1.00
36.11
8
ATOM
3130
N
HIS
B
126
67.837
9.368
9.601
1.00
34.73
7
ATOM
3131
CA
HIS
B
126
67.849
8.102
10.308
1.00
33.50
6
ATOM
3132
C
HIS
B
126
66.493
7.708
10.877
1.00
32.20
6
ATOM
3133
O
HIS
B
126
65.982
6.611
10.531
1.00
31.89
8
ATOM
3134
CB
HIS
B
126
68.894
8.136
11.442
1.00
32.39
6
ATOM
3135
CG
HIS
B
126
68.767
6.907
12.285
1.00
30.02
6
ATOM
3136
ND1
HIS
B
126
69.142
5.669
11.764
1.00
32.16
7
ATOM
3137
CD2
HIS
B
126
68.315
6.679
13.524
1.00
28.99
6
ATOM
3138
CE1
HIS
B
126
68.928
4.739
12.670
1.00
30.29
6
ATOM
3139
NE2
HIS
B
126
68.411
5.323
13.726
1.00
31.28
7
ATOM
3140
N
PHE
B
127
65.874
8.567
11.680
1.00
28.23
7
ATOM
3141
CA
PHE
B
127
64.599
8.199
12.287
1.00
27.72
6
ATOM
3142
C
PHE
B
127
63.495
8.234
11.213
1.00
26.35
6
ATOM
3143
O
PHE
B
127
62.599
7.393
11.386
1.00
26.75
8
ATOM
3144
CB
PHE
B
127
64.268
9.034
13.528
1.00
27.25
6
ATOM
3145
CG
PHE
B
127
65.109
8.550
14.698
1.00
28.04
6
ATOM
3146
CD1
PHE
B
127
66.034
9.472
15.239
1.00
27.72
6
ATOM
3147
CD2
PHE
B
127
65.127
7.278
15.203
1.00
26.78
6
ATOM
3148
CE1
PHE
B
127
66.838
9.035
16.291
1.00
26.75
6
ATOM
3149
CE2
PHE
B
127
65.919
6.858
16.231
1.00
29.31
6
ATOM
3150
CZ
PHE
B
127
66.844
7.755
16.771
1.00
26.94
6
ATOM
3151
N
ARG
B
128
63.652
9.015
10.140
1.00
26.25
7
ATOM
3152
CA
ARG
B
128
62.665
8.940
9.054
1.00
26.31
6
ATOM
3153
C
ARG
B
128
62.641
7.529
8.474
1.00
27.01
6
ATOM
3154
O
ARG
B
128
61.607
6.896
8.176
1.00
27.70
8
ATOM
3155
CB
ARG
B
128
62.995
9.950
7.986
1.00
29.81
6
ATOM
3156
CG
ARG
B
128
62.174
9.865
6.694
1.00
28.97
6
ATOM
3157
CD
ARG
B
128
62.614
10.959
5.713
1.00
31.50
6
ATOM
3158
NE
ARG
B
128
62.199
12.249
6.307
1.00
36.12
7
ATOM
3159
CZ
ARG
B
128
62.359
13.422
5.685
1.00
36.94
6
ATOM
3160
NH1
ARG
B
128
62.917
13.437
4.474
1.00
36.92
7
ATOM
3161
NH2
ARG
B
128
61.956
14.553
6.237
1.00
36.80
7
ATOM
3162
N
GLY
B
129
63.823
6.942
8.316
1.00
25.53
7
ATOM
3163
CA
GLY
B
129
63.959
5.579
7.803
1.00
25.39
6
ATOM
3164
C
GLY
B
129
63.296
4.587
8.744
1.00
24.86
6
ATOM
3165
O
GLY
B
129
62.618
3.654
8.238
1.00
24.05
8
ATOM
3166
N
VAL
B
130
63.374
4.723
10.054
1.00
23.36
7
ATOM
3167
CA
VAL
B
130
62.752
3.848
11.024
1.00
22.23
6
ATOM
3168
C
VAL
B
130
61.208
3.977
10.944
1.00
23.73
6
ATOM
3169
O
VAL
B
130
60.528
2.931
10.910
1.00
21.98
8
ATOM
3170
CB
VAL
B
130
63.156
4.153
12.443
1.00
24.21
6
ATOM
3171
CG1
VAL
B
130
62.503
3.325
13.534
1.00
24.51
6
ATOM
3172
CG2
VAL
B
130
64.713
3.953
12.537
1.00
24.12
6
ATOM
3173
N
SER
B
131
60.667
5.199
11.057
1.00
21.64
7
ATOM
3174
CA
SER
B
131
59.218
5.336
11.014
1.00
21.18
6
ATOM
3175
C
SER
B
131
58.706
4.864
9.647
1.00
21.42
6
ATOM
3176
O
SER
B
131
57.688
4.304
9.684
1.00
22.71
8
ATOM
3177
CB
SER
B
131
58.790
6.781
11.406
1.00
20.10
6
ATOM
3178
OG
SER
B
131
59.534
7.744
10.678
1.00
22.33
8
ATOM
3179
N
THR
B
132
59.376
5.073
8.538
1.00
21.18
7
ATOM
3180
CA
THR
B
132
58.883
4.600
7.250
1.00
22.97
6
ATOM
3181
C
THR
B
132
58.795
3.079
7.224
1.00
25.11
6
ATOM
3182
O
THR
B
132
57.728
2.514
6.885
1.00
19.95
8
ATOM
3183
CB
THR
B
132
59.742
5.139
6.108
1.00
23.70
6
ATOM
3184
OG1
THR
B
132
59.721
6.590
6.182
1.00
21.14
8
ATOM
3185
CG2
THR
B
132
59.214
4.628
4.749
1.00
21.10
6
ATOM
3186
N
ILE
B
133
59.876
2.374
7.590
1.00
23.47
7
ATOM
3187
CA
ILE
B
133
59.792
0.897
7.444
1.00
22.30
6
ATOM
3188
C
ILE
B
133
58.868
0.339
8.499
1.00
20.08
6
ATOM
3189
O
ILE
B
133
58.186
−0.702
8.247
1.00
20.82
8
ATOM
3190
CB
ILE
B
133
61.163
0.202
7.503
1.00
22.40
6
ATOM
3191
CG1
ILE
B
133
61.076
−1.270
7.056
1.00
22.66
6
ATOM
3192
CG2
ILE
B
133
61.699
0.252
8.924
1.00
22.72
6
ATOM
3193
CD1
ILE
B
133
60.726
−1.465
5.594
1.00
24.76
6
ATOM
3194
N
VAL
B
134
58.775
0.887
9.716
1.00
19.44
7
ATOM
3195
CA
VAL
B
134
57.874
0.272
10.678
1.00
19.92
6
ATOM
3196
C
VAL
B
134
56.425
0.507
10.228
1.00
19.95
6
ATOM
3197
O
VAL
B
134
55.596
−0.408
10.340
1.00
18.76
8
ATOM
3198
CB
VAL
B
134
58.087
0.785
12.093
1.00
20.66
6
ATOM
3199
CG1
VAL
B
134
57.101
0.289
13.127
1.00
21.02
6
ATOM
3200
CG2
VAL
B
134
59.472
0.315
12.628
1.00
23.22
6
ATOM
3201
N
SER
B
135
56.098
1.693
9.701
1.00
21.84
7
ATOM
3202
CA
SER
B
135
54.738
1.882
9.197
1.00
21.43
6
ATOM
3203
C
SER
B
135
54.448
0.852
8.088
1.00
20.41
6
ATOM
3204
O
SER
B
135
53.335
0.320
8.054
1.00
19.83
8
ATOM
3205
CB
SER
B
135
54.490
3.262
8.563
1.00
25.05
6
ATOM
3206
OG
SER
B
135
54.496
4.192
9.637
1.00
30.48
8
ATOM
3207
N
LYS
B
136
55.430
0.706
7.189
1.00
18.76
7
ATOM
3208
CA
LYS
B
136
55.189
−0.267
6.067
1.00
20.34
6
ATOM
3209
C
LYS
B
136
54.944
−1.659
6.626
1.00
19.06
6
ATOM
3210
O
LYS
B
136
54.010
−2.371
6.185
1.00
18.19
8
ATOM
3211
CB
LYS
B
136
56.351
−0.243
5.052
1.00
20.12
6
ATOM
3212
CG
LYS
B
136
56.143
−1.143
3.805
1.00
20.78
6
ATOM
3213
CD
LYS
B
136
57.014
−0.638
2.664
1.00
22.99
6
ATOM
3214
CE
LYS
B
136
56.995
−1.594
1.478
1.00
25.34
6
ATOM
3215
NZ
LYS
B
136
57.435
−0.897
0.229
1.00
25.62
7
ATOM
3216
N
LEU
B
137
55.713
−2.120
7.604
1.00
17.80
7
ATOM
3217
CA
LEU
B
137
55.582
−3.427
8.237
1.00
19.98
6
ATOM
3218
C
LEU
B
137
54.275
−3.552
8.976
1.00
19.20
6
ATOM
3219
O
LEU
B
137
53.616
−4.573
8.857
1.00
18.56
8
ATOM
3220
CB
LEU
B
137
56.745
−3.696
9.220
1.00
19.53
6
ATOM
3221
CG
LEU
B
137
58.074
−4.009
8.556
1.00
22.60
6
ATOM
3222
CD1
LEU
B
137
59.179
−3.990
9.627
1.00
18.94
6
ATOM
3223
CD2
LEU
B
137
58.043
−5.360
7.886
1.00
20.42
6
ATOM
3224
N
PHE
B
138
53.777
−2.469
9.583
1.00
16.81
7
ATOM
3225
CA
PHE
B
138
52.487
−2.532
10.200
1.00
17.03
6
ATOM
3226
C
PHE
B
138
51.342
−2.677
9.163
1.00
15.57
6
ATOM
3227
O
PHE
B
138
50.365
−3.369
9.434
1.00
17.73
8
ATOM
3228
CB
PHE
B
138
52.183
−1.237
10.974
1.00
17.43
6
ATOM
3229
CG
PHE
B
138
52.989
−1.110
12.277
1.00
18.89
6
ATOM
3230
CD1
PHE
B
138
52.929
0.069
12.997
1.00
18.99
6
ATOM
3231
CD2
PHE
B
138
53.729
−2.164
12.784
1.00
19.88
6
ATOM
3232
CE1
PHE
B
138
53.604
0.229
14.200
1.00
18.80
6
ATOM
3233
CE2
PHE
B
138
54.411
−2.031
14.006
1.00
21.38
6
ATOM
3234
CZ
PHE
B
138
54.324
−0.829
14.750
1.00
19.09
6
ATOM
3235
N
ASN
B
139
51.457
−2.015
8.033
1.00
18.34
7
ATOM
3236
CA
ASN
B
139
50.419
−2.157
7.032
1.00
17.77
6
ATOM
3237
C
ASN
B
139
50.464
−3.511
6.357
1.00
18.27
6
ATOM
3238
O
ASN
B
139
49.403
−4.059
5.975
1.00
20.66
8
ATOM
3239
CB
ASN
B
139
50.565
−1.044
5.974
1.00
19.21
6
ATOM
3240
CG
ASN
B
139
50.220
0.335
6.571
1.00
23.72
6
ATOM
3241
OD1
ASN
B
139
49.304
0.418
7.359
1.00
24.33
8
ATOM
3242
ND2
ASN
B
139
50.901
1.344
6.090
1.00
25.57
7
ATOM
3243
N
LEU
B
140
51.670
−4.126
6.251
1.00
17.43
7
ATOM
3244
CA
LEU
B
140
51.816
−5.435
5.643
1.00
19.77
6
ATOM
3245
C
LEU
B
140
51.392
−6.531
6.585
1.00
21.88
6
ATOM
3246
O
LEU
B
140
50.667
−7.465
6.154
1.00
22.03
8
ATOM
3247
CB
LEU
B
140
53.291
−5.684
5.198
1.00
18.61
6
ATOM
3248
CG
LEU
B
140
53.850
−4.849
4.059
1.00
20.20
6
ATOM
3249
CD1
LEU
B
140
55.377
−5.000
3.978
1.00
21.39
6
ATOM
3250
CD2
LEU
B
140
53.219
−5.272
2.744
1.00
21.81
6
ATOM
3251
N
VAL
B
141
51.714
−6.509
7.876
1.00
19.81
7
ATOM
3252
CA
VAL
B
141
51.423
−7.589
8.813
1.00
19.15
6
ATOM
3253
C
VAL
B
141
50.129
−7.384
9.575
1.00
18.23
6
ATOM
3254
O
VAL
B
141
49.508
−8.383
9.942
1.00
20.17
8
ATOM
3255
CB
VAL
B
141
52.613
−7.729
9.811
1.00
18.50
6
ATOM
3256
CG1
VAL
B
141
52.402
−8.790
10.886
1.00
19.99
6
ATOM
3257
CG2
VAL
B
141
53.895
−8.020
9.003
1.00
21.20
6
ATOM
3258
N
GLN
B
142
49.697
−6.125
9.766
1.00
19.03
7
ATOM
3259
CA
GLN
B
142
48.456
−5.803
10.496
1.00
18.67
6
ATOM
3260
C
GLN
B
142
48.367
−6.472
11.813
1.00
18.44
6
ATOM
3261
O
GLN
B
142
47.434
−7.193
12.153
1.00
18.66
8
ATOM
3262
CB
GLN
B
142
47.254
−6.242
9.585
1.00
23.65
6
ATOM
3263
CG
GLN
B
142
47.341
−5.370
8.311
1.00
27.77
6
ATOM
3264
CD
GLN
B
142
46.179
−5.714
7.395
1.00
31.00
6
ATOM
3265
OE1
GLN
B
142
45.039
−5.391
7.745
1.00
34.74
8
ATOM
3266
NE2
GLN
B
142
46.447
−6.335
6.281
1.00
33.99
7
ATOM
3267
N
PRO
B
143
49.444
−6.363
12.645
1.00
19.66
7
ATOM
3268
CA
PRO
B
143
49.526
−7.003
13.913
1.00
21.32
6
ATOM
3269
C
PRO
B
143
48.579
−6.373
14.939
1.00
20.88
6
ATOM
3270
O
PRO
B
143
48.162
−5.222
14.777
1.00
23.53
8
ATOM
3271
CB
PRO
B
143
50.974
−6.829
14.398
1.00
19.63
6
ATOM
3272
CG
PRO
B
143
51.245
−5.445
13.833
1.00
20.10
6
ATOM
3273
CD
PRO
B
143
50.576
−5.419
12.433
1.00
20.21
6
ATOM
3274
N
ASP
B
144
48.242
−7.127
15.964
1.00
19.65
7
ATOM
3275
CA
ASP
B
144
47.481
−6.572
17.069
1.00
19.58
6
ATOM
3276
C
ASP
B
144
48.443
−5.798
17.998
1.00
20.96
6
ATOM
3277
O
ASP
B
144
48.078
−4.862
18.701
1.00
21.10
8
ATOM
3278
CB
ASP
B
144
46.769
−7.645
17.857
1.00
21.71
6
ATOM
3279
CG
ASP
B
144
45.715
−8.336
16.977
1.00
29.09
6
ATOM
3280
OD1
ASP
B
144
46.026
−9.413
16.419
1.00
28.54
8
ATOM
3281
OD2
ASP
B
144
44.670
−7.652
16.763
1.00
29.74
8
ATOM
3282
N
ILE
B
145
49.639
−6.395
18.133
1.00
19.56
7
ATOM
3283
CA
ILE
B
145
50.662
−5.948
19.117
1.00
20.94
6
ATOM
3284
C
ILE
B
145
52.010
−5.887
18.446
1.00
19.85
6
ATOM
3285
O
ILE
B
145
52.279
−6.676
17.481
1.00
19.52
8
ATOM
3286
CB
ILE
B
145
50.680
−6.958
20.269
1.00
21.71
6
ATOM
3287
CG1
ILE
B
145
49.386
−6.954
21.122
1.00
24.70
6
ATOM
3288
CG2
ILE
B
145
51.900
−6.729
21.173
1.00
26.93
6
ATOM
3289
CD1
ILE
B
145
49.072
−8.328
21.695
1.00
28.80
6
ATOM
3290
N
ALA
B
146
52.910
−4.978
18.807
1.00
20.13
7
ATOM
3291
CA
ALA
B
146
54.247
−4.939
18.221
1.00
20.86
6
ATOM
3292
C
ALA
B
146
55.243
−4.703
19.396
1.00
23.49
6
ATOM
3293
O
ALA
B
146
54.897
−3.879
20.234
1.00
21.46
8
ATOM
3294
CB
ALA
B
146
54.442
−3.869
17.206
1.00
21.57
6
ATOM
3295
N
CYS
B
147
56.282
−5.520
19.470
1.00
21.24
7
ATOM
3296
CA
CYS
B
147
57.227
−5.418
20.634
1.00
21.57
6
ATOM
3297
C
CYS
B
147
58.514
−4.835
20.232
1.00
19.68
6
ATOM
3298
O
CYS
B
147
59.148
−5.086
19.189
1.00
23.55
8
ATOM
3299
CB
CYS
B
147
57.487
−6.803
21.192
1.00
25.97
6
ATOM
3300
SG
CYS
B
147
56.049
−7.649
21.811
1.00
30.41
16
ATOM
3301
N
PHE
B
148
59.070
−3.904
21.116
1.00
21.36
7
ATOM
3302
CA
PHE
B
148
60.268
−3.195
20.823
1.00
19.98
6
ATOM
3303
C
PHE
B
148
61.134
−3.123
22.146
1.00
19.23
6
ATOM
3304
O
PHE
B
148
60.479
−3.140
23.148
1.00
23.93
8
ATOM
3305
CB
PHE
B
148
60.072
−1.760
20.374
1.00
22.31
6
ATOM
3306
CG
PHE
B
148
59.349
−1.636
19.056
1.00
21.62
6
ATOM
3307
CD1
PHE
B
148
57.968
−1.677
19.110
1.00
22.35
6
ATOM
3308
CD2
PHE
B
148
60.045
−1.548
17.891
1.00
24.41
6
ATOM
3309
CE1
PHE
B
148
57.226
−1.664
17.918
1.00
21.17
6
ATOM
3310
CE2
PHE
B
148
59.307
−1.425
16.674
1.00
23.20
6
ATOM
3311
CZ
PHE
B
148
57.930
−1.509
16.754
1.00
19.10
6
ATOM
3312
N
GLY
B
149
62.415
−3.168
22.002
1.00
22.90
7
ATOM
3313
CA
GLY
B
149
63.243
−3.177
23.235
1.00
24.26
6
ATOM
3314
C
GLY
B
149
63.315
−1.783
23.884
1.00
26.58
6
ATOM
3315
O
GLY
B
149
63.397
−0.779
23.199
1.00
27.16
8
ATOM
3316
N
GLU
B
150
63.380
−1.759
25.212
1.00
27.01
7
ATOM
3317
CA
GLU
B
150
63.530
−0.425
25.870
1.00
29.68
6
ATOM
3318
C
GLU
B
150
64.894
0.200
25.737
1.00
31.07
6
ATOM
3319
O
GLU
B
150
65.020
1.425
25.978
1.00
30.50
8
ATOM
3320
CB
GLU
B
150
63.214
−0.532
27.368
1.00
31.68
6
ATOM
3321
CG
GLU
B
150
61.747
−0.632
27.660
1.00
34.09
6
ATOM
3322
CD
GLU
B
150
61.359
−0.743
29.111
1.00
37.99
6
ATOM
3323
OE1
GLU
B
150
62.205
−0.936
30.001
1.00
38.43
8
ATOM
3324
OE2
GLU
B
150
60.143
−0.643
29.350
1.00
40.17
8
ATOM
3325
N
LYS
B
151
65.951
−0.544
25.401
1.00
29.23
7
ATOM
3326
CA
LYS
B
151
67.258
0.093
25.292
1.00
31.41
6
ATOM
3327
C
LYS
B
151
67.273
1.220
24.300
1.00
31.27
6
ATOM
3328
O
LYS
B
151
67.936
2.260
24.433
1.00
27.21
8
ATOM
3329
CB
LYS
B
151
68.320
−0.926
24.878
1.00
34.10
6
ATOM
3330
CG
LYS
B
151
69.755
−0.397
24.923
1.00
37.66
6
ATOM
3331
CD
LYS
B
151
70.640
−1.476
24.317
1.00
41.05
6
ATOM
3332
CE
LYS
B
151
72.080
−1.431
24.765
1.00
43.98
6
ATOM
3333
NZ
LYS
B
151
72.893
−0.452
23.975
1.00
44.59
7
ATOM
3334
N
ASP
B
152
66.506
1.027
23.164
1.00
28.39
7
ATOM
3335
CA
ASP
B
152
66.518
2.032
22.110
1.00
28.38
6
ATOM
3336
C
ASP
B
152
65.332
2.937
22.374
1.00
28.23
6
ATOM
3337
O
ASP
B
152
64.210
2.803
21.783
1.00
26.26
8
ATOM
3338
CB
ASP
B
152
66.440
1.375
20.725
1.00
28.61
6
ATOM
3339
N
PHE
B
153
65.516
3.702
23.467
1.00
25.07
7
ATOM
3340
CA
PHE
B
153
64.373
4.471
23.974
1.00
26.53
6
ATOM
3341
C
PHE
B
153
63.892
5.520
22.974
1.00
21.61
6
ATOM
3342
O
PHE
B
153
62.708
5.839
23.024
1.00
24.77
8
ATOM
3343
CB
PHE
B
153
64.730
s.118
25.330
1.00
26.51
6
ATOM
3344
CG
PHE
B
153
65.779
6.167
25.190
1.00
29.71
6
ATOM
3345
CD1
PHE
B
153
65.443
7.493
24.943
1.00
29.96
6
ATOM
3346
CD2
PHE
B
153
67.132
5.855
25.398
1.00
29.77
6
ATOM
3347
CE1
PHE
B
153
66.423
8.454
24.846
1.00
31.18
6
ATOM
3348
CE2
PHE
B
153
68.099
6.820
25.256
1.00
28.84
6
ATOM
3349
CZ
PHE
B
153
67.763
8.135
24.997
1.00
31.32
6
ATOM
3350
N
GLN
B
154
64.740
6.002
22.113
1.00
23.01
7
ATOM
3351
CA
GLN
B
154
64.352
7.012
21.149
1.00
24.58
6
ATOM
3352
C
GLN
B
154
63.443
6.353
20.075
1.00
24.87
6
ATOM
3353
O
GLN
B
154
62.466
6.997
19.7D7
1.00
23.87
8
ATOM
3354
CB
GLN
B
154
65.558
7.664
20.502
1.00
26.01
6
ATOM
3355
CG
GLN
B
154
65.117
8.877
19.710
1.00
28.34
6
ATOM
3356
CD
GLN
B
154
66.171
9.934
19.456
1.00
30.51
6
ATOM
3357
OE1
GLN
B
154
67.342
9.742
19.766
1.00
32.27
8
ATOM
3358
NE2
GLN
B
154
65.742
11.030
18.839
1.00
28.70
7
ATOM
3359
N
GLN
B
155
63.841
5.183
19.619
1.00
24.42
7
ATOM
3360
CA
GLN
B
155
62.944
4.439
18.714
1.00
24.63
6
ATOM
3361
C
GLN
B
155
61.612
4.204
19.382
1.00
22.70
6
ATOM
3362
O
GLN
B
155
60.577
4.285
18.652
1.00
24.30
8
ATOM
3363
CB
GLN
B
155
63.549
3.094
18.268
1.00
25.06
6
ATOM
3364
CG
GLN
B
155
64.450
3.209
17.029
1.00
29.61
6
ATOM
3365
CD
GLN
B
155
64.506
1.856
16.285
1.00
32.67
6
ATOM
3366
OE1
GLN
B
155
65.360
1.610
15.440
1.00
37.92
8
ATOM
3367
NE2
GLN
B
155
63.610
0.953
16.599
1.00
28.61
7
ATOM
3368
N
LEU
B
156
61.522
3.748
20.602
1.00
20.20
7
ATOM
3369
CA
LEU
B
156
60.288
3.409
21.273
1.00
22.81
6
ATOM
3370
C
LEU
B
156
59.381
4.671
21.280
1.00
25.01
6
ATOM
3371
O
LEU
B
156
58.192
4.596
20.961
1.00
22.03
8
ATOM
3372
CB
LEU
B
156
60.549
2.887
22.651
1.00
23.28
6
ATOM
3373
CG
LEU
B
156
59.393
2.429
23.497
1.00
22.55
6
ATOM
3374
CD1
LEU
B
156
58.484
1.403
22.784
1.80
24.60
6
ATOM
3375
CD2
LEU
B
156
59.895
1.814
24.812
1.00
24.72
6
ATOM
3376
N
ALA
B
157
59.971
5.799
21.745
1.00
21.98
7
ATOM
3377
CA
ALA
B
157
59.149
7.006
21.699
1.00
23.16
6
ATOM
3378
C
ALA
B
157
58.684
7.366
20.300
1.00
21.84
6
ATOM
3379
O
ALA
B
157
57.504
7.836
20.225
1.00
22.95
8
ATOM
3380
CB
ALA
B
157
59.953
8.235
22.216
1.00
21.48
6
ATOM
3381
N
LEU
B
158
59.510
7.286
19.278
1.00
20.55
7
ATOM
3382
CA
LEU
B
158
59.209
7.601
17.902
1.00
24.17
6
ATOM
3383
C
LEU
B
158
58.018
6.737
17.408
1.00
24.35
6
ATOM
3384
O
LEU
B
158
57.063
7.345
16.896
1.00
21.76
8
ATOM
3385
CB
LEU
B
158
60.387
7.347
16.959
1.00
23.67
6
ATOM
3386
CG
LEU
B
158
60.332
7.840
15.511
1.00
25.33
6
ATOM
3387
CD1
LEU
B
158
60.910
9.254
15.385
1.00
25.04
6
ATOM
3388
CD2
LEU
B
158
61.078
6.855
14.633
1.00
24.59
6
ATOM
3389
N
ILE
B
159
58.085
5.451
17.683
1.00
21.94
7
ATOM
3390
CA
ILE
B
159
56.938
4.578
17.235
1.00
22.18
6
ATOM
3391
C
ILE
B
159
55.685
4.727
18.032
1.00
24.01
6
ATOM
3392
O
ILE
B
159
54.587
4.804
17.414
1.00
21.79
8
ATOM
3393
CB
ILE
B
159
57.436
3.108
17.263
1.00
21.63
6
ATOM
3394
CG1
ILE
B
159
58.615
3.036
16.314
1.00
21.10
6
ATOM
3395
CG2
ILE
B
159
56.305
2.118
16.906
1.00
21.29
6
ATOM
3396
CD1
ILE
B
159
58.290
3.361
14.848
1.00
27.17
6
ATOM
3397
N
ARG
B
160
55.764
5.016
19.357
1.80
21.20
7
ATOM
3398
CA
ARG
B
160
54.563
5.304
20.113
1.00
23.22
6
ATOM
3399
C
ARG
B
160
53.911
6.620
19.579
1.00
20.84
6
ATOM
3400
O
ARG
B
160
52.688
6.684
19.482
1.00
22.99
8
ATOM
3401
CB
ARG
B
160
54.786
5.438
21.627
1.00
22.64
6
ATOM
3402
CG
ARG
B
160
54.975
4.035
22.266
1.00
25.40
6
ATOM
3403
CD
ARG
B
160
55.364
4.303
23.720
0.50
28.99
6
ATOM
3404
NE
ARG
B
160
55.627
3.143
24.540
0.50
32.14
7
ATOM
3405
CZ
ARG
B
160
54.843
2.116
24.819
0.50
32.06
6
ATOM
3406
NH1
ARG
B
160
53.609
1.993
24.361
0.50
31.32
7
ATOM
3407
NH2
ARG
B
160
55.288
1.143
25.624
0.50
32.40
7
ATOM
3408
N
LYS
B
161
54.699
7.617
19.257
1.00
20.06
7
ATOM
3409
CA
LYS
B
161
54.121
8.866
18.707
1.00
19.89
6
ATOM
3410
C
LYS
B
161
53.502
8.570
17.331
1.00
20.88
6
ATOM
3411
O
LYS
B
161
52.418
9.085
17.017
1.00
20.38
8
ATOM
3412
CB
LYS
B
161
55.172
9.998
18.633
1.00
21.42
6
ATOM
3413
CG
LYS
B
161
54.474
11.290
18.133
1.00
23.56
6
ATOM
3414
CD
LYS
B
161
55.345
12.508
18.131
1.00
27.88
6
ATOM
3415
CE
LYS
B
161
54.736
13.692
17.336
1.00
31.75
6
ATOM
3416
NZ
LYS
B
161
53.349
13.890
17.879
1.00
29.32
7
ATOM
3417
N
MET
B
162
54.244
7.875
16.465
1.00
19.25
7
ATOM
3418
CA
MET
B
162
53.744
7.586
15.106
1.00
20.25
6
ATOM
3419
C
MET
B
162
52.443
6.849
15.190
1.00
20.77
6
ATOM
3420
O
MET
B
162
51.432
7.100
14.451
1.00
20.50
8
ATOM
3421
CB
MET
B
162
54.864
6.798
14.378
1.00
20.27
6
ATOM
3422
CG
MET
B
162
54.438
6.504
12.918
1.00
20.30
6
ATOM
3423
SD
MET
B
162
55.575
5.209
12.231
1.00
23.99
16
ATOM
3424
CE
MET
B
162
54.976
3.754
13.066
1.00
22.75
6
ATOM
3425
N
VAL
B
163
52.331
5.858
16.110
1.00
19.38
7
ATOM
3426
CA
VAL
B
163
51.106
5.095
16.243
1.00
20.12
6
ATOM
3427
C
VAL
B
163
49.926
5.955
16.693
1.00
22.03
6
ATOM
3428
O
VAL
B
163
48.820
5.841
16.163
1.00
19.78
8
ATOM
3429
CB
VAL
B
163
51.310
3.926
17.212
1.00
19.66
6
ATOM
3430
CG1
VAL
B
163
50.044
3.269
17.672
1.00
20.89
6
ATOM
3431
CG2
VAL
B
163
52.253
2.958
16.455
1.00
20.73
6
ATOM
3432
N
ALA
B
164
50.127
6.771
17.688
1.00
20.47
7
ATOM
3433
CA
ALA
B
164
49.065
7.634
18.189
1.00
21.69
6
ATOM
3434
C
ALA
B
164
48.642
8.624
17.101
1.00
20.50
6
ATOM
3435
O
ALA
B
164
47.419
8.750
16.892
1.00
23.25
8
ATOM
3436
CB
ALA
B
164
49.604
8.359
19.418
1.00
20.80
6
ATOM
3437
N
ASP
B
165
49.612
9.237
16.440
1.00
19.12
7
ATOM
3438
CA
ASP
B
165
49.190
10.233
15.409
1.00
18.46
6
ATOM
3439
C
ASP
B
165
48.550
9.577
14.207
1.00
22.82
6
ATOM
3440
O
ASP
B
165
47.594
10.145
13.660
1.00
22.60
8
ATOM
3441
CB
ASP
B
165
50.392
10.996
14.943
1.00
18.70
6
ATOM
3442
CG
ASP
B
165
51.018
12.009
15.941
1.00
18.80
6
ATOM
3443
OD1
ASP
B
165
50.354
12.300
16.916
1.00
21.84
8
ATOM
3444
OD2
ASP
B
165
52.112
12.486
15.692
1.00
21.56
8
ATOM
3445
N
MET
B
166
49.185
8.526
13.694
1.00
19.28
7
ATOM
3446
CA
MET
B
166
48.660
7.953
12.411
1.00
20.68
6
ATOM
3447
C
MET
B
166
47.436
7.082
12.604
1.00
21.52
6
ATOM
3448
O
MET
B
166
46.935
6.605
11.577
1.00
22.25
8
ATOM
3449
CB
MET
B
166
49.878
7.292
11.723
1.00
17.15
6
ATOM
3450
CG
MET
B
166
50.905
8.348
11.281
1.00
21.78
6
ATOM
3451
SD
MET
B
166
50.266
9.743
10.357
1.00
21.48
16
ATOM
3452
CE
MET
B
166
49.315
9.048
8.969
1.00
22.58
6
ATOM
3453
N
GLY
B
167
46.947
6.745
13.792
1.00
22.34
7
ATOM
3454
CA
GLY
B
167
45.725
5.983
14.001
1.00
21.60
6
ATOM
3455
C
GLY
B
167
45.804
4.480
13.881
1.00
21.23
6
ATOM
3456
O
GLY
B
167
44.803
3.783
13.677
1.00
19.88
8
ATOM
3457
N
PHE
B
168
47.043
3.939
13.961
1.00
21.11
7
ATOM
3458
CA
PHE
B
168
47.170
2.494
13.958
1.00
20.42
6
ATOM
3459
C
PHE
B
168
46.553
1.828
15.193
1.00
20.83
6
ATOM
3460
O
PHE
B
168
46.842
2.233
16.321
1.00
22.53
8
ATOM
3461
CB
PHE
B
168
48.653
2.079
13.921
1.00
21.51
6
ATOM
3462
CG
PHE
B
168
49.420
2.244
12.648
1.00
21.26
6
ATOM
3463
CD1
PHE
B
168
50.305
3.310
12.535
1.00
21.28
6
ATOM
3464
CD2
PHE
B
168
49.352
1.351
11.604
1.00
21.16
6
ATOM
3465
CE1
PHE
B
168
51.095
3.489
11.409
1.00
22.13
6
ATOM
3466
CE2
PHE
B
168
50.080
1.550
10.442
1.00
24.10
6
ATOM
3467
CZ
PHE
B
168
50.978
2.592
10.348
1.00
20.59
6
ATOM
3468
N
ASP
B
169
45.751
0.812
14.997
1.00
22.55
7
ATOM
3469
CA
ASP
B
169
45.089
0.089
16.054
1.00
23.63
6
ATOM
3470
C
ASP
B
169
46.010
−1.072
16.556
1.00
23.14
6
ATOM
3471
O
ASP
B
169
45.637
−2.215
16.493
1.00
23.77
8
ATOM
3472
CB
ASP
B
169
43.773
−0.497
15.594
1.00
27.60
6
ATOM
3473
CG
ASP
B
169
42.879
−1.031
16.711
1.00
30.74
6
ATOM
3474
OD1
ASP
B
169
43.197
−0.784
17.892
1.00
34.41
8
ATOM
3475
OD2
ASP
B
169
41.884
−1.685
16.342
1.00
34.81
8
ATOM
3476
N
ILE
B
170
47.137
−0.643
17.058
1.00
20.48
7
ATOM
3477
CA
ILE
B
170
48.196
−1.584
17.457
1.00
19.43
6
ATOM
3478
C
ILE
B
170
48.725
−1.236
18.834
1.00
21.42
6
ATOM
3479
O
ILE
B
170
49.048
−0.083
19.071
1.00
22.91
8
ATOM
3480
CB
ILE
B
170
49.351
−1.526
16.434
1.00
19.13
6
ATOM
3481
CG1
ILE
B
170
48.940
−1.849
14.994
1.00
21.06
6
ATOM
3482
CG2
ILE
B
170
50.464
−2.519
16.854
1.00
20.00
6
ATOM
3483
CD1
ILE
B
170
50.054
−1.568
13.974
1.00
23.10
6
ATOM
3484
N
GLU
B
171
48.847
−2.233
19.720
1.00
20.51
7
ATOM
3485
CA
GLU
B
171
49.415
−1.968
21.050
1.00
22.48
6
ATOM
3486
C
GLU
B
171
50.925
−1.992
20.961
1.00
23.14
6
ATOM
3487
O
GLU
B
171
51.470
−3.024
20.518
1.00
23.79
8
ATOM
3488
CB
GLU
B
171
48.824
−2.974
22.034
1.00
24.29
6
ATOM
3489
CG
GLU
B
171
49.506
−2.861
23.391
1.00
28.59
6
ATOM
3490
CD
GLU
B
171
49.089
−3.843
24.453
1.00
33.66
6
ATOM
3491
OE1
GLU
B
171
48.310
−4.782
24.246
1.00
34.21
8
ATOM
3492
OE2
GLU
B
171
49.580
−3.608
25.609
1.00
37.13
8
ATOM
3493
N
ILE
B
172
51.637
−0.956
21.410
1.00
21.22
7
ATOM
3494
CA
ILE
B
172
53.093
−0.965
21.349
1.00
19.30
6
ATOM
3495
C
ILE
B
172
53.656
−1.362
22.720
1.00
24.29
6
ATOM
3496
O
ILE
B
172
53.145
−0.847
23.730
1.00
25.41
8
ATOM
3497
CB
ILE
B
172
53.631
0.401
20.893
1.00
20.79
6
ATOM
3498
CG1
ILE
B
172
53.086
0.809
19.509
1.00
22.57
6
ATOM
3499
CG2
ILE
B
172
55.162
0.435
20.888
1.00
22.05
6
ATOM
3500
CD1
ILE
B
172
53.459
−0.175
18.386
1.00
21.95
6
ATOM
3501
N
VAL
B
173
54.392
−2.471
22.752
1.00
21.27
7
ATOM
3502
CA
VAL
B
173
54.895
−3.034
24.024
1.00
25.99
6
ATOM
3503
C
VAL
B
173
56.363
−2.785
24.113
1.00
25.58
6
ATOM
3504
O
VAL
B
173
57.087
−3.255
23.240
1.00
22.50
8
ATOM
3505
CB
VAL
B
173
54.583
−4.552
24.123
1.00
25.82
6
ATOM
3506
CG1
VAL
B
173
55.242
−5.122
25.406
1.00
26.85
6
ATOM
3507
CG2
VAL
B
173
53.094
−4.779
24.096
1.00
27.94
6
ATOM
3508
N
GLY
B
174
56.820
−2.085
25.189
1.00
24.62
7
ATOM
3509
CA
GLY
B
174
58.270
−1.862
25.313
1.00
23.53
6
ATOM
3510
C
GLY
B
174
58.740
−3.002
26.282
1.00
23.91
6
ATOM
3511
O
GLY
B
174
57.998
−3.288
27.218
1.00
26.78
8
ATOM
3512
N
VAL
B
175
59.801
−3.641
25.849
1.00
22.58
7
ATOM
3513
CA
VAL
B
175
60.234
−4.783
26.676
1.00
24.09
6
ATOM
3514
C
VAL
B
175
61.523
−4.341
27.430
1.00
23.90
6
ATOM
3515
O
VAL
B
175
62.502
−4.011
26.762
1.00
24.10
8
ATOM
3516
CB
VAL
B
175
60.476
−6.015
25.853
1.00
24.37
6
ATOM
3517
CG1
VAL
B
175
60.852
−7.180
26.767
1.00
28.33
6
ATOM
3518
CG2
VAL
B
175
59.219
−6.353
24.984
1.00
24.52
6
ATOM
3519
N
PRO
B
176
61.469
−4.464
28.728
1.00
28.58
7
ATOM
3520
CA
PRO
B
176
62.648
−4.211
29.574
1.00
32.47
6
ATOM
3521
C
PRO
B
176
63.888
−4.974
29.180
1.00
32.41
6
ATOM
3522
O
PRO
B
176
63.831
−6.135
28.746
1.00
28.92
8
ATOM
3523
CB
PRO
B
176
62.159
−4.588
30.980
1.00
33.03
6
ATOM
3524
CG
PRO
B
176
60.685
−4.380
30.922
1.00
34.15
6
ATOM
3525
CD
PRO
B
176
60.320
−4.916
29.543
1.00
28.09
6
ATOM
3526
N
ILE
B
177
65.121
−4.418
29.353
1.00
31.48
7
ATOM
3527
CA
ILE
B
177
66.307
−5.079
28.865
1.00
32.30
6
ATOM
3528
C
ILE
B
177
66.572
−6.407
29.607
1.00
30.07
6
ATOM
3529
O
ILE
B
177
66.054
−6.698
30.686
1.00
32.04
8
ATOM
3530
CB
ILE
B
177
67.641
−4.292
28.903
1.00
33.70
6
ATOM
3531
CG1
ILE
B
177
68.066
−3.943
30.331
1.00
33.12
6
ATOM
3532
CG2
ILE
B
177
67.518
−3.039
28.030
1.00
34.28
6
ATOM
3533
CD1
ILE
B
177
69.430
−3.243
30.349
1.00
34.81
6
ATOM
3534
N
MET
B
178
67.408
−7.204
28.952
1.00
32.08
7
ATOM
3535
CA
MET
B
178
67.674
−8.503
29.572
1.00
35.37
6
ATOM
3536
C
MET
B
178
68.620
−8.292
30.772
1.00
34.12
6
ATOM
3537
O
MET
B
178
69.597
−7.573
30.642
1.00
31.98
8
ATOM
3538
CB
MET
B
178
68.295
−9.532
28.641
1.00
40.27
6
ATOM
3539
CG
MET
B
178
67.437
−10.819
28.679
1.00
44.21
6
ATOM
3540
SD
MET
B
178
68.203
−12.124
27.749
1.00
51.85
16
ATOM
3541
CE
MET
B
178
69.561
−11.316
26.916
1.00
48.86
6
ATOM
3542
N
ARG
B
179
68.313
−8.994
31.814
1.00
35.69
7
ATOM
3543
CA
ARG
B
179
69.085
−8.847
33.060
1.00
36.43
6
ATOM
3544
C
ARG
B
179
69.292
−10.188
33.715
1.00
37.86
6
ATOM
3545
O
ARG
B
179
68.430
−11.054
33.618
1.00
38.23
8
ATOM
3546
CB
ARG
B
179
68.260
−7.887
33.870
1.00
36.62
6
ATOM
3547
CG
ARG
B
179
68.473
−7.248
35.163
1.00
38.40
6
ATOM
3548
CD
ARG
B
179
67.373
−6.311
35.598
1.00
34.70
6
ATOM
3549
NE
ARG
B
179
67.202
−5.122
34.808
1.00
31.82
7
ATOM
3550
CZ
ARG
B
179
68.057
−4.149
34.534
1.00
32.71
6
ATOM
3551
NH1
ARG
B
179
69.308
−4.167
34.984
1.00
30.99
7
ATOM
3552
NH2
ARG
B
179
67.715
−3.067
33.831
1.00
33.25
7
ATOM
3553
N
ALA
B
180
70.363
−10.335
34.477
1.00
36.11
7
ATOM
3554
CA
ALA
B
180
70.602
−11.562
35.235
1.00
36.60
6
ATOM
3555
C
ALA
B
180
69.640
−11.614
36.404
1.00
36.37
6
ATOM
3556
O
ALA
B
180
68.929
−10.685
36.743
1.00
36.44
8
ATOM
3557
CB
ALA
B
180
72.048
−11.541
35.689
1.00
36.08
6
ATOM
3558
N
LYS
B
181
69.621
−12.775
37.102
1.00
37.25
7
ATOM
3559
CA
LYS
B
181
68.797
−12.903
38.292
1.00
38.41
6
ATOM
3560
C
LYS
B
181
69.223
−11.942
39.395
1.00
37.82
6
ATOM
3561
O
LYS
B
181
68.366
−11.482
40.158
1.00
40.11
8
ATOM
3562
CB
LYS
B
181
68.862
−14.317
38.895
1.00
39.54
6
ATOM
3563
N
ASP
B
182
70.495
−11.584
39.503
1.00
36.65
7
ATOM
3564
CA
ASP
B
182
70.935
−10.663
40.548
1.00
35.51
6
ATOM
3565
C
ASP
B
182
70.714
−9.206
40.091
1.00
35.06
6
ATOM
3566
O
ASP
B
182
71.004
−8.303
40.868
1.00
33.11
8
ATOM
3567
CB
ASP
B
182
72.392
−10.861
40.981
1.00
37.04
6
ATOM
3568
CG
ASP
B
182
73.414
−10.661
39.890
1.00
38.43
6
ATOM
3569
OD1
ASP
B
182
73.047
−10.265
38.753
1.00
38.66
8
ATOM
3570
OD2
ASP
B
182
74.624
−10.938
40.116
1.00
38.45
8
ATOM
3571
N
GLY
B
183
70.283
−8.992
38.840
1.00
35.23
7
ATOM
3572
CA
GLY
B
183
69.907
−7.618
38.467
1.00
32.81
6
ATOM
3573
C
GLY
B
183
70.883
−7.003
37.494
1.00
33.61
6
ATOM
3574
O
GLY
B
183
70.523
−5.956
36.928
1.00
33.06
8
ATOM
3575
N
LEU
B
184
72.029
−7.592
37.220
1.00
31.99
7
ATOM
3576
CA
LEU
B
184
72.977
−7.004
36.286
1.00
32.29
6
ATOM
3577
C
LEU
B
184
72.517
−7.011
34.826
1.00
33.46
6
ATOM
3578
O
LEU
B
184
72.300
−8.130
34.314
1.00
32.16
8
ATOM
3579
CB
LEU
B
184
74.325
−7.737
36.370
1.00
32.38
6
ATOM
3580
CG
LEU
B
184
75.481
−7.019
35.655
1.00
32.34
6
ATOM
3581
CD1
LEU
B
184
75.643
−5.559
36.125
1.00
34.61
6
ATOM
3582
CD2
LEU
B
184
76.748
−7.838
35.853
1.00
34.57
6
ATOM
3583
N
ALA
B
185
72.466
−5.818
34.204
1.00
32.96
7
ATOM
3584
CA
ALA
B
185
72.099
−5.821
32.780
1.00
33.17
6
ATOM
3585
C
ALA
B
185
73.053
−6.670
31.950
1.00
35.69
6
ATOM
3586
O
ALA
B
185
74.281
−6.510
32.057
1.00
35.57
8
ATOM
3587
CB
ALA
B
185
72.076
−4.368
32.316
1.00
29.95
6
ATOM
1443
N
LEU
B
186
72.752
−7.823
31.203
1.00
16.87
ATOM
1444
CA
LEU
B
186
73.699
−8.676
30.476
1.00
16.99
ATOM
1445
O
LEU
B
186
74.354
−7.793
29.406
1.00
17.67
ATOM
1446
O
LEU
B
186
73.662
−7.050
28.666
1.00
20.34
ATOM
1447
CB
LEU
B
186
73.001
−9.890
29.872
1.00
16.87
ATOM
1448
CG
LEU
B
186
72.315
−10.841
30.851
1.00
18.67
ATOM
1449
CD1
LEU
B
186
71.803
−12.062
30.097
1.00
20.67
ATOM
1450
CD2
LEU
B
186
73.289
−11.257
31.936
1.00
17.31
ATOM
1451
N
SER
B
187
75.650
−7.991
29.285
1.00
18.83
ATOM
1452
CA
SER
B
187
76.407
−7.179
28.327
1.00
17.18
ATOM
1453
C
SER
B
187
77.754
−7.771
28.079
1.00
17.64
ATOM
1454
O
SER
B
187
78.405
−8.305
28.987
1.00
18.63
ATOM
1455
CB
SER
B
187
76.597
−5.762
28.933
1.00
20.23
ATOM
1456
OG
SER
B
187
77.485
−4.989
28.093
1.00
20.91
ATOM
1457
N
SER
B
188
78.290
−7.564
26.832
1.00
17.55
ATOM
1458
CA
SER
B
188
79.706
−7.917
26.649
1.00
17.70
ATOM
1459
C
SER
B
188
80.653
−7.182
27.579
1.00
17.74
ATOM
1460
O
SER
B
188
81.764
−7.648
27.944
1.00
18.92
ATOM
1461
CB
SER
B
188
80.127
−7.598
25.196
1.00
19.73
ATOM
1462
OG
SER
B
188
79.893
−6.208
24.915
1.00
20.84
ATOM
1463
N
ARG
B
189
80.298
−6.012
28.096
1.00
18.16
ATOM
1464
CA
ARG
B
189
81.104
−5.205
28.988
1.00
19.85
ATOM
1465
C
ARG
B
189
81.386
−5.989
30.311
1.00
20.33
ATOM
1466
O
ARG
B
189
82.356
−5.612
30.969
1.00
21.91
ATOM
1467
CB
ARG
B
189
80.426
−3.848
29.284
1.00
20.55
ATOM
1468
CG
ARG
B
189
80.245
−3.075
27.973
1.00
22.89
ATOM
1469
CD
ARG
B
189
79.609
−1.707
28.273
1.00
23.21
ATOM
1470
NE
ARG
B
189
79.461
−1.073
26.939
1.00
25.97
ATOM
1471
CZ
ARG
B
189
79.880
0.157
26.683
1.00
28.29
ATOM
1472
NH1
ARG
B
189
80.387
0.915
27.617
1.00
26.60
ATOM
1473
NH2
ARG
B
189
79.714
0.627
25.429
1.00
28.41
ATOM
1474
N
ASN
B
190
80.441
−6.790
30.763
1.00
19.42
ATOM
1475
CA
ASN
B
190
80.639
−7.442
32.041
1.00
19.64
ATOM
1476
C
ASN
B
190
81.891
−8.271
32.059
1.00
22.61
ATOM
1477
O
ASN
B
190
82.467
−8.717
33.097
1.00
23.27
ATOM
1478
CB
ASN
B
190
79.437
−8.347
32.355
1.00
19.54
ATOM
1479
CG
ASN
B
190
78.168
−7.518
32.494
1.00
21.41
ATOM
1480
OD1
ASN
B
190
77.045
−8.077
32.323
1.00
21.40
ATOM
1481
ND2
ASN
B
190
78.310
−6.244
32.814
1.00
19.16
ATOM
1497
N
GLY
B
191
82.333
−8.712
30.735
1.00
27.44
ATOM
1498
CA
GLY
B
191
83.554
−9.514
30.632
1.00
28.04
ATOM
1499
C
GLY
B
191
84.823
−8.796
31.035
1.00
29.70
ATOM
1500
O
GLY
B
191
85.815
−9.487
31.266
1.00
31.47
ATOM
1482
N
TYR
B
192
84.825
−7.581
31.228
1.00
26.92
ATOM
1483
CA
TYR
B
192
86.032
−6.786
31.629
1.00
29.88
ATOM
1484
C
TYR
B
192
86.854
−6.581
33.125
1.00
29.91
ATOM
1485
O
TYR
B
192
87.053
−5.998
33.601
1.00
34.28
ATOM
1486
CB
TYR
B
192
86.154
−5.424
30.922
1.00
30.32
ATOM
1487
CG
TYR
B
192
86.340
−5.687
29.438
1.00
32.17
ATOM
1488
CD1
TYR
B
192
85.211
−5.943
28.667
1.00
32.38
ATOM
1489
CD2
TYR
B
192
87.596
−5.764
28.842
1.00
34.00
ATOM
1490
CE1
TYR
B
192
85.313
−6.234
27.337
1.00
35.21
ATOM
1491
CE2
TYR
B
192
87.703
−6.056
27.486
1.00
34.55
ATOM
1492
CZ
TYR
B
192
86.578
−6.276
26.747
1.00
36.66
ATOM
1493
OH
TYR
B
192
86.631
−6.577
25.395
1.00
38.33
ATOM
1494
N
LEU
B
193
85.033
−7.028
33.865
1.00
28.20
ATOM
1495
CA
LEU
B
193
85.075
−6.900
35.299
1.00
26.63
ATOM
1496
C
LEU
B
193
85.870
−7.994
35.986
1.00
27.15
ATOM
1497
O
LEU
B
193
85.690
−9.155
35.614
1.00
28.28
ATOM
1498
CB
LEU
B
193
83.651
−6.979
35.888
1.00
26.20
ATOM
1499
CG
LEU
B
193
82.648
−5.971
35.339
1.00
25.58
ATOM
1500
CD1
LEU
B
193
81.223
−6.375
35.649
1.00
24.08
ATOM
1501
CD2
LEU
B
193
82.909
−4.563
35.910
1.00
27.77
ATOM
1502
N
THR
B
194
86.596
−7.704
37.090
1.00
28.42
ATOM
1503
CA
THR
B
194
87.177
−8.819
37.838
1.00
27.62
ATOM
1504
C
THR
B
194
86.087
−9.564
38.585
1.00
25.74
ATOM
1505
O
THR
B
194
84.983
−8.990
38.712
1.00
26.48
ATOM
1506
CB
THR
B
194
88.236
−8.313
38.835
1.00
29.34
ATOM
1507
OG1
THR
B
194
87.611
−7.354
39.693
1.00
38.55
ATOM
1508
CG2
THR
B
194
89.370
−7.647
38.064
1.00
32.65
ATOM
3620
N
ALA
B
195
86.095
−11.397
38.739
1.00
45.01
7
ATOM
3621
CA
ALA
B
195
85.137
−12.052
39.619
1.00
45.61
6
ATOM
3622
C
ALA
B
195
84.702
−11.095
40.732
1.00
46.90
6
ATOM
3623
O
ALA
B
195
83.510
−11.093
41.082
1.00
45.91
8
ATOM
3624
CB
ALA
B
195
85.717
−13.336
48.196
1.00
46.79
6
ATOM
3625
N
GLU
B
196
85.603
−18.288
41.278
1.00
47.33
7
ATOM
3626
CA
GLU
B
196
85.242
−9.350
42.330
1.00
48.34
6
ATOM
3627
C
GLU
B
196
84.313
−8.252
41.828
1.00
46.99
6
ATOM
3628
O
GLU
B
196
83.325
−7.912
42.497
1.00
47.72
8
ATOM
3629
CB
GLU
B
196
86.459
−8.634
42.959
1.00
52.20
6
ATOM
3630
CG
GLU
B
196
86.011
−7.646
44.018
1.00
56.19
6
ATOM
3631
CD
GLU
B
196
86.989
−6.639
44.543
1.00
59.41
6
ATOM
3632
OE1
GLU
B
196
88.104
−6.474
43.993
1.00
61.45
8
ATOM
3633
OE2
GLU
B
196
86.639
−5.966
45.555
1.00
61.84
8
ATOM
3634
N
GLN
B
197
84.641
−7.664
40.687
1.00
44.75
7
ATOM
3635
CA
GLN
B
197
83.801
−6.624
40.095
1.00
43.46
6
ATOM
3636
C
GLN
B
197
82.428
−7.188
39.782
1.00
42.72
6
ATOM
3637
O
GLN
B
197
81.425
−6.478
39.983
1.00
41.97
8
ATOM
3638
CB
GLN
B
197
84.430
−6.018
38.832
1.00
43.86
6
ATOM
3639
CG
GLN
B
197
85.754
−5.346
39.203
1.00
46.24
6
ATOM
3640
CD
GLN
B
197
86.485
−4.709
38.047
1.00
48.63
6
ATOM
3641
OE1
GLN
B
197
86.387
−5.148
36.902
1.00
50.12
8
ATOM
3642
NE2
GLN
B
197
87.247
−3.655
38.397
1.00
49.65
7
ATOM
3643
N
ARG
B
198
82.339
−8.436
39.342
1.00
40.11
7
ATOM
3644
CA
ARG
B
198
81.024
−9.023
39.025
1.00
40.65
6
ATOM
3645
C
ARG
B
198
80.231
−9.134
40.321
1.00
40.50
6
ATOM
3646
O
ARG
B
198
79.001
−9.070
40.226
1.00
40.26
8
ATOM
3647
CB
ARG
B
198
81.196
−10.331
38.255
1.00
38.75
6
ATOM
3648
CG
ARG
B
198
79.950
−11.169
37.980
1.00
40.23
6
ATOM
3649
CD
ARG
B
198
78.984
−10.360
37.114
1.00
38.56
6
ATOM
3650
NE
ARG
B
198
77.712
−10.999
36.860
1.00
40.33
7
ATOM
3651
CZ
ARG
B
198
76.685
−10.913
37.703
1.00
38.73
6
ATOM
3652
NH1
ARG
B
198
76.828
−10.212
38.843
1.00
37.38
7
ATOM
3653
NH2
ARG
B
198
75.530
−11.506
37.383
1.00
39.11
7
ATOM
3654
N
LYS
B
199
80.821
−9.198
41.506
1.00
40.18
7
ATOM
3655
CA
LYS
B
199
80.067
−9.237
42.738
1.00
41.84
6
ATOM
3656
C
LYS
B
199
79.519
−7.843
43.083
1.00
39.14
6
ATOM
3657
O
LYS
B
199
78.440
−7.806
43.660
1.00
39.85
8
ATOM
3658
CB
LYS
B
199
80.852
−9.706
43.969
1.00
44.70
6
ATOM
3659
CG
LYS
B
199
81.675
−10.963
43.783
1.00
48.43
6
ATOM
3660
CD
LYS
B
199
82.186
−11.540
45.087
1.00
50.67
6
ATOM
3661
CE
LYS
B
199
82.837
−10.559
46.037
1.00
52.79
6
ATOM
3662
NZ
LYS
B
199
84.285
−10.286
45.751
1.00
55.36
7
ATOM
3663
N
ILE
B
200
80.245
−6.791
42.754
1.00
36.48
7
ATOM
3664
CA
ILE
B
200
79.815
−5.425
43.013
1.00
36.30
6
ATOM
3665
C
ILE
B
200
78.867
−4.836
41.964
1.00
34.09
6
ATOM
3666
O
ILE
B
200
77.970
−4.048
42.300
1.00
31.98
8
ATOM
3667
CB
ILE
B
200
81.036
−4.477
43.052
1.00
37.30
6
ATOM
3668
CG1
ILE
B
200
81.938
−4.835
44.261
1.00
39.39
6
ATOM
3669
CG2
ILE
B
200
80.668
−2.995
43.087
1.00
38.32
6
ATOM
3670
CD1
ILE
B
200
83.228
−4.024
44.171
1.00
39.23
6
ATOM
3671
N
ALA
B
201
78.923
−5.343
40.749
1.00
31.89
7
ATOM
3672
CA
ALA
B
201
78.199
−4.790
39.605
1.00
30.33
6
ATOM
3673
C
ALA
B
201
76.683
−4.738
39.757
1.00
30.26
6
ATOM
3674
O
ALA
B
201
76.126
−3.736
39.270
1.00
28.19
8
ATOM
3675
CB
ALA
B
201
78.588
−5.549
38.327
1.00
31.33
6
ATOM
3676
N
PRO
B
202
75.978
−5.632
40.395
1.00
29.89
7
ATOM
3677
CA
PRO
B
202
74.538
−5.483
40.618
1.00
31.17
6
ATOM
3678
C
PRO
B
202
74.130
−4.220
41.350
1.00
30.89
6
ATOM
3679
O
PRO
B
202
72.942
−3.842
41.356
1.00
33.70
8
ATOM
3680
CB
PRO
B
202
74.171
−6.714
41.422
1.00
31.80
6
ATOM
3681
CG
PRO
B
202
75.203
−7.727
41.041
1.00
32.51
6
ATOM
3682
CD
PRO
B
202
76.485
−6.926
40.935
1.00
30.92
6
ATOM
3683
N
GLY
B
203
75.003
−3.520
42.079
1.00
30.61
7
ATOM
3684
CA
GLY
B
203
74.724
−2.274
42.775
1.00
29.71
6
ATOM
3685
C
GLY
B
203
74.185
−1.180
41.844
1.00
29.14
6
ATOM
3686
O
GLY
B
203
73.382
−0.333
42.278
1.00
27.39
8
ATOM
3687
N
LEU
B
204
74.569
−1.208
40.562
1.00
26.29
7
ATOM
3688
CA
LEU
B
204
74.116
−0.193
39.634
1.00
27.87
6
ATOM
3689
C
LEU
B
204
72.595
−0.279
39.482
1.00
26.50
6
ATOM
3690
O
LEU
B
204
71.878
0.736
39.532
1.00
26.32
8
ATOM
3691
CB
LEU
B
204
74.789
−0.294
38.259
1.00
28.45
6
ATOM
3692
CG
LEU
B
204
74.362
0.731
37.212
1.00
29.87
6
ATOM
3693
CD1
LEU
B
204
74.600
2.168
37.697
1.00
31.40
6
ATOM
3694
CD2
LEU
B
204
75.087
0.559
35.887
1.00
32.44
6
ATOM
3695
N
TYR
B
205
72.132
−1.509
39.245
1.00
26.81
7
ATOM
3696
CA
TYR
B
205
70.667
−1.619
39.081
1.00
28.26
6
ATOM
3697
C
TYR
B
205
69.946
−1.322
40.382
1.00
28.28
6
ATOM
3698
O
TYR
B
205
68.816
−0.829
40.340
1.00
27.87
8
ATOM
3699
CB
TYR
B
205
70.328
−2.995
38.524
1.00
27.88
6
ATOM
3700
CG
TYR
B
205
68.848
−3.144
38.265
1.00
30.23
6
ATOM
3701
CD1
TYR
B
205
68.193
−2.323
37.360
1.00
30.41
6
ATOM
3702
CD2
TYR
B
205
68.111
−4.106
38.935
1.00
32.30
6
ATOM
3703
CE1
TYR
B
205
66.838
−2.493
37.115
1.00
31.17
6
ATOM
3704
CE2
TYR
B
205
66.743
−4.304
38.698
1.00
32.16
6
ATOM
3705
CZ
TYR
B
205
66.134
−3.480
37.784
1.00
33.79
6
ATOM
3706
OH
TYR
B
205
64.774
−3.587
37.529
1.00
36.69
8
ATOM
3707
N
LYS
B
206
70.554
−1.567
41.568
1.00
27.79
7
ATOM
3708
CA
LYS
B
206
69.949
−1.137
42.812
1.00
28.48
6
ATOM
3709
C
LYS
B
206
69.794
0.379
42.849
1.00
26.89
6
ATOM
3710
O
LYS
B
206
68.729
0.847
43.295
1.00
26.06
8
ATOM
3711
CB
LYS
B
206
70.814
−1.650
44.005
1.00
31.12
6
ATOM
3712
CG
LYS
B
206
70.702
−3.191
44.056
1.00
35.12
6
ATOM
3713
CD
LYS
B
206
71.439
−3.803
45.235
1.00
38.80
6
ATOM
3714
CE
LYS
B
206
71.267
−5.329
45.230
1.00
41.11
6
ATOM
3715
NZ
LYS
B
206
72.055
−5.939
46.361
1.00
44.45
7
ATOM
3716
N
VAL
B
207
70.786
1.151
42.450
1.00
24.10
7
ATOM
3717
CA
VAL
B
207
70.698
2.623
42.437
1.00
23.57
6
ATOM
3718
C
VAL
B
207
69.692
3.075
41.353
1.00
25.00
6
ATOM
3719
O
VAL
B
207
68.785
3.854
41.709
1.00
25.30
8
ATOM
3720
CB
VAL
B
207
72.075
3.263
42.273
1.00
25.80
6
ATOM
3721
CG1
VAL
B
207
71.998
4.765
42.088
1.00
24.61
6
ATOM
3722
CG2
VAL
B
207
72.941
2.900
43.507
1.00
26.07
6
ATOM
3723
N
LEU
B
208
69.679
2.455
40.200
1.00
25.37
7
ATOM
3724
CA
LEU
B
208
68.640
2.782
39.185
1.00
25.10
6
ATOM
3725
C
LEU
B
208
67.243
2.553
39.694
1.00
24.92
6
ATOM
3726
O
LEU
B
208
66.280
3.338
39.468
1.00
25.42
8
ATOM
3727
CB
LEU
B
208
68.989
1.910
37.985
1.00
26.66
6
ATOM
3728
CG
LEU
B
208
68.261
2.079
36.661
1.00
30.34
6
ATOM
3729
CD1
LEU
B
208
68.389
3.525
36.163
1.00
32.04
6
ATOM
3730
CD2
LEU
B
208
68.793
1.084
35.646
1.00
31.70
6
ATOM
3731
N
SER
B
209
67.019
1.416
40.355
1.00
26.22
7
ATOM
3732
CA
SER
B
209
65.726
1.035
40.907
1.00
29.64
6
ATOM
3733
C
SER
B
209
65.293
2.025
41.988
1.00
30.28
6
ATOM
3734
O
SER
B
209
64.107
2.380
42.055
1.00
30.20
8
ATOM
3735
CB
SER
B
209
65.710
−0.386
41.480
1.00
30.00
6
ATOM
3736
OG
SER
B
209
65.923
−1.312
40.425
1.00
32.79
8
ATOM
3737
N
SER
B
210
66.262
2.526
42.772
1.00
29.87
7
ATOM
3738
CA
SER
B
210
65.938
3.533
43.764
1.00
30.73
6
ATOM
3739
C
SER
B
210
65.469
4.839
43.141
1.00
28.63
6
ATOM
3740
O
SER
B
210
64.551
5.481
43.694
1.00
30.02
8
ATOM
3741
CB
SER
B
210
67.171
3.837
44.652
1.00
33.65
6
ATOM
3742
OG
SER
B
210
66.847
4.965
45.451
1.00
38.88
8
ATOM
3743
N
ILE
B
211
66.115
5.259
42.067
1.00
26.67
7
ATOM
3744
CA
ILE
B
211
65.727
6.462
41.337
1.00
26.97
6
ATOM
3745
C
ILE
B
211
64.283
6.278
40.860
1.00
29.84
6
ATOM
3746
O
ILE
B
211
63.426
7.151
41.011
1.00
29.98
8
ATOM
3747
CB
ILE
B
211
66.584
6.759
40.124
1.00
26.70
6
ATOM
3748
CC1
ILE
B
211
68.031
7.036
40.607
1.00
26.03
6
ATOM
3749
CG2
ILE
B
211
66.046
7.935
39.290
1.00
27.20
6
ATOM
3750
CD1
ILE
B
211
69.081
7.179
39.551
1.00
25.43
6
ATOM
3751
N
ALA
B
212
64.062
5.111
40.250
1.00
29.63
7
ATOM
3752
CA
ALA
B
212
62.703
4.840
39.732
1.00
31.76
6
ATOM
3753
C
ALA
B
212
61.680
4.874
40.827
1.00
33.70
6
ATOM
3754
O
ALA
B
212
60.601
5.488
40.669
1.00
35.70
8
ATOM
3755
CB
ALA
B
212
62.713
3.477
39.041
1.00
30.18
6
ATOM
3756
N
ASP
B
213
61.985
4.267
41.976
1.00
35.57
7
ATOM
3757
CA
ASP
B
213
61.051
4.267
43.097
1.00
37.44
6
ATOM
3758
C
ASP
B
213
60.766
5.705
43.541
1.00
38.51
6
ATOM
3759
O
ASP
B
213
59.588
5.981
43.821
1.00
39.54
8
ATOM
3760
CB
ASP
B
213
61.540
3.469
44.294
1.00
40.83
6
ATOM
3761
CG
ASP
B
213
61.594
1.978
44.075
1.00
43.42
6
ATOM
3762
OD1
ASP
B
213
60.952
1.468
43.127
1.00
44.23
8
ATOM
3763
OD2
ASP
B
213
62.266
1.294
44.889
1.00
45.13
8
ATOM
3764
N
LYS
B
214
61.739
6.605
43.622
1.00
36.89
7
ATOM
3765
CA
LYS
B
214
61.439
7.980
44.023
1.00
37.14
6
ATOM
3766
C
LYS
B
214
60.553
8.695
43.015
1.00
38.10
6
ATOM
3767
O
LYS
B
214
59.689
9.521
43.354
1.00
38.08
8
ATOM
3768
CB
LYS
B
214
62.734
8.783
44.210
1.00
35.35
6
ATOM
3769
CG
LYS
B
214
63.592
8.274
45.353
1.00
34.18
6
ATOM
3770
CD
LYS
B
214
64.924
9.016
45.447
1.00
33.76
6
ATOM
3771
CE
LYS
B
214
65.708
8.660
46.703
1.00
35.46
6
ATOM
3772
NZ
LYS
B
214
66.968
9.471
46.836
1.00
33.81
7
ATOM
3773
N
LEU
B
215
60.824
8.468
41.720
1.00
37.41
7
ATOM
3774
CA
LEU
B
215
60.005
9.116
40.679
1.00
38.52
6
ATOM
3775
C
LEU
B
215
58.575
8.587
40.776
1.00
41.72
6
ATOM
3776
O
LEU
B
215
57.606
9.372
40.631
1.00
41.98
8
ATOM
3777
CB
LEU
B
215
60.604
8.904
39.310
1.00
37.43
6
ATOM
3778
CG
LEU
B
215
61.897
9.594
38.900
1.00
36.45
6
ATOM
3779
CD1
LEU
B
215
62.313
9.105
37.529
1.00
36.60
6
ATOM
3780
CD2
LEU
B
215
61.767
11.119
38.869
1.00
37.66
6
ATOM
3781
N
GLN
B
216
58.409
7.300
41.061
1.00
42.52
7
ATOM
3782
CA
CLN
B
216
57.077
6.739
41.231
1.00
46.61
6
ATOM
3783
C
GLN
B
216
56.353
7.337
42.439
1.00
47.19
6
ATOM
3784
O
GLN
B
216
55.125
7.438
42.427
1.00
48.78
8
ATOM
3785
CB
GLN
B
216
57.069
5.232
41.449
1.00
48.29
6
ATOM
3786
CG
GLN
B
216
57.290
4.444
40.180
1.00
53.02
6
ATOM
3787
CD
GLN
B
216
56.839
3.002
40.322
1.00
54.94
6
ATOM
3788
OE1
GLN
B
216
55.736
2.658
39.896
1.00
57.54
8
ATOM
3789
NE2
GLN
B
216
57.710
2.210
40.927
1.00
55.50
7
ATOM
3790
N
ALA
B
217
57.092
7.678
43.486
1.00
46.68
7
ATOM
3791
CA
ALA
B
217
56.502
8.282
44.665
1.00
47.12
6
ATOM
3792
C
ALA
B
217
56.114
9.746
44.444
1.00
46.63
6
ATOM
3793
O
ALA
B
217
55.403
10.274
45.308
1.00
47.81
8
ATOM
3794
CB
ALA
B
217
57.460
8.177
45.853
1.00
46.15
6
ATOM
3795
N
GLY
B
218
56.519
10.406
43.374
1.00
45.52
7
ATOM
3796
CA
GLY
B
218
56.156
11.790
43.127
1.00
45.00
6
ATOM
3797
C
GLY
B
218
57.308
12.764
43.230
1.00
45.03
6
ATOM
3798
O
GLY
B
218
57.199
13.970
42.964
1.00
45.86
8
ATOM
3799
N
GLU
B
219
58.491
12.255
43.605
1.00
43.84
7
ATOM
3800
CA
GLU
B
219
59.664
13.121
43.708
1.00
43.09
6
ATOM
3801
C
GLU
B
219
60.052
13.746
42.388
1.00
40.95
6
ATOM
3802
O
GLU
B
219
60.141
13.088
41.333
1.00
39.42
8
ATOM
3803
CB
GLU
B
219
60.804
12.270
44.287
1.00
45.88
6
ATOM
3804
CG
GLU
B
219
61.238
12.787
45.633
1.00
50.50
6
ATOM
3805
CD
GLU
B
219
62.401
12.048
46.269
1.00
52.33
6
ATOM
3806
OE1
GLU
B
219
62.065
11.125
47.052
1.00
54.16
8
ATOM
3807
OE2
GLU
B
219
63.564
12.388
46.016
1.00
53.19
8
ATOM
3808
N
ARG
B
220
60.247
15.065
42.373
1.00
38.26
7
ATOM
3809
CA
ARG
B
220
60.572
15.785
41.151
1.00
38.87
6
ATOM
3810
C
ARG
B
220
61.803
16.664
41.272
1.00
38.94
6
ATOM
3811
O
ARG
B
220
62.119
17.358
40.305
1.00
39.85
8
ATOM
3812
CB
ARG
B
220
59.396
16.676
40.670
1.00
39.03
6
ATOM
3813
CG
ARG
B
220
58.187
15.871
40.179
1.00
39.62
6
ATOM
3814
CD
ARG
B
220
58.562
15.016
38.972
1.00
39.07
6
ATOM
3815
NE
ARG
B
220
57.490
14.110
38.632
1.00
39.25
7
ATOM
3816
CZ
ARG
B
220
57.184
12.886
39.019
1.00
39.75
6
ATOM
3817
NH1
ARG
B
220
57.946
12.211
39.893
1.00
39.07
7
ATOM
3818
NH2
ARG
B
220
56.073
12.331
38.529
1.00
38.25
7
ATOM
3819
N
ASP
B
221
62.564
16.577
42.361
1.00
38.00
7
ATOM
3820
CA
ASP
B
221
63.792
17.372
42.433
1.00
38.21
6
ATOM
3821
C
ASP
B
221
64.911
16.557
41.791
1.00
36.88
6
ATOM
3822
O
ASP
B
221
65.691
15.899
42.474
1.00
36.84
8
ATOM
3823
CB
ASP
B
221
64.146
17.760
43.866
1.00
40.08
6
ATOM
3824
CG
ASP
B
221
65.276
18.775
43.867
1.00
40.98
6
ATOM
3825
OD1
ASP
B
221
66.189
18.865
43.017
1.00
40.33
8
ATOM
3826
OD2
ASP
B
221
65.237
19.583
44.824
1.00
45.27
8
ATOM
3827
N
LEU
B
222
64.940
16.559
40.472
1.00
36.51
7
ATOM
3828
CA
LEU
B
222
65.839
15.703
39.697
1.00
35.37
6
ATOM
3829
C
LEU
B
222
67.312
15.852
40.004
1.00
34.02
6
ATOM
3830
O
LEU
B
222
68.053
14.855
40.041
1.00
31.24
8
ATOM
3831
CB
LEU
B
222
65.575
15.983
38.203
1.00
35.83
6
ATOM
3832
CG
LEU
B
222
64.144
15.686
37.720
1.00
38.11
6
ATOM
3833
CD1
LEU
B
222
64.187
15.314
36.239
1.00
38.86
6
ATOM
3834
CD2
LEU
B
222
63.430
14.608
38.526
1.00
36.91
6
ATOM
3835
N
ASP
B
223
67.763
17.101
40.153
1.00
33.49
7
ATOM
3836
CA
ASP
B
223
69.154
17.349
40.442
1.00
33.63
6
ATOM
3837
C
ASP
B
223
69.524
16.656
41.751
1.00
31.73
6
ATOM
3838
O
ASP
B
223
70.620
16.132
41.870
1.00
31.34
8
ATOM
3839
CB
ASP
B
223
69.494
18.827
40.653
1.00
34.33
6
ATOM
3840
N
GLU
B
224
68.635
16.790
42.733
1.00
31.71
7
ATOM
3841
CA
GLU
B
224
68.909
16.161
44.035
1.00
31.51
6
ATOM
3842
C
GLU
B
224
68.836
14.656
43.974
1.00
29.02
6
ATOM
3843
O
GLU
B
224
69.667
13.945
44.502
1.00
28.00
8
ATOM
3844
CB
GLU
B
224
67.907
16.696
45.089
1.00
34.56
6
ATOM
3845
CG
GLU
B
224
68.123
16.063
46.454
1.00
37.72
6
ATOM
3846
CD
GLU
B
224
69.389
16.542
47.140
1.00
42.79
6
ATOM
3847
OE1
GLU
B
224
70.120
17.403
46.574
1.00
43.28
8
ATOM
3848
OE2
GLU
B
224
69.660
16.051
48.273
1.00
43.45
8
ATOM
3849
N
ILE
B
225
67.863
14.079
43.231
1.00
27.24
7
ATOM
3850
CA
ILE
B
225
67.835
12.642
43.056
1.00
26.19
6
ATOM
3851
C
ILE
B
225
69.109
12.145
42.417
1.00
25.15
6
ATOM
3852
O
ILE
B
225
69.651
11.121
42.828
1.00
26.25
8
ATOM
3853
CB
ILE
B
225
66.632
12.214
42.152
1.00
28.29
6
ATOM
3854
CG1
ILE
B
225
65.340
12.494
42.878
1.00
29.03
6
ATOM
3855
CG2
ILE
B
225
66.803
10.740
41.776
1.00
25.65
6
ATOM
3856
CD1
ILE
B
225
64.109
12.596
42.001
1.00
31.93
6
ATOM
3857
N
ILE
B
226
69.578
12.801
41.373
1.00
26.43
7
ATOM
3858
CA
ILE
B
226
70.786
12.406
40.641
1.00
25.84
6
ATOM
3859
C
ILE
B
226
72.040
12.551
41.500
1.00
27.10
6
ATOM
3860
O
ILE
B
226
72.923
11.716
41.451
1.00
24.94
8
ATOM
3861
CB
ILE
B
226
70.923
13.170
39.304
1.00
27.17
6
ATOM
3862
CG1
ILE
B
226
69.753
12.662
38.429
1.00
27.18
6
ATOM
3863
CG2
ILE
B
226
72.280
12.981
38.632
1.00
27.48
6
ATOM
3864
CD1
ILE
B
226
69.562
13.504
37.159
1.00
27.31
6
ATOM
3865
N
THR
B
227
72.095
13.642
42.283
1.00
25.81
7
ATOM
3866
CA
THR
B
227
73.300
13.811
43.112
1.00
25.80
6
ATOM
3867
C
THR
B
227
73.368
12.725
44.157
1.00
24.81
6
ATOM
3868
O
THR
B
227
74.457
12.188
44.484
1.00
23.72
8
ATOM
3869
CB
THR
B
227
73.230
15.226
43.714
1.00
25.87
6
ATOM
3870
OG1
THR
B
227
73.461
16.226
42.719
1.00
27.10
8
ATOM
3871
CG2
THR
B
227
74.317
15.419
44.776
1.00
30.13
6
ATOM
3872
N
ILE
B
228
72.202
12.447
44.753
1.00
21.50
7
ATOM
3873
CA
ILE
B
228
72.230
11.384
45.756
1.00
21.63
6
ATOM
3874
C
ILE
B
228
72.645
10.046
45.160
1.00
23.87
6
ATOM
3875
O
ILE
B
228
73.410
9.242
45.679
1.00
22.19
8
ATOM
3876
CB
ILE
B
228
70.892
11.236
46.481
1.00
21.84
6
ATOM
3877
CG1
ILE
B
228
70.746
12.501
47.397
1.00
24.08
6
ATOM
3878
CG2
ILE
B
228
70.762
9.964
47.278
1.00
22.76
6
ATOM
3879
CD1
ILE
B
228
69.295
12.583
47.901
1.00
26.19
6
ATOM
3880
N
ALA
B
229
72.035
9.747
43.962
1.00
23.45
7
ATOM
3881
CA
ALA
B
229
72.386
8.510
43.308
1.00
24.32
6
ATOM
3882
C
ALA
B
229
73.835
8.419
42.943
1.00
21.10
6
ATOM
3883
O
ALA
B
229
74.403
7.325
43.107
1.00
23.01
8
ATOM
3884
CB
ALA
B
229
71.481
8.404
42.050
1.00
22.78
6
ATOM
3885
N
GLY
B
230
74.533
9.496
42.596
1.00
22.98
7
ATOM
3886
CA
GLY
B
230
75.940
9.540
42.325
1.00
25.69
6
ATOM
3887
C
GLY
B
230
76.731
9.266
43.636
1.00
25.98
6
ATOM
3888
O
GLY
B
230
77.669
8.455
43.656
1.00
23.67
8
ATOM
3889
N
GLN
B
231
76.233
9.789
44.748
1.00
25.92
7
ATOM
3890
CA
GLN
B
231
76.907
9.478
46.035
1.00
27.99
6
ATOM
3891
C
GLN
B
231
76.700
8.048
46.427
1.00
26.47
6
ATOM
3892
O
GLN
B
231
77.666
7.384
46.850
1.00
25.84
8
ATOM
3893
CB
GLN
B
231
76.407
10.471
47.120
1.00
28.03
6
ATOM
3894
CG
GLN
B
231
76.834
10.043
48.531
1.00
32.38
6
ATOM
3895
CD
GLN
B
231
78.316
10.219
48.756
1.00
32.95
6
ATOM
3896
OE1
GLN
B
231
79.045
10.701
47.905
1.00
33.95
8
ATOM
3897
NE2
GLN
B
231
78.780
9.786
49.922
1.00
36.62
7
ATOM
3898
N
GLU
B
232
75.516
7.434
46.178
1.00
26.86
7
ATOM
3899
CA
GLU
B
232
75.285
6.024
46.475
1.00
25.40
6
ATOM
3900
C
GLU
B
232
76.193
5.139
45.605
1.00
27.57
6
ATOM
3901
O
GLU
B
232
76.802
4.178
46.110
1.00
28.11
8
ATOM
3902
CB
GLU
B
232
73.827
5.559
46.287
1.00
27.07
6
ATOM
3903
CG
GLU
B
232
72.820
6.282
47.171
1.00
30.63
6
ATOM
3904
CD
GLU
B
232
71.375
5.946
46.930
1.00
34.51
6
ATOM
3905
OE1
GLU
B
232
71.033
5.379
45.860
1.00
37.23
8
ATOM
3906
OE2
GLU
B
232
70.510
6.232
47.794
1.00
35.98
8
ATOM
3907
N
LEU
B
233
76.346
5.489
44.313
1.00
26.60
7
ATOM
3908
CA
LEU
B
233
77.272
4.700
43.490
1.00
26.30
6
ATOM
3909
C
LEU
B
233
78.710
4.784
44.024
1.00
28.83
6
ATOM
3910
O
LEU
B
233
79.402
3.781
44.040
1.00
28.19
8
ATOM
3911
CB
LEU
B
233
77.171
5.171
42.025
1.00
27.72
6
ATOM
3912
CG
LEU
B
233
75.816
4.809
41.372
1.00
26.70
6
ATOM
3913
CD1
LEU
B
233
75.511
5.576
40.104
1.00
27.51
6
ATOM
3914
CD2
LEU
B
233
75.819
3.312
41.048
1.00
28.08
6
ATOM
3915
N
ASN
B
234
79.166
6.006
44.330
1.00
31.21
7
ATOM
3916
CA
ASN
B
234
80.540
6.248
44.790
1.00
32.86
6
ATOM
3917
C
ASN
B
234
80.761
5.404
46.020
1.00
32.80
6
ATOM
3918
O
ASN
B
234
81.764
4.675
46.099
1.00
34.18
8
ATOM
3919
CB
ASN
B
234
80.775
7.750
45.048
1.00
33.46
6
ATOM
3920
CG
ASN
B
234
82.187
8.099
45.503
1.00
38.46
6
ATOM
3921
OD1
ASN
B
234
82.545
7.889
46.687
1.00
39.27
8
ATOM
3922
ND2
ASN
B
234
83.042
8.646
44.636
1.00
38.37
7
ATOM
3923
N
GLU
B
235
79.781
5.385
46.942
1.00
32.30
7
ATOM
3924
CA
GLU
B
235
79.995
4.556
48.156
1.00
34.69
6
ATOM
3925
C
GLU
B
235
80.036
3.082
47.880
1.00
35.00
6
ATOM
3926
O
GLU
B
235
80.783
2.325
48.548
1.00
34.91
8
ATOM
3927
CB
GLU
B
235
78.927
4.941
49.210
1.00
35.01
6
ATOM
3928
N
LYS
B
236
79.431
2.541
46.819
1.00
32.85
7
ATOM
3929
CA
LYS
B
236
79.476
1.161
46.438
1.00
32.12
6
ATOM
3930
C
LYS
B
236
80.733
0.795
45.662
1.00
31.23
6
ATOM
3931
O
LYS
B
236
81.027
−0.387
45.442
1.00
32.24
8
ATOM
3932
CB
LYS
B
236
78.257
0.838
45.530
1.00
31.56
6
ATOM
3933
CG
LYS
B
236
76.968
0.739
46.321
1.00
33.04
6
ATOM
3934
CD
LYS
B
236
75.825
0.425
45.347
1.00
34.58
6
ATOM
3935
CE
LYS
B
236
74.486
0.657
46.017
1.00
38.11
6
ATOM
3936
NZ
LYS
B
236
74.152
−0.406
47.008
1.00
41.00
7
ATOM
3937
N
GLY
B
237
81.463
1.790
45.196
1.00
31.15
7
ATOM
3938
CA
GLY
B
237
82.701
1.595
44.467
1.00
32.69
6
ATOM
3939
C
GLY
B
237
82.728
2.025
43.030
1.00
33.87
6
ATOM
3940
O
GLY
B
237
83.730
1.798
42.345
1.00
36.00
8
ATOM
3941
N
PHE
B
238
81.635
2.625
42.522
1.00
30.77
7
ATOM
3942
CA
PHE
B
238
81.579
3.079
41.154
1.00
31.26
6
ATOM
3943
C
PHE
B
238
82.111
4.488
41.041
1.00
32.04
6
ATOM
3944
O
PHE
B
238
82.216
5.186
42.067
1.00
32.73
8
ATOM
3945
CB
PHE
B
238
80.125
3.016
40.628
1.00
31.33
6
ATOM
3946
CG
PHE
B
238
79.481
1.668
40.628
1.00
29.12
6
ATOM
3947
CD1
PHE
B
238
78.935
1.079
41.736
1.00
29.70
6
ATOM
3948
CD2
PHE
B
238
79.401
0.975
39.390
1.00
29.67
6
ATOM
3949
CE1
PHE
B
238
78.325
−0.181
41.661
1.00
30.02
6
ATOM
3950
CE2
PHE
B
238
78.805
−0.265
39.328
1.09
28.39
6
ATOM
3951
CZ
PHE
B
238
78.268
−0.858
40.457
1.00
29.71
6
ATOM
3952
N
ARG
B
239
82.539
4.918
39.876
1.00
32.94
7
ATOM
3953
CA
ARG
B
239
83.050
6.269
39.716
1.00
35.99
6
ATOM
3954
C
ARG
B
239
82.426
6.906
38.487
1.00
38.53
6
ATOM
3955
O
ARG
B
239
81.735
6.244
37.694
1.00
38.62
8
ATOM
3956
CB
ARG
B
239
84.581
6.280
39.597
1.00
35.70
6
ATOM
3957
CG
ARG
B
239
85.340
5.894
40.856
1.00
36.08
6
ATOM
3958
CD
ARG
B
239
85.108
6.926
41.956
1.00
35.58
6
ATOM
3959
NE
ARG
B
239
85.710
6.612
43.215
1.00
36.21
7
ATOM
3960
CZ
ARG
B
239
85.280
5.815
44.190
1.00
37.41
6
ATOM
3961
NH1
ARG
B
239
84.113
5.159
44.129
1.00
35.39
7
ATOM
3962
NH2
ARG
B
239
86.015
5.707
45.288
1.00
35.70
7
ATOM
3963
N
ALA
B
240
82.667
8.199
38.339
1.00
38.40
7
ATOM
3964
CA
ALA
B
240
82.310
8.977
37.152
1.00
39.45
6
ATOM
3965
C
ALA
B
240
80.954
8.630
36.553
1.00
39.96
6
ATOM
3966
O
ALA
B
240
80.846
8.388
35.348
1.00
41.59
8
ATOM
3967
CB
ALA
B
240
83.408
8.761
36.103
1.00
39.64
6
ATOM
3968
N
ASP
B
241
79.899
8.687
37.369
1.00
39.86
7
ATOM
3969
CA
ASP
B
241
78.567
8.382
36.881
1.00
37.91
6
ATOM
3970
C
ASP
B
241
78.087
9.495
35.947
1.00
39.44
6
ATOM
3971
O
ASP
B
241
78.464
10.658
36.063
1.00
38.78
8
ATOM
3972
CB
ASP
B
241
77.554
8.232
38.028
1.00
39.68
6
ATOM
3973
CG
ASP
B
241
77.464
9.573
38.758
1.00
42.34
6
ATOM
3974
OD1
ASP
B
241
76.577
10.419
38.447
1.00
44.14
8
ATOM
3975
OD2
ASP
B
241
78.353
9.828
39.610
1.00
41.04
8
ATOM
3976
N
ASP
B
242
77.220
9.122
35.028
1.00
36.17
7
ATOM
3977
CA
ASP
B
242
76.543
10.050
34.122
1.00
36.78
6
ATOM
3978
C
ASP
B
242
75.102
9.548
34.108
1.00
32.97
6
ATOM
3979
O
ASP
B
242
74.890
8.412
33.654
1.00
32.78
8
ATOM
3980
CB
ASP
B
242
77.160
10.107
32.755
1.00
41.35
6
ATOM
3981
CG
ASP
B
242
76.317
10.792
31.704
1.00
46.81
6
ATOM
3982
OD1
ASP
B
242
76.414
10.318
30.543
1.00
50.98
8
ATOM
3983
OD2
ASP
B
242
75.539
11.741
31.944
1.00
49.34
8
ATOM
3984
N
ILE
B
243
74.204
10.301
34.710
1.00
29.36
7
ATOM
3985
CA
ILE
B
243
72.817
9.893
34.861
1.00
27.87
6
ATOM
3986
C
ILE
B
243
71.890
10.907
34.213
1.00
28.93
6
ATOM
3987
O
ILE
B
243
71.986
12.098
34.489
1.00
28.18
8
ATOM
3988
CB
ILE
B
243
72.407
9.746
36.339
1.00
28.09
6
ATOM
3989
CG1
ILE
B
243
73.240
8.680
37.065
1.00
28.98
6
ATOM
3990
CG2
ILE
B
243
70.934
9.373
36.477
1.00
26.56
6
ATOM
3991
CD1
ILE
B
243
73.044
8.655
38.575
1.00
28.71
6
ATOM
3992
N
GLN
B
244
70.912
10.442
33.437
1.00
27.35
7
ATOM
3993
CA
GLN
B
244
69.944
11.390
32.837
1.00
29.56
6
ATOM
3994
C
GLN
B
244
68.550
10.906
33.126
1.00
28.63
6
ATOM
3995
O
GLN
B
244
68.328
9.670
33.170
1.00
28.44
8
ATOM
3996
CB
GLN
B
244
70.154
11.546
31.342
1.00
32.37
6
ATOM
3997
CG
GLN
B
244
71.494
11.871
30.754
1.00
33.10
6
ATOM
3998
N
ILE
B
245
67.580
11.792
33.287
1.00
28.47
7
ATOM
3999
CA
ILE
B
245
66.194
11.454
33.560
1.00
27.98
6
ATOM
4000
C
ILE
B
245
65.367
12.295
32.544
1.00
29.53
6
ATOM
4001
O
ILE
B
245
65.647
13.473
32.427
1.00
28.72
8
ATOM
4002
CB
ILE
B
245
65.647
11.723
34.955
1.00
30.08
6
ATOM
4003
CG1
ILE
B
245
66.275
10.837
36.048
1.00
31.65
6
ATOM
4004
CG2
ILE
B
245
64.136
11.475
34.988
1.00
30.80
6
ATOM
4005
CD1
ILE
B
245
65.994
11.415
37.433
1.00
33.41
6
ATOM
4006
N
ARG
B
246
64.608
11.578
31.703
1.00
28.63
7
ATOM
4007
CA
ARG
B
246
63.903
12.319
30.635
1.00
29.40
6
ATOM
4008
C
ARG
B
246
62.475
11.841
30.597
1.00
29.33
6
ATOM
4009
O
ARG
B
246
62.198
10.775
31.136
1.00
29.29
8
ATOM
4010
CB
ARG
B
246
64.481
12.084
29.252
1.00
33.51
6
ATOM
4011
CG
ARG
B
246
65.896
12.479
29.026
1.00
37.29
6
ATOM
4012
CD
ARG
B
246
66.517
12.212
27.672
1.00
42.16
6
ATOM
4013
NE
ARG
B
246
67.527
13.251
27.472
1.00
47.11
7
ATOM
4014
CZ
ARG
B
246
68.770
13.142
27.056
1.00
50.44
6
ATOM
4015
NH1
ARG
B
246
69.318
11.970
26.737
1.00
53.10
7
ATOM
4016
NH2
ARG
B
246
69.502
14.252
26.974
1.00
51.57
7
ATOM
4017
N
ASP
B
247
61.544
12.634
30.039
1.00
28.70
7
ATOM
4018
CA
ASP
B
247
60.185
12.189
29.792
1.00
29.87
6
ATOM
4019
C
ASP
B
247
60.289
11.146
28.656
1.00
25.96
6
ATOM
4020
O
ASP
B
247
60.989
11.431
27.671
1.00
27.47
8
ATOM
4021
CB
ASP
B
247
59.303
13.349
29.389
1.00
31.15
6
ATOM
4022
CG
ASP
B
247
57.894
13.014
28.997
1.00
33.47
6
ATOM
4023
OD1
ASP
B
247
57.667
12.084
28.184
1.00
32.45
8
ATOM
4024
OD2
ASP
B
247
56.982
13.703
29.524
1.00
33.36
8
ATOM
4025
N
ALA
B
248
59.759
9.981
28.873
1.00
27.20
7
ATOM
4026
CA
ALA
B
248
59.987
8.893
27.906
1.00
28.58
6
ATOM
4027
C
ALA
B
248
59.141
9.055
26.643
1.00
29.88
6
ATOM
4028
O
ALA
B
248
59.444
8.315
25.702
1.00
29.99
8
ATOM
4029
CB
ALA
B
248
59.652
7.572
28.566
1.00
28.03
6
ATOM
4030
N
ASP
B
249
58.121
9.877
26.724
1.00
28.08
7
ATOM
4031
CA
ASP
B
249
57.293
10.116
25.513
1.00
30.80
6
ATOM
4032
C
ASP
B
249
57.764
11.262
24.667
1.00
29.85
6
ATOM
4033
O
ASP
B
249
57.690
11.217
23.402
1.00
30.23
8
ATOM
4034
CB
ASP
B
249
55.853
10.392
25.955
1.00
32.78
6
ATOM
4035
CG
ASP
B
249
55.226
9.204
26.623
1.00
37.46
6
ATOM
4036
OD1
ASP
B
249
55.538
8.084
26.164
1.00
39.14
8
ATOM
4037
OD2
ASP
B
249
54.448
9.329
27.595
1.00
39.72
8
ATOM
4038
N
THR
B
250
58.264
12.361
25.283
1.00
26.32
7
ATOM
4039
CA
THR
B
250
58.710
13.526
24.523
1.00
27.61
6
ATOM
4040
C
THR
B
250
60.191
13.683
24.413
1.00
26.93
6
ATOM
4041
O
THR
B
250
60.785
14.328
23.570
1.00
28.19
8
ATOM
4042
CB
THR
B
250
58.162
14.831
25.186
1.00
30.35
6
ATOM
4043
OG1
THR
B
250
58.797
14.978
26.457
1.00
31.06
8
ATOM
4044
CG2
THR
B
250
56.677
14.760
25.380
1.00
32.40
6
ATOM
4045
N
LEU
B
251
60.891
12.958
25.324
1.00
27.41
7
ATOM
4046
CA
LEU
B
251
62.336
12.857
25.461
1.00
30.17
6
ATOM
4047
C
LEU
B
251
62.928
14.204
25.968
1.00
31.32
6
ATOM
4048
O
LEU
B
251
64.110
14.434
25.775
1.00
33.84
8
ATOM
4049
CB
LEU
B
251
63.096
12.483
24.205
1.00
30.53
6
ATOM
4050
CG
LEU
B
251
62.568
11.151
23.560
1.00
30.23
6
ATOM
4051
CD1
LEU
B
251
63.382
10.891
22.307
1.00
31.95
6
ATOM
4052
CD2
LEU
B
251
62.575
10.004
24.541
1.00
30.44
6
ATOM
4053
N
LEU
B
252
62.054
15.017
26.483
1.00
33.09
7
ATOM
4054
CA
LEU
B
252
62.441
16.323
27.015
1.00
34.68
6
ATOM
4055
C
LEU
B
252
62.530
16.162
28.519
1.00
35.10
6
ATOM
4056
O
LEU
B
252
62.436
15.037
29.003
1.00
30.04
8
ATOM
4057
CB
LEU
B
252
61.439
17.401
26.633
1.00
35.48
6
ATOM
4058
CG
LEU
B
252
61.476
17.664
25.106
1.00
38.16
6
ATOM
4059
CD1
LEU
B
252
60.219
18.416
24.715
1.00
38.56
6
ATOM
4060
CD2
LEU
B
252
62.782
18.361
24.789
1.00
38.57
6
ATOM
4061
N
GLU
B
253
62.625
17.316
29.217
1.00
36.82
7
ATOM
4062
CA
GLU
B
253
62.731
17.220
30.668
1.00
39.59
6
ATOM
4063
C
GLU
B
253
61.417
16.777
31.259
1.00
39.50
6
ATOM
4064
O
GLU
B
253
60.403
17.042
30.591
1.00
40.91
8
ATOM
4065
CB
GLU
B
253
63.103
18.586
31.274
1.00
42.93
6
ATOM
4066
CG
GLU
B
253
64.342
19.202
30.643
1.00
48.27
6
ATOM
4067
CD
GLU
B
253
65.560
18.356
30.999
1.00
51.88
6
ATOM
4068
OE1
GLU
B
253
65.758
18.143
32.226
1.00
54.42
8
ATOM
4069
OE2
GLU
B
253
66.259
17.915
30.063
1.00
53.71
8
ATOM
4070
N
VAL
B
254
61.405
16.130
32.403
1.00
39.00
7
ATOM
4071
CA
VAL
B
254
60.167
15.751
33.062
1.00
40.35
6
ATOM
4072
C
VAL
B
254
59.384
16.991
33.488
1.00
43.05
6
ATOM
4073
O
VAL
B
254
59.955
17.997
33.903
1.00
42.79
8
ATOM
4074
CB
VAL
B
254
60.425
14.856
34.285
1.00
39.32
6
ATOM
4075
CG1
VAL
B
254
59.162
14.614
35.088
1.00
37.70
6
ATOM
4076
CG2
VAL
B
254
61.054
13.553
33.783
1.00
38.29
6
ATOM
4077
N
SER
B
255
58.070
16.937
33.293
1.00
46.50
7
ATOM
4078
CA
SER
B
255
57.178
18.041
33.641
1.00
47.57
6
ATOM
4079
C
SER
B
255
56.027
17.520
34.498
1.00
48.72
6
ATOM
4080
O
SER
B
255
56.063
16.436
35.062
1.00
49.33
8
ATOM
4081
CB
SER
B
255
56.663
18.739
32.379
1.00
47.97
6
ATOM
4082
OG
SER
B
255
55.566
18.022
31.814
1.00
50.04
8
ATOM
4083
N
GLU
B
256
54.990
18.358
34.593
1.00
48.58
7
ATOM
4084
CA
GLU
B
256
53.787
18.010
35.346
1.00
49.19
6
ATOM
4085
C
GLU
B
256
52.838
17.201
34.488
1.00
49.15
6
ATOM
4086
O
GLU
B
256
51.953
16.493
34.969
1.00
50.39
8
ATOM
4087
CB
GLU
B
256
53.154
19.321
35.844
1.00
49.68
6
ATOM
4088
N
THR
B
257
53.078
17.241
33.177
1.00
48.71
7
ATOM
4089
CA
THR
B
257
52.306
16.471
32.211
1.00
49.54
6
ATOM
4090
C
THR
B
257
52.962
15.121
31.914
1.00
48.26
6
ATOM
4091
O
THR
B
257
52.333
14.259
31.285
1.00
48.37
8
ATOM
4092
CB
THR
B
257
52.146
17.265
30.913
1.00
50.65
6
ATOM
4093
OG1
THR
B
257
53.430
17.717
30.454
1.00
52.73
8
ATOM
4094
CG2
THR
B
257
51.277
18.496
31.154
1.00
52.44
6
ATOM
4095
N
SER
B
258
54.201
14.933
32.368
1.00
44.00
7
ATOM
4096
CA
SER
B
258
54.923
13.690
32.124
1.00
43.02
6
ATOM
4097
C
SER
B
258
54.197
12.470
32.665
1.00
41.05
6
ATOM
4098
O
SER
B
258
53.785
12.435
33.808
1.00
40.25
8
ATOM
4099
CB
SER
B
258
56.315
13.710
32.765
1.00
39.95
6
ATOM
4100
OG
SER
B
258
57.171
14.561
32.020
1.00
37.63
8
ATOM
4101
N
LYS
B
259
54.041
11.453
31.819
1.00
40.55
7
ATOM
4102
CA
LYS
B
259
53.347
10.253
32.275
1.00
40.93
6
ATOM
4103
C
LYS
B
259
54.339
9.094
32.390
1.00
38.96
6
ATOM
4104
O
LYS
B
259
54.036
8.130
33.071
1.00
39.56
8
ATOM
4105
CB
LYS
B
259
52.193
9.870
31.340
1.00
44.20
6
ATOM
4106
CG
LYS
B
259
51.223
11.038
31.184
1.00
47.43
6
ATOM
4107
CD
LYS
B
259
49.868
10.656
30.608
1.00
50.95
6
ATOM
4108
CE
LYS
B
259
48.814
11.646
31.143
1.00
52.15
6
ATOM
4109
NZ
LYS
B
259
47.678
11.728
30.177
1.00
54.34
7
ATOM
4110
N
ARG
B
260
55.446
9.187
31.695
1.00
38.03
7
ATOM
4111
CA
ARG
B
260
56.469
8.146
31.706
1.00
36.81
6
ATOM
4112
C
ARG
B
260
57.852
8.765
31.794
1.00
33.36
6
ATOM
4113
O
ARG
B
260
58.150
9.717
31.075
1.00
30.91
8
ATOM
4114
CB
ARG
B
260
56.438
7.267
30.445
1.00
38.22
6
ATOM
4115
CG
ARG
B
260
55.182
6.504
30.103
1.00
42.83
6
ATOM
4116
CD
ARG
B
260
55.389
5.584
28.896
1.00
43.79
6
ATOM
4117
NE
ARG
B
260
54.174
4.856
28.536
1.00
46.34
7
ATOM
4118
N
ALA
B
261
58.808
8.142
32.519
1.00
31.91
7
ATOM
4119
CA
ALA
B
261
60.182
8.623
32.486
1.00
28.39
6
ATOM
4120
C
ALA
B
261
61.176
7.524
32.106
1.00
25.89
6
ATOM
4121
O
ALA
B
261
60.882
6.354
32.381
1.00
29.01
8
ATOM
4122
CB
ALA
B
261
68.695
9.169
33.836
1.00
29.25
6
ATOM
4123
N
VAL
B
262
62.238
7.874
31.454
1.00
27.17
7
ATOM
4124
CA
VAL
B
262
63.325
6.947
31.122
1.00
29.12
6
ATOM
4125
C
VAL
B
262
64.544
7.432
31.944
1.00
28.50
6
ATOM
4126
O
VAL
B
262
64.860
8.605
31.932
1.00
27.83
8
ATOM
4127
CB
VAL
B
262
63.659
6.838
29.647
1.00
30.51
6
ATOM
4128
CG1
VAL
B
262
63.902
8.231
29.043
1.00
30.91
6
ATOM
4129
CG2
VAL
B
262
64.881
5.958
29.356
1.00
30.63
6
ATOM
4130
N
ILE
B
263
65.221
6.505
32.611
1.00
29.18
7
ATOM
4131
CA
ILE
B
263
66.406
6.792
33.454
1.00
27.39
6
ATOM
4132
C
ILE
B
263
67.590
6.119
32.790
1.00
25.94
6
ATOM
4133
O
ILE
B
263
67.437
4.906
32.507
1.00
25.04
8
ATOM
4134
CB
ILE
B
263
66.243
6.278
34.881
1.00
29.45
6
ATOM
4135
CG1
ILE
B
263
64.898
6.687
35.497
1.00
29.18
6
ATOM
4136
CG2
ILE
B
263
67.369
6.819
35.758
1.00
29.13
6
ATOM
4137
CD1
ILE
B
263
64.395
5.672
36.508
1.00
32.09
6
ATOM
4138
N
LEU
B
264
68.626
6.784
32.377
1.00
25.66
7
ATOM
4139
CA
LEU
B
264
69.795
6.289
31.701
1.00
27.04
6
ATOM
4140
C
LEU
B
264
70.978
6.430
32.666
1.00
29.07
6
ATOM
4141
O
LEU
B
264
71.152
7.574
33.143
1.00
29.50
8
ATOM
4142
CB
LEU
B
264
70.153
7.070
30.438
1.00
29.75
6
ATOM
4143
CG
LEU
B
264
68.950
7.229
29.452
1.00
32.20
6
ATOM
4144
CD1
LEU
B
264
69.399
8.095
28.298
1.00
33.01
6
ATOM
4145
CD2
LEU
B
264
68.453
5.842
29.091
1.00
31.89
6
ATOM
4146
N
VAL
B
265
71.753
5.394
32.886
1.00
29.03
7
ATOM
4147
CA
VAL
B
265
72.864
5.494
33.821
1.00
32.13
6
ATOM
4148
C
VAL
B
265
74.099
4.822
33.213
1.00
34.01
6
ATOM
4149
O
VAL
B
265
74.044
3.750
32.557
1.00
34.46
8
ATOM
4150
CB
VAL
B
265
72.642
4.856
35.202
1.00
32.74
6
ATOM
4151
CG1
VAL
B
265
71.525
5.474
36.025
1.00
33.45
6
ATOM
4152
CG2
VAL
B
265
72.331
3.361
35.046
1.00
33.30
6
ATOM
4153
N
ALA
B
266
75.219
5.485
33.397
1.00
33.41
7
ATOM
4154
CA
ALA
B
266
76.501
4.926
33.000
1.00
32.14
6
ATOM
4155
C
ALA
B
266
77.411
5.092
34.221
1.00
32.17
6
ATOM
4156
O
ALA
B
266
77.390
6.213
34.746
1.00
32.13
8
ATOM
4157
CB
ALA
B
266
77.139
5.570
31.794
1.00
32.99
6
ATOM
4158
N
ALA
B
267
78.175
4.058
34.569
1.00
31.42
7
ATOM
4159
CA
ALA
B
267
79.107
4.338
35.679
1.00
32.75
6
ATOM
4160
C
ALA
B
267
80.356
3.503
35.491
1.00
35.34
6
ATOM
4161
O
ALA
B
267
80.213
2.423
34.884
1.00
36.90
8
ATOM
4162
CB
ALA
B
267
78.446
4.006
36.993
1.00
31.22
6
ATOM
4163
N
TRP
B
268
81.511
3.868
36.036
1.00
36.69
7
ATOM
4164
CA
TRP
B
268
82.665
2.974
35.881
1.00
38.65
6
ATOM
4165
C
TRP
B
268
82.910
2.113
37.105
1.00
40.28
6
ATOM
4166
O
TRP
B
268
82.777
2.579
38.235
1.00
38.57
5
ATOM
4167
CB
TRP
B
268
83.927
3.805
35.609
1.00
40.65
6
ATOM
4168
CG
TRP
B
268
83.860
4.563
34.319
1.00
43.80
6
ATOM
4169
CD1
TRP
B
268
83.114
5.662
34.040
1.00
44.47
6
ATOM
4170
CD2
TRP
B
268
84.577
4.256
33.115
1.00
45.14
6
ATOM
4171
NE1
TRP
B
268
83.311
6.063
32.729
1.00
45.41
7
ATOM
4172
CE2
TRP
B
268
84.199
5.211
32.144
1.00
45.95
6
ATOM
4173
CE3
TRP
B
268
85.470
3.244
32.757
1.00
45.65
6
ATOM
4174
CZ2
TRP
B
268
84.703
5.199
30.836
1.00
46.17
6
ATOM
4175
CZ3
TRP
B
268
85.984
3.242
31.463
1.00
46.00
6
ATOM
4176
CH2
TRP
B
268
85.596
4.206
30.522
1.00
45.63
6
ATOM
4177
N
LEU
B
269
83.300
0.869
36.821
1.00
39.18
7
ATOM
4178
CA
LEU
B
269
83.691
−0.026
37.916
1.00
43.86
6
ATOM
4179
C
LEU
B
269
85.093
−0.471
37.522
1.00
46.33
6
ATOM
4180
O
LEU
B
269
85.247
−0.946
36.400
1.00
47.07
5
ATOM
4181
CB
LEU
B
269
82.635
−1.086
38.058
1.00
43.77
6
ATOM
4182
CG
LEU
B
269
82.651
−2.072
39.212
1.00
44.62
6
ATOM
4183
CD1
LEU
B
269
82.571
−1.312
40.537
1.00
44.46
6
ATOM
4184
CD2
LEU
B
269
81.518
−3.080
39.046
1.00
42.39
6
ATOM
4185
N
GLY
B
270
86.102
−0.049
38.293
1.00
48.41
7
ATOM
4186
CA
GLY
B
270
87.475
−0.340
37.862
1.00
51.49
6
ATOM
4187
C
GLY
B
270
87.681
0.391
36.532
1.00
54.10
6
ATOM
4188
O
GLY
B
270
87.397
1.588
36.464
1.00
54.18
8
ATOM
4189
N
ASP
B
271
88.108
−0.331
35.503
1.00
56.24
7
ATOM
4190
CA
ASP
B
271
88.288
0.320
34.199
1.00
56.89
6
ATOM
4191
C
ASP
B
271
87.142
−0.096
33.280
1.00
54.99
6
ATOM
4192
O
ASP
B
271
87.162
0.231
32.097
1.00
55.57
8
ATOM
4193
CB
ASP
B
271
89.670
0.026
33.618
1.00
60.69
6
ATOM
4194
CG
ASP
B
271
90.400
−1.175
34.164
1.00
64.16
6
ATOM
4195
OD1
ASP
B
271
89.789
−2.194
34.571
1.00
65.71
8
ATOM
4196
OD2
ASP
B
271
91.657
−1.179
34.206
1.00
66.40
8
ATOM
4197
N
ALA
B
272
86.129
−0.780
33.807
1.00
52.97
7
ATOM
4198
CA
ALA
B
272
84.966
−1.186
33.031
1.00
50.67
6
ATOM
4199
C
ALA
B
272
83.843
−0.149
33.103
1.00
50.64
6
ATOM
4200
O
ALA
B
272
83.482
0.315
34.203
1.00
49.32
8
ATOM
4201
CB
ALA
B
272
84.389
−2.501
33.520
1.00
50.42
6
ATOM
4202
N
ARG
B
273
83.255
0.166
31.958
1.00
47.60
7
ATOM
4203
CA
ARG
B
273
82.163
1.131
31.939
1.00
46.77
6
ATOM
4204
C
ARG
B
273
80.841
0.398
31.804
1.00
45.84
6
ATOM
4205
O
ARG
B
273
80.636
−0.256
30.770
1.00
46.17
8
ATOM
4206
CB
ARG
B
273
82.312
2.144
30.804
1.00
48.87
6
ATOM
4207
CG
ARG
B
273
81.234
3.214
30.839
1.00
49.86
6
ATOM
4208
CD
ARG
B
273
81.436
4.283
29.773
1.00
52.81
6
ATOM
4209
NE
ARG
B
273
80.277
5.174
29.733
1.00
54.38
7
ATOM
4210
CZ
ARG
B
273
79.665
5.669
28.671
1.00
55.34
6
ATOM
4211
NH1
ARG
B
273
80.083
5.410
27.433
1.00
56.45
7
ATOM
4212
NH2
ARG
B
273
78.606
6.455
28.819
1.00
54.66
7
ATOM
4213
N
LEU
B
274
79.992
0.448
32.821
1.00
41.38
7
ATOM
4214
CA
LEU
B
274
78.715
−0.229
32.792
1.00
37.98
6
ATOM
4215
C
LEU
B
274
77.584
0.737
32.506
1.00
37.26
6
ATOM
4216
O
LEU
B
274
77.586
1.908
32.909
1.00
36.11
8
ATOM
4217
CB
LEU
B
274
78.395
−0.939
34.118
1.00
38.68
6
ATOM
4218
CG
LEU
B
274
79.554
−1.797
34.654
1.00
41.26
6
ATOM
4219
CD1
LEU
B
274
79.161
−2.469
35.960
1.00
41.73
6
ATOM
4220
CD2
LEU
B
274
79.999
−2.827
33.625
1.00
42.85
6
ATOM
4221
N
ILE
B
275
76.603
0.270
31.724
1.00
35.74
7
ATOM
4222
CA
ILE
B
275
75.493
1.141
31.372
1.00
33.53
6
ATOM
4223
C
ILE
B
275
74.202
0.402
31.685
1.00
32.45
6
ATOM
4224
O
ILE
B
275
74.121
−0.836
31.733
1.00
31.50
8
ATOM
4225
CB
ILE
B
275
75.466
1.658
29.914
1.00
36.92
6
ATOM
4226
CG1
ILE
B
275
75.105
0.527
28.946
1.00
37.93
6
ATOM
4227
CG2
ILE
B
275
76.794
2.331
29.537
1.00
36.91
6
ATOM
4228
CD1
ILE
B
275
74.962
1.004
27.506
1.00
38.53
6
ATOM
4229
N
ASP
B
276
73.124
1.174
31.933
1.00
28.46
7
ATOM
4230
CA
ASP
B
276
71.866
0.517
32.262
1.00
30.30
6
ATOM
4231
C
ASP
B
276
70.716
1.517
32.068
1.00
29.63
6
ATOM
4232
O
ASP
B
276
71.081
2.666
31.835
1.00
27.88
8
ATOM
4233
CB
ASP
B
276
71.937
−0.066
33.671
1.00
32.97
6
ATOM
4234
CG
ASP
B
276
70.851
−1.058
33.987
1.00
34.63
6
ATOM
4235
OD1
ASP
B
276
69.857
−1.272
33.231
1.00
37.08
8
ATOM
4236
OD2
ASP
B
276
70.931
−1.716
35.054
1.00
35.37
8
ATOM
4237
N
ASN
B
277
69.478
1.072
32.012
1.00
30.76
7
ATOM
4238
CA
ASN
B
277
68.339
1.963
31.738
1.00
31.92
6
ATOM
4239
C
ASN
B
277
67.121
1.388
32.426
1.00
29.27
6
ATOM
4240
O
ASN
B
277
67.035
0.187
32.641
1.00
30.64
8
ATOM
4241
CB
ASN
B
277
68.041
2.214
30.258
1.00
37.99
6
ATOM
4242
CG
ASN
B
277
66.700
1.999
29.601
1.00
41.20
6
ATOM
4243
OD1
ASN
B
277
65.702
1.397
30.046
1.00
41.98
8
ATOM
4244
ND2
ASN
B
277
66.503
2.495
28.345
1.00
41.86
7
ATOM
4245
N
LYS
B
278
66.149
2.219
32.760
1.00
28.29
7
ATOM
4246
CA
LYS
B
278
64.891
1.736
33.328
1.00
30.58
6
ATOM
4247
C
LYS
B
278
63.822
2.756
32.929
1.00
33.32
6
ATOM
4248
O
LYS
B
278
64.130
3.940
32.793
1.00
32.01
8
ATOM
4249
CB
LYS
B
278
64.919
1.486
34.834
1.00
31.32
6
ATOM
4250
CG
LYS
B
278
63.617
0.953
35.422
1.00
35.08
6
ATOM
4251
CD
LYS
B
278
63.793
0.340
36.790
1.00
38.13
6
ATOM
4252
CE
LYS
B
278
63.031
−0.950
37.108
1.00
39.29
6
ATOM
4253
NZ
LYS
B
278
63.193
−1.103
38.612
1.00
44.44
7
ATOM
4254
N
MET
B
279
62.625
2.256
32.594
1.00
33.66
7
ATOM
4255
CA
MET
B
279
61.488
3.102
32.303
1.00
36.39
6
ATOM
4256
C
MET
B
279
60.543
3.014
33.483
1.00
35.26
6
ATOM
4257
O
MET
B
279
60.470
1.929
34.090
1.00
38.21
8
ATOM
4258
CB
MET
B
279
60.797
2.708
30.965
1.00
38.06
6
ATOM
4259
CG
MET
B
279
61.358
3.604
29.846
1.00
42.01
6
ATOM
4260
SD
MET
B
279
61.219
2.888
28.222
1.00
48.77
16
ATOM
4261
CE
MET
B
279
62.632
3.595
27.392
1.00
46.06
6
ATOM
4262
N
VAL
B
280
59.853
4.082
33.859
1.00
34.69
7
ATOM
4263
CA
VAL
B
280
58.937
4.046
34.991
1.00
37.86
6
ATOM
4264
C
VAL
B
280
57.655
4.778
34.624
1.00
39.91
6
ATOM
4265
O
VAL
B
280
57.722
5.842
33.971
1.00
39.57
8
ATOM
4266
CB
VAL
B
280
59.605
4.627
36.262
1.00
40.03
6
ATOM
4267
CG1
VAL
B
280
60.582
5.734
35.894
1.00
40.43
6
ATOM
4268
CG2
VAL
B
280
58.595
5.132
37.286
1.00
41.28
6
ATOM
4269
N
GLU
B
281
56.521
4.221
35.046
1.00
42.47
7
ATOM
4270
CA
GLU
B
281
55.243
4.911
34.809
1.00
45.74
6
ATOM
4271
C
GLU
B
281
54.973
5.919
35.910
1.00
47.07
6
ATOM
4272
O
GLU
B
281
55.370
5.595
37.039
1.00
46.25
8
ATOM
4273
CB
GLU
B
281
54.152
3.848
34.719
1.00
47.41
6
ATOM
4274
CG
GLU
B
281
54.308
2.918
33.516
1.00
48.19
6
ATOM
4275
CD
GLU
B
281
53.705
3.562
32.275
1.00
50.10
6
ATOM
4276
OE1
GLU
B
281
52.718
4.312
32.460
1.00
51.21
8
ATOM
4277
OE2
GLU
B
281
54.203
3.330
31.153
1.00
50.72
8
ATOM
4278
N
LEU
B
282
54.358
7.077
35.662
1.00
49.43
7
ATOM
4279
CA
LEU
B
282
54.144
8.043
36.731
1.00
52.69
6
ATOM
4280
C
LEU
B
282
52.714
8.211
37.222
1.00
56.10
6
ATOM
4281
O
LEU
B
282
51.741
8.259
36.479
1.00
57.86
8
ATOM
4282
CB
LEU
B
282
54.654
9.413
36.232
1.00
51.33
6
ATOM
4283
CG
LEU
B
282
56.153
9.442
35.898
1.00
51.16
6
ATOM
4284
CD1
LEU
B
282
56.568
10.774
35.313
1.00
49.90
6
ATOM
4285
CD2
LEU
B
282
56.959
9.109
37.146
1.00
50.87
6
ATOM
4286
N
ALA
B
283
52.591
8.404
38.527
1.00
58.60
7
ATOM
4287
CA
ALA
B
283
51.340
8.572
39.260
1.00
61.51
6
ATOM
4288
C
ALA
B
283
50.222
7.659
38.748
1.00
62.69
6
ATOM
4289
O
ALA
B
283
49.365
7.240
39.565
1.00
64.21
8
ATOM
4290
CB
ALA
B
283
50.878
10.031
39.215
1.00
61.28
Water
ATOM
4303
O
WAT
W
1
33.957
17.885
−21.689
1.00
20.48
ATOM
4304
O
WAT
W
2
37.847
13.185
4.982
1.00
21.45
ATOM
4305
O
WAT
W
3
63.980
−1.350
11.191
1.00
28.46
ATOM
4306
O
WAT
W
4
56.095
−1.331
−2.328
1.00
33.26
ATOM
4307
O
WAT
W
5
33.170
18.137
−24.293
1.00
23.96
ATOM
4308
O
WAT
W
6
37.215
10.622
−2.497
1.00
25.23
ATOM
4309
O
WAT
W
7
34.408
20.030
−20.099
1.00
22.90
ATOM
4310
O
WAT
W
8
44.843
0.417
12.211
1.00
25.44
ATOM
4311
O
WAT
W
9
32.057
20.794
−18.723
1.00
21.33
ATOM
4312
O
WAT
W
10
39.891
15.086
5.128
1.00
21.17
ATOM
4313
O
WAT
W
11
60.554
9.975
11.882
1.00
23.86
ATOM
4314
O
WAT
W
12
47.956
16.767
16.754
1.00
25.70
ATOM
4315
O
WAT
W
13
26.013
19.028
0.123
1.00
29.25
ATOM
4316
O
WAT
W
14
41.289
15.802
−0.016
1.00
29.45
ATOM
4317
O
WAT
W
15
26.238
26.828
−12.429
1.00
26.43
ATOM
4318
O
WAT
W
16
42.677
−8.069
14.438
1.00
49.57
ATOM
4319
O
WAT
W
17
44.205
−22.405
7.937
1.00
26.54
ATOM
4320
O
WAT
W
18
41.204
15.438
2.596
1.00
28.73
ATOM
4321
O
WAT
W
19
50.665
6.851
−9.161
1.00
28.82
ATOM
4322
O
WAT
W
20
45.856
11.020
16.763
1.00
28.19
ATOM
4323
O
WAT
W
21
56.240
9.146
22.228
1.00
29.25
ATOM
4324
O
WAT
W
22
34.167
22.025
−17.131
1.00
24.52
ATOM
4325
O
WAT
W
23
46.937
−3.706
12.756
1.00
34.74
ATOM
4326
O
WAT
W
24
42.413
2.422
14.402
1.00
33.61
ATOM
4327
O
WAT
W
25
41.229
−21.204
14.206
1.00
24.13
ATOM
4328
O
WAT
W
26
41.221
12.093
−6.937
1.00
25.26
ATOM
4329
O
WAT
W
27
24.372
15.958
−5.041
1.00
27.65
ATOM
4330
O
WAT
W
28
35.615
−12.052
11.939
1.00
30.34
ATOM
4331
O
WAT
W
29
37.895
12.192
−4.849
1.00
26.69
ATOM
4332
O
WAT
W
30
52.106
20.252
−2.182
1.00
28.30
ATOM
4333
O
WAT
W
31
68.369
9.094
44.468
1.00
25.44
ATOM
4334
O
WAT
W
32
56.344
0.572
−4.129
1.00
43.47
ATOM
4335
O
WAT
W
33
23.101
20.797
−4.005
1.00
36.59
ATOM
4336
O
WAT
W
34
49.261
−5.331
2.868
1.00
26.99
ATOM
4337
O
WAT
W
35
47.984
−9.414
25.007
1.00
26.83
ATOM
4338
O
WAT
W
36
42.604
−1.487
5.352
1.00
30.62
ATOM
4339
O
WAT
W
37
62.274
−5.597
10.141
1.00
27.42
ATOM
4340
O
WAT
W
38
26.216
16.962
−12.131
1.00
28.51
ATOM
4341
O
WAT
W
39
30.958
20.957
−10.945
1.00
28.67
ATOM
4342
O
WAT
W
40
34.816
15.313
17.023
1.00
30.79
ATOM
4343
O
WAT
W
41
49.918
15.022
17.578
1.00
28.50
ATOM
4344
O
WAT
W
42
51.910
5.889
8.625
1.00
38.44
ATOM
4345
O
WAT
W
43
62.846
−1.187
14.226
1.00
46.50
ATOM
4346
O
WAT
W
44
25.403
26.593
−16.292
1.00
39.06
ATOM
4347
O
WAT
W
45
30.520
20.301
5.385
1.00
32.49
ATOM
4348
O
WAT
W
46
45.010
−17.167
2.635
1.00
34.22
ATOM
4349
O
WAT
W
47
47.032
−2.770
5.031
1.00
22.23
ATOM
4350
O
WAT
W
48
48.414
1.477
−5.713
1.00
29.51
ATOM
4351
O
WAT
W
49
31.672
7.463
−13.621
1.00
36.04
ATOM
4352
O
WAT
W
50
62.969
0.366
20.839
1.00
25.12
ATOM
4353
O
WAT
W
51
52.181
16.341
18.209
1.00
33.67
ATOM
4354
O
WAT
W
52
34.216
17.207
10.342
1.00
25.68
ATOM
4355
O
WAT
W
53
52.739
13.892
−0.142
1.00
24.81
ATOM
4356
O
WAT
W
54
48.513
−7.403
4.595
1.00
33.10
ATOM
4357
O
WAT
W
55
50.165
3.786
7.424
1.00
31.96
ATOM
4358
O
WAT
W
56
61.601
−10.884
−3.900
1.00
38.55
ATOM
4359
O
WAT
W
57
40.862
−13.477
5.834
1.00
26.78
ATOM
4360
O
WAT
W
58
73.540
−3.703
38.069
1.00
28.56
ATOM
4361
O
WAT
W
59
53.267
18.858
−0.006
1.00
28.15
ATOM
4362
O
WAT
W
60
47.896
−10.104
11.452
1.00
29.42
ATOM
4363
O
WAT
W
61
32.210
13.233
−12.282
1.00
31.94
ATOM
4364
O
WAT
W
62
48.007
11.908
18.269
1.00
37.69
ATOM
4365
O
WAT
W
63
29.173
9.259
−17.716
1.00
30.38
ATOM
4366
O
WAT
W
64
35.297
19.389
9.031
1.00
29.80
ATOM
4367
O
WAT
W
65
40.504
2.299
−10.545
1.00
32.49
ATOM
4368
O
WAT
W
66
41.958
−10.772
13.351
1.00
42.64
ATOM
4369
O
WAT
W
67
36.143
16.525
−1.066
1.00
34.59
ATOM
4370
O
WAT
W
68
62.385
−11.067
−1.312
1.00
33.16
ATOM
4371
O
WAT
W
69
65.110
11.392
10.350
1.00
28.97
ATOM
4372
O
WAT
W
70
63.427
−3.415
19.364
1.00
27.45
ATOM
4373
O
WAT
W
71
68.617
14.525
33.511
1.00
37.55
ATOM
4374
O
WAT
W
72
61.639
−4.893
17.918
1.00
24.98
ATOM
4375
O
WAT
W
73
66.736
4.204
19.794
1.00
30.21
ATOM
4376
O
WAT
W
74
55.982
12.796
22..001
1.00
36.21
ATOM
4377
O
WAT
W
75
64.346
6.123
−5.386
1.00
40.37
ATOM
4378
O
WAT
W
76
65.025
−2.313
32.956
1.00
37.41
ATOM
4379
O
WAT
W
77
44.448
−0.359
−6.294
1.00
29.00
ATOM
4380
O
WAT
W
78
48.675
−0.966
−4.566
1.00
35.26
ATOM
4381
O
WAT
W
79
31.748
14.620
−27.469
1.00
30.01
ATOM
4382
O
WAT
W
80
22.272
14.300
−4.370
1.00
33.41
ATOM
4383
O
WAT
W
81
61.185
6.162
25.319
1.00
33.42
ATOM
4384
O
WAT
W
82
25.793
11.693
−9.261
1.00
32.09
ATOM
4385
O
WAT
W
83
44.087
16.403
−7.636
1.00
30.17
ATOM
4386
O
WAT
W
84
42.576
−4.126
6.016
1.00
55.25
ATOM
4387
O
WAT
W
85
68.891
7.733
20.798
1.00
37.85
ATOM
4388
O
WAT
W
86
70.712
−5.611
41.295
1.00
34.04
ATOM
4389
O
WAT
W
87
43.384
−22.647
14.391
1.00
41.78
ATOM
4390
O
WAT
W
88
70.983
−8.966
9.646
1.00
33.63
ATOM
4391
O
WAT
W
89
75.957
−17.895
11.852
1.00
47.71
ATOM
4392
O
WAT
W
90
63.730
−0.759
18.432
1.00
34.78
ATOM
4393
O
WAT
W
91
31.689
15.534
−14.467
1.00
32.23
ATOM
4394
O
WAT
W
92
44.527
−11.830
12.755
1.00
34.17
ATOM
4395
O
WAT
W
93
20.677
30.620
−24.626
1.00
31.71
ATOM
4396
O
WAT
W
94
44.639
17.338
−10.200
1.00
34.48
ATOM
4397
O
WAT
W
95
75.731
12.312
36.456
1.00
43.57
ATOM
4398
O
WAT
W
96
44.412
10.904
19.269
1.00
42.19
ATOM
4399
O
WAT
W
97
22.294
30.665
−27.831
1.00
34.67
ATOM
4400
O
WAT
W
98
61.020
1.839
−4.047
1.00
32.70
ATOM
4401
O
WAT
W
99
63.564
−3.241
9.033
1.00
26.37
ATOM
4402
O
WAT
W
100
58.754
3.167
−4.838
1.00
32.36
ATOM
4403
O
WAT
W
101
65.772
−9.474
4.700
1.00
28.90
ATOM
4404
O
WAT
W
102
68.154
15.020
30.966
1.00
48.55
ATOM
4405
O
WAT
W
103
69.423
3.142
26.541
1.00
37.38
ATOM
4406
O
WAT
W
104
46.011
16.393
−32.096
1.00
35.12
ATOM
4407
O
WAT
W
105
29.379
18.412
−31.086
1.00
39.01
ATOM
4408
O
WAT
W
106
45.917
−11.276
10.149
1.00
27.62
ATOM
4409
O
WAT
W
107
24.739
28.644
−17.280
1.00
32.77
ATOM
4410
O
WAT
W
108
79.205
12.257
45.859
1.00
41.16
ATOM
4411
O
WAT
W
109
73.058
−3.265
35.431
1.00
33.63
ATOM
4412
O
WAT
W
110
46.854
−9.240
3.826
1.00
36.79
ATOM
4413
O
WAT
W
111
25.850
9.001
−9.625
1.00
34.69
ATOM
4414
O
WAT
W
112
62.047
8.655
0.423
1.00
33.56
ATOM
4415
O
WAT
W
113
37.663
10.928
−18.842
1.00
34.05
ATOM
4416
O
WAT
W
114
34.619
21.383
−14.295
1.00
30.74
ATOM
4417
O
WAT
W
115
58.523
21.835
−8.875
1.00
37.34
ATOM
4418
O
WAT
W
116
28.178
28.182
−10.656
1.00
43.64
ATOM
4419
O
WAT
W
117
66.395
−3.417
24.653
1.00
32.24
ATOM
4420
O
WAT
W
118
51.651
21.138
16.503
1.00
35.04
ATOM
4421
O
WAT
W
119
46.184
−9.790
13.725
1.00
38.61
ATOM
4422
O
WAT
W
120
77.317
−2.960
44.894
1.00
29.27
ATOM
4423
O
WAT
W
121
53.189
17.937
10.605
1.00
29.73
ATOM
4424
O
WAT
W
122
36.010
12.829
−10.679
1.00
33.47
ATOM
4425
O
WAT
W
123
34.086
3.401
−11.327
1.00
50.83
ATOM
4426
O
WAT
W
124
67.551
−6.941
−3.458
1.00
40.00
ATOM
4427
O
WAT
W
125
22.839
14.210
−21.134
1.00
33.56
ATOM
4428
O
WAT
W
126
46.144
1.450
−7.279
1.00
34.78
ATOM
4429
O
WAT
W
127
44.101
21.525
16.698
1.00
39.31
ATOM
4430
O
WAT
W
128
53.306
5.434
−16.838
1.00
54.57
ATOM
4431
O
WAT
W
129
50.250
1.205
22.740
1.00
28.98
ATOM
4432
O
WAT
W
130
26.485
19.155
−29.949
1.00
29.98
ATOM
4433
O
WAT
W
131
24.707
18.542
−27.822
1.00
37.35
ATOM
4434
O
WAT
W
132
67.710
5.567
21.896
1.00
29.04
ATOM
4435
O
WAT
W
133
45.674
−4.052
19.840
1.00
36.16
ATOM
4436
O
WAT
W
134
24.220
25.124
−21.068
1.00
34.59
ATOM
4437
O
WAT
W
135
61.598
17.680
13.540
1.00
42.71
ATOM
4438
O
WAT
W
136
49.468
−7.110
25.310
1.00
38.94
ATOM
4439
O
WAT
W
137
66.911
11.234
12.429
1.00
37.05
ATOM
4440
O
WAT
W
138
57.148
2.737
30.896
1.00
48.38
ATOM
4441
O
WAT
W
139
34.489
9.771
−18.467
1.00
30.91
ATOM
4442
O
WAT
W
140
32.760
21.132
4.304
1.00
29.66
ATOM
4443
O
WAT
W
141
49.857
−2.000
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1.00
39.89
ATOM
4444
O
WAT
W
142
54.890
−1.411
27.207
1.00
47.87
ATOM
4445
O
WAT
W
143
64.172
15.675
32.993
1.00
36.07
ATOM
4446
O
WAT
W
144
55.868
−7.470
−4.555
1.00
42.27
ATOM
4447
O
WAT
W
145
44.776
21.855
−19.009
1.00
46.18
ATOM
4448
O
WAT
W
146
81.842
9.124
42.112
1.00
41.17
ATOM
4449
O
WAT
W
147
65.891
12.184
46.900
1.00
41.27
ATOM
4450
O
WAT
W
148
61.870
−0.694
32.618
1.00
36.54
ATOM
4451
O
WAT
W
149
53.665
−22.423
14.114
1.00
45.13
ATOM
4452
O
WAT
W
150
78.486
−11.509
9.153
1.00
39.16
ATOM
4453
O
WAT
W
151
57.272
24.770
−5.465
1.00
53.97
ATOM
4454
O
WAT
W
152
76.932
13.052
43.714
1.00
34.28
ATOM
4455
O
WAT
W
153
46.722
−10.271
21.629
1.00
39.60
ATOM
4456
O
WAT
W
154
71.871
−14.779
14.884
1.00
41.12
ATOM
4457
O
WAT
W
155
75.221
−2.490
33.675
1.00
36.01
ATOM
4458
O
WAT
W
156
79.538
8.216
41.312
1.00
39.15
ATOM
4459
O
WAT
W
157
37.416
−3.706
5.762
1.00
38.40
ATOM
4460
O
WAT
W
158
35.517
15.310
19.620
1.00
36.39
ATOM
4461
O
WAT
W
159
51.237
5.731
5.785
1.00
34.79
ATOM
4462
O
WAT
W
160
51.381
−1.632
26.211
1.00
44.45
ATOM
4463
O
WAT
W
161
43.466
16.232
−32.007
1.00
52.60
ATOM
4464
O
WAT
W
162
75.662
12.257
40.222
1.00
38.37
ATOM
4465
O
WAT
W
163
32.057
−13.826
10.708
1.00
39.45
ATOM
4466
O
WAT
W
164
44.346
0.072
6.468
1.00
36.40
ATOM
4467
O
WAT
W
165
52.324
−2.560
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1.00
46.60
ATOM
4468
O
WAT
W
166
57.861
8.649
−15.458
1.00
41.61
ATOM
4469
O
WAT
W
167
67.132
−5.044
15.257
1.00
40.23
ATOM
4470
O
WAT
W
168
59.264
−1.197
31.588
1.00
51.30
ATOM
4471
O
WAT
W
169
51.835
3.346
23.021
1.00
39.67
ATOM
4472
O
WAT
W
170
57.419
−5.177
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1.00
35.72
ATOM
4473
O
WAT
W
171
48.627
11.775
20.770
1.00
47.02
ATOM
4474
O
WAT
W
172
64.778
−5.263
25.321
1.00
34.04
ATOM
4475
O
WAT
W
173
21.644
11.926
−2.423
1.00
35.54
ATOM
4476
O
WAT
W
174
40.345
0.581
13.671
1.00
59.11
ATOM
4477
O
WAT
W
175
65.019
−5.440
32.798
1.00
40.87
ATOM
4478
O
WAT
W
176
44.228
−7.202
4.474
1.00
39.61
ATOM
4479
O
WAT
W
177
83.719
10.000
40.277
1.00
42.80
ATOM
4480
O
WAT
W
178
68.408
−7.591
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1.00
38.18
ATOM
4481
O
WAT
W
179
63.973
−9.992
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1.00
51.42
ATOM
4482
O
WAT
W
180
39.726
7.902
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1.00
49.92
ATOM
4483
O
WAT
W
181
55.044
0.850
−6.811
1.00
51.09
ATOM
4484
O
WAT
W
182
25.424
1.610
−6.315
1.00
30.30
ATOM
4485
O
WAT
W
183
25.655
20.392
−3.870
1.00
43.57
ATOM
4486
O
WAT
W
184
43.760
−10.333
15.054
1.00
39.92
ATOM
4487
O
WAT
W
185
46.383
19.180
−9.597
1.00
33.30
ATOM
4488
O
WAT
W
186
57.924
9.404
−18.128
1.00
44.22
ATOM
4489
O
WAT
W
187
58.234
−16.451
0.308
1.00
36.17
ATOM
4490
O
WAT
W
188
38.059
−19.859
11.817
1.00
32.02
ATOM
4491
O
WAT
W
189
42.349
23.603
0.069
1.00
55.22
ATOM
4492
O
WAT
W
190
62.117
0.301
41.059
1.00
47.46
ATOM
4493
O
WAT
W
191
39.146
34.096
6.333
1.00
35.61
ATOM
4494
O
WAT
W
192
52.021
−17.641
1.723
1.00
36.52
ATOM
4495
O
WAT
W
193
30.405
15.315
−12.140
1.00
40.90
ATOM
4496
O
WAT
W
194
56.589
6.376
−25.137
1.00
50.29
ATOM
4497
O
WAT
W
195
32.292
21.747
−31.418
1.00
30.10
ATOM
4498
O
WAT
W
196
25.932
26.262
−31.876
1.00
33.19
ATOM
4499
O
WAT
W
197
44.253
27.169
0.607
1.00
41.25
ATOM
4500
O
WAT
W
198
31.985
18.702
10.898
1.00
43.36
ATOM
4501
O
WAT
W
199
66.104
14.551
9.666
1.00
42.15
ATOM
4502
O
WAT
W
200
65.400
14.447
48.384
1.00
54.11
ATOM
4503
O
WAT
W
201
23.164
26.745
−32.350
1.00
43.78
ATOM
4504
O
WAT
W
202
36.449
−19.529
9.775
1.00
56.52
ATOM
4505
O
WAT
W
203
37.955
9.830
−30.717
1.00
42.18
ATOM
4506
O
WAT
W
204
80.612
−6.612
30.354
1.00
58.09
ATOM
4507
O
WAT
W
205
42.193
−5.177
3.641
1.00
53.40
ATOM
4508
O
WAT
W
206
34.846
19.253
−0.441
1.00
43.51
ATOM
4509
O
WAT
W
207
55.615
−2.982
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1.00
46.41
ATOM
4510
O
WAT
W
208
51.625
4.220
−8.519
1.00
45.10
ATOM
4511
O
WAT
W
209
25.739
8.524
−24.942
1.00
36.13
ATOM
4512
O
WAT
W
210
68.747
17.314
21.066
1.00
43.56
ATOM
4513
O
WAT
W
211
84.666
3.989
47.339
1.00
56.35
ATOM
4514
O
WAT
W
212
39.125
28.472
0.851
1.00
43.49
ATOM
4515
O
WAT
W
213
40.758
−6.436
1.126
1.00
43.08
ATOM
4516
O
WAT
W
214
65.742
−7.673
25.260
1.00
39.84
ATOM
4517
O
WAT
W
215
68.113
7.014
26.268
1.00
44.06
ATOM
4518
O
WAT
W
216
50.292
24.666
−37.803
1.00
47.27
ATOM
4519
O
WAT
W
217
76.215
−4.709
32.421
1.00
35.98
ATOM
4520
O
WAT
W
218
28.732
31.945
−22.056
1.00
33.29
ATOM
4521
O
WAT
W
219
74.218
14.100
34.912
1.00
76.11
ATOM
4522
O
WAT
W
220
57.961
0.451
28.074
1.00
47.45
ATOM
4523
O
WAT
W
221
32.590
10.932
−11.111
1.00
49.96
ATOM
4524
O
WAT
W
222
51.203
−19.722
11.498
1.00
41.52
ATOM
4525
O
WAT
W
223
55.448
−14.143
−4.633
1.00
36.90
ATOM
4526
O
WAT
W
224
21.981
23.670
−26.954
1.00
35.03
ATOM
4527
O
WAT
W
225
38.572
−13.668
7.579
1.00
39.66
ATOM
4528
O
WAT
W
226
56.707
−16.581
26.316
1.00
35.78
ATOM
4529
O
WAT
W
227
70.225
2.519
46.317
1.00
45.99
ATOM
4530
O
WAT
W
228
36.498
21.585
14.126
1.00
33.98
ATOM
4531
O
WAT
W
229
61.790
−13.520
−4.514
1.00
50.15
ATOM
4532
O
WAT
W
230
64.989
−1.584
30.303
1.00
36.47
ATOM
4533
O
WAT
W
231
38.229
27.188
10.218
1.00
45.56
ATOM
4534
O
WAT
W
232
67.835
−7.729
5.083
1.00
34.03
ATOM
4535
O
WAT
W
233
45.674
22.663
18.801
1.00
65.84
ATOM
4536
O
WAT
W
234
43.579
−5.428
17.882
1.00
43.49
ATOM
4537
O
WAT
W
235
64.221
5.067
46.860
1.00
41.97
ATOM
4538
O
WAT
W
236
72.469
18.804
43.000
1.00
36.08
ATOM
4539
O
WAT
W
237
43.180
3.609
16.574
1.00
59.75
ATOM
4540
O
WAT
W
238
34.121
16.290
−13.499
1.00
46.11
ATOM
4541
O
WAT
W
239
62.037
17.693
20.122
1.00
50.69
ATOM
4542
O
WAT
W
240
37.376
10.472
−16.234
1.00
45.81
ATOM
4543
O
WAT
W
241
26.431
22.009
−0.233
1.00
46.92
ATOM
4544
O
WAT
W
242
25.310
12.750
−11.978
1.00
50.59
ATOM
4545
O
WAT
W
243
19.671
9.916
−3.708
1.00
49.70
ATOM
4546
O
WAT
W
244
38.186
21.703
16.967
1.00
35.43
ATOM
4547
O
WAT
W
245
40.977
−0.520
−8.992
1.00
51.53
ATOM
4548
O
WAT
W
246
17.264
17.138
1.436
1.00
65.65
ATOM
4549
O
WAT
W
247
59.212
−16.788
−2.401
1.00
43.21
ATOM
4550
O
WAT
W
248
77.330
−11.434
7.852
1.00
51.89
ATOM
4551
O
WAT
W
249
22.908
25.131
−34.628
1.00
44.65
ATOM
4552
O
WAT
W
250
37.272
2.059
20.950
1.00
42.62
ATOM
4553
O
WAT
W
251
78.365
−12.406
10.087
1.00
55.28
ATOM
4554
O
WAT
W
252
31.173
17.182
−10.252
1.00
47.60
ATOM
4555
O
WAT
W
253
48.516
−12.376
−1.883
1.00
33.36
ATOM
4556
O
WAT
W
254
43.940
18.919
−6.022
1.00
54.48
ATOM
4557
O
WAT
W
255
30.610
3.062
18.104
1.00
46.62
ATOM
4558
O
WAT
W
256
72.364
2.032
11.881
1.00
60.78
ATOM
4559
O
WAT
W
257
36.491
−6.172
6.630
1.00
48.36
ATOM
4560
O
WAT
W
258
65.789
−10.191
31.731
1.00
42.15
ATOM
4561
O
WAT
W
259
59.438
15.957
21.720
1.00
40.75
ATOM
4562
O
WAT
W
260
31.766
20.345
7.940
1.00
41.46
ATOM
4563
O
WAT
W
261
38.175
22.668
9.740
1.00
36.51
ATOM
4564
O
WAT
W
262
69.731
20.766
38.855
1.00
45.16
ATOM
4565
O
WAT
W
263
25.834
32.385
−27.930
1.00
39.41
ATOM
4566
O
WAT
W
264
70.140
−4.383
3.316
1.00
42.01
ATOM
4567
O
WAT
W
265
17.686
28.637
−27.597
1.00
36.50
ATOM
4568
O
WAT
W
266
38.498
10.397
17.979
1.00
38.49
ATOM
4569
O
WAT
W
267
41.552
17.448
−14.793
1.00
45.70
ATOM
4570
O
WAT
W
268
43.965
−4.267
15.684
1.00
47.33
ATOM
4571
O
WAT
W
269
24.247
23.631
−0.377
1.00
52.61
ATOM
4572
O
WAT
W
270
39.439
16.949
−2.045
1.00
40.49
ATOM
4573
O
WAT
W
271
49.374
23.294
3.413
1.00
46.56
ATOM
4574
O
WAT
W
272
39.872
8.421
−18.197
1.00
45.41
ATOM
4575
O
WAT
W
273
46.466
−1.275
7.239
1.00
47.88
ATOM
4576
O
WAT
W
274
29.019
38.205
−20.300
1.00
61.46
ATOM
4577
O
WAT
W
275
69.375
1.409
13.444
1.00
43.48
ATOM
4578
O
WAT
W
276
72.207
3.732
29.386
1.00
40.43
ATOM
4579
O
WAT
W
277
39.712
37.170
0.051
1.00
39.08
ATOM
4580
O
WAT
W
278
48.094
−1.929
10.639
1.00
35.23
ATOM
4581
O
WAT
W
279
46.176
−0.007
10.070
1.00
57.82
ATOM
4582
O
WAT
W
280
34.060
14.226
−7.694
1.00
47.69
ATOM
4583
O
WAT
W
281
66.985
−1.458
15.223
1.00
40.31
ATOM
4584
O
WAT
W
282
69.909
−11.226
6.382
1.00
54.99
ATOM
4585
O
WAT
W
283
27.681
22.895
8.733
1.00
41.91
ATOM
4586
O
WAT
W
284
44.274
−3.092
9.331
1.00
47.80
ATOM
4587
O
WAT
W
285
35.726
14.777
−5.459
1.00
63.96
ATOM
4588
O
WAT
W
286
36.355
13.676
−2.214
1.00
51.47
ATOM
4589
O
WAT
W
287
45.262
7.207
17.415
1.00
54.68
ATOM
4590
O
WAT
W
288
68.185
20.756
43.230
1.00
51.92
ATOM
4591
O
WAT
W
289
61.045
16.189
10.892
1.00
47.39
ATOM
4592
O
WAT
W
290
37.948
29.641
−14.217
1.00
51.54
ATOM
4593
O
WAT
W
291
25.752
1.732
16.571
1.00
50.52
ATOM
4594
O
WAT
W
292
21.651
4.509
5.878
1.00
55.37
ATOM
4595
O
WAT
W
293
57.826
3.992
44.663
1.00
46.21
ATOM
4596
O
WAT
W
294
66.103
19.731
40.130
1.00
39.58
ATOM
4597
O
WAT
W
295
46.479
4.707
17.542
1.00
44.15
ATOM
4598
O
WAT
W
296
71.219
−3.422
0.474
1.00
42.17
ATOM
4599
O
WAT
W
297
39.881
2.904
14.591
1.00
39.80
ATOM
4600
O
WAT
W
298
56.543
16.797
18.584
1.00
46.72
ATOM
4601
O
WAT
W
299
61.789
−18.999
2.206
1.00
57.02
ATOM
4602
O
WAT
W
300
42.705
10.878
−13.312
1.00
41.71
ATOM
4603
O
WAT
W
301
69.432
7.509
6.399
1.00
56.46
ATOM
4604
O
WAT
W
302
50.399
1.771
−8.208
1.00
46.36
ATOM
4605
O
WAT
W
303
80.707
8.597
32.436
1.00
57.84
ATOM
4606
O
WAT
W
304
35.950
−3.190
−6.617
1.00
47.01
ATOM
4607
O
WAT
W
305
63.191
13.663
10.338
1.00
47.69
ATOM
4608
O
WAT
W
306
32.746
17.045
16.882
1.00
38.37
ATOM
4609
O
WAT
W
307
55.795
22.081
−3.121
1.00
45.39
ATOM
4610
O
WAT
W
308
52.917
−15.266
−5.084
1.00
58.04
ATOM
4611
O
WAT
W
309
32.990
20.281
−2.705
1.00
41.15
ATOM
4612
O
WAT
W
310
65.221
−0.521
13.373
1.00
50.04
ATOM
4613
O
WAT
W
311
31.445
8.146
−16.640
1.00
47.12
ATOM
4614
O
WAT
W
312
70.526
−1.084
−1.047
1.00
43.90
ATOM
4615
O
WAT
W
313
67.588
−6.363
21.900
1.00
57.15
ATOM
4616
O
WAT
W
314
66.096
−4.686
20.242
1.00
69.24
ATOM
4617
O
WAT
W
315
47.292
23.337
13.967
1.00
42.45
ATOM
4618
O
WAT
W
316
77.697
−6.690
46.864
1.00
61.61
ATOM
4619
O
WAT
W
317
57.134
18.189
−19.802
1.00
61.48
ATOM
4620
O
WAT
W
318
56.615
6.099
−16.259
1.00
55.28
ATOM
4621
O
WAT
W
319
70.759
17.127
50.284
1.00
46.60
ATOM
4622
O
WAT
W
320
72.021
−17.283
5.694
1.00
53.07
ATOM
4623
O
WAT
W
321
23.729
4.269
−4.449
1.00
58.06
ATOM
4624
O
WAT
W
322
22.138
20.117
−24.492
1.00
37.83
ATOM
4625
O
WAT
W
323
40.526
13.448
−0.063
1.00
54.95
ATOM
4626
O
WAT
W
324
28.034
−4.586
23.421
1.00
50.98
ATOM
4627
O
WAT
W
325
38.920
16.623
−33.391
1.00
53.48
ATOM
4628
O
WAT
W
326
77.040
−7.476
27.616
1.00
73.56
ATOM
4629
O
WAT
W
327
68.678
−0.075
28.998
1.00
51.90
ATOM
4630
O
WAT
W
328
46.505
7.743
−11.664
1.00
43.38
ATOM
4631
O
WAT
W
329
43.657
18.299
−3.514
1.00
20.00
ATOM
4632
O
WAT
W
330
40.596
13.269
−4.354
1.00
20.00
ATOM
4633
O
WAT
W
331
66.428
−1.404
17.847
1.00
20.00
ATOM
4634
O
WAT
W
332
41.584
19.897
−1.703
1.00
20.00
ATOM
4635
O
WAT
W
333
41.694
22.971
−4.274
1.00
20.00
ATOM
4636
O
WAT
W
334
67.997
3.764
15.541
1.00
20.00
ATOM
4637
O
WAT
W
335
60.537
18.286
2.068
1.00
20.00
ATOM
4638
O
WAT
W
336
56.447
20.428
10.716
1.00
20.00
ATOM
4639
O
WAT
W
337
55.557
22.546
9.246
1.00
20.00
ATOM
4640
O
WAT
W
338
58.179
16.183
−0.749
1.00
20.00
ATOM
4641
O
WAT
W
339
58.887
16.112
−3.916
1.00
20.00
ATOM
4642
O
WAT
W
340
63.509
11.351
2.806
1.00
20.00
ATOM
4643
O
WAT
W
341
62.716
14.296
1.151
1.00
20.00
ATOM
4644
O
WAT
W
342
39.563
−4.272
12.971
1.00
20.00
ATOM
4645
O
WAT
W
343
39.743
−6.346
11.592
1.00
20.00
ATOM
4646
O
WAT
W
344
44.345
−8.782
9.282
1.00
20.00
ATOM
4647
O
WAT
W
345
38.126
−6.949
4.925
1.00
20.00
ATOM
4648
O
WAT
W
346
41.558
−9.568
2.423
1.00
20.00
ATOM
4649
O
WAT
W
347
46.133
−8.864
−1.132
1.00
20.00
ATOM
4650
O
WAT
W
348
42.431
12.582
19.513
1.00
20.00
ATOM
4651
O
WAT
W
349
39.817
3.709
21.589
1.00
20.00
ATOM
4652
O
WAT
W
350
40.535
5.544
20.119
1.00
20.00
ATOM
4653
O
WAT
W
351
41.467
8.090
20.981
1.00
20.00
ATOM
4654
O
WAT
W
352
61.469
16.879
−5.628
1.00
20.00
ATOM
4655
O
WAT
W
353
57.522
13.280
−9.676
1.00
20.00
ATOM
4656
O
WAT
W
354
57.275
9.042
−5.426
1.00
20.00
ATOM
4657
O
WAT
W
355
59.327
5.417
−6.085
1.00
20.00
ATOM
4658
O
WAT
W
356
52.962
−4.323
−3.179
1.00
20.00
ATOM
4659
O
WAT
W
357
36.344
−8.909
7.979
1.00
20.00
ATOM
4660
O
WAT
W
358
42.391
30.320
−15.418
1.00
20.00
ATOM
4661
O
WAT
W
359
52.354
18.876
−21.657
1.00
20.00
ATOM
4662
O
WAT
W
360
85.510
2.059
39.934
1.00
20.00
ATOM
4663
O
WAT
W
361
86.895
4.068
37.822
1.00
20.00
ATOM
4664
O
WAT
W
362
81.610
8.015
30.106
1.00
20.00
ATOM
4665
O
WAT
W
363
81.600
7.773
49.392
1.00
20.00
ATOM
4666
O
WAT
W
364
76.414
9.988
52.505
1.00
20.00
ATOM
4667
O
WAT
W
365
67.897
8.778
49.346
1.00
20.00
ATOM
4668
O
WAT
W
366
63.858
2.436
46.800
1.00
20.00
ATOM
4669
O
WAT
W
367
71.953
1.096
48.138
1.00
20.00
ATOM
4670
O
WAT
W
368
89.873
−11.648
35.808
1.00
20.00
ATOM
4671
O
WAT
W
369
88.460
−12.813
38.004
1.00
20.00
ATOM
4672
O
WAT
W
370
91.761
−9.669
35.928
1.00
20.00
ATOM
4673
O
WAT
W
371
88.580
−15.367
38.475
1.00
20.00
ATOM
4674
O
WAT
W
372
76.861
−9.543
44.348
1.00
20.00
ATOM
4675
O
WAT
W
373
74.471
−6.743
45.210
1.00
20.00
ATOM
4676
O
WAT
W
374
79.402
−2.424
46.754
1.00
20.00
ATOM
4677
O
WAT
W
375
75.647
−0.122
49.778
1.00
20.00
ATOM
4678
O
WAT
W
376
77.752
1.584
49.411
1.00
20.00
ATOM
4679
O
WAT
W
377
37.468
−4.589
21.373
1.00
20.00
ATOM
4680
O
WAT
W
378
45.334
−7.735
21.716
1.00
20.00
ATOM
4681
O
WAT
W
379
46.136
−5.299
22.588
1.00
20.00
ATOM
4682
O
WAT
W
380
43.144
−7.232
20.423
1.00
20.00
ATOM
4683
O
WAT
W
381
42.129
−4.775
20.988
1.00
20.00
ATOM
4684
O
WAT
W
382
47.659
−14.000
24.499
1.00
20.00
ATOM
4685
O
WAT
W
383
41.892
−6.834
15.632
1.00
20.00
ATOM
4686
O
WAT
W
384
42.961
−8.398
13.868
1.00
20.00
TABLE 2
Composition of defined minimal culture medium for
selenium-containing PS. All components were
filter-sterilized through 0.22 μm filters, except where indicated.
Compound
Stock conc.
Volume
Comments
M9 medium a
1′
250 ml
Autoclaved.
MgSO 4
1 M
250 μl
Autoclaved separately from
M9 medium to avoid
precipitation.
D-glucose
4% w/v
25 ml
Not autoclaved, since that
caused glucose to
caramelize (yellow colour);
filter sterilized instead.
Thiamine
0.5% w/v
25 μl
Prepared stock and stored at
−20° C.; since repeated
cycles of freeze and thaw
do not damage it.
FeSO 4
4.2 g/l
250 μl
Prepared stock and stored at
−20° C., to prevent
oxidation.
Ampicillin
100 mg/ml
250 μl
Filter sterilized and stored
as aliquots - cycles of
freeze and thaw were avoided.
IPTG
70 mg/ml
250 μl
L-arginine
2.53% w/v
5 ml
Supplemented for AT1371
deficiency; prepared
together as single stock.
L-histidine
0.31% w/v
L-proline
4.6% w/v
Adenine
1.35% w/v
L-lysine
12.5 g/l
2 ml
Cocktail for methionine
pathway inhibition; prepared
as one stock. Final
concentrations were 100 and
50 mg/l respectively.
L-phenylalanine
12.5 g/l
L-threonine
12.5 g/l
L-isoleucine
6.25 g/l
L-leucine
6.25 g/l
L-valine
6.25 g/l
L-seleno-
Final conc:
No need to sterilise, to
methionine
50 mg/l
minimise risk of oxidation.
Dissolved in water directly
in bottle in which
supplied, then added.
a Sambrook, J., Fritsch, E. F. & Maniatis, T. (1989). Molecular cloning: a laboratory manual, 2nd ed. Cold Spring Harbour Laboratory Press, Cold Spring Harbor, N.Y.
TABLE 3
Crystallographic
refinement
No. reflexions (test set)
77294 (4062)
Test set is ex-
cluded from re-
finement for
cross-validation
No. restraints
15730
Restraints in TNT
with a weight
assigned
No. parameters
20236
Weight for geom.
3
restraints (TNT)
Final model parameters
Residues
566
Hetero
1 Tris,
2 ethanediol
No. water molecules
622
No. non-hydrogen atoms
5059
Resolution range (Å)
45-1.7
Refinement convergence
R free
24.9
R factor calculated
using test re-
flexions
R factor
22.6
R factor =
Σ h ||F obs | − |F calc ||/
Σ h |F obs |, w/o test
reflexions.
DDQ (score, ranking)
UFO
0.71 (bottom 25%)
“Unassigned
positive Feature
left-Over score”
DDQ-R
15.2 (bottom 25%)
Ratio of Shift and
Water peak
contributions.
Average B-factor,
subunit A (Å 2 )
33.9
subunit B (Å 2 )
36.4
waters (Å 2 )
47.8
Wilson distribution
28.0
B factor (Å 2 )
Model quality
Ramachandran plot
% residues in most
92.2
favoured region
% residues in generously-
7.4
allowed region
No. residues in dis-
0
allowed region
Rms deviation from ideal
Covalent bond lengths (Å)
0.018
(“root mean square”)
Bond angles (°)
1.41
Planar groups (Å)
0.007
Procheck criteria
% bond lengths outside
2.6
expected limits
% bond angles outside
3.1
expected limits
% planar groups outside
1.0
expected limits
WhatCheck criteria
No. unsaturated H-bonds
2
No. residues in unusual
14
environments | A crystal of pantothenate synthetase (PS) has a monoclinic space group P2 1 and unit cell dimensions of a=66.0±0.2 Å, b=78.1±0.2 Å, c=77.1±0.2 Å and β=103.7±0.2°. | 2 |
TECHNICAL FIELD
[0001] The present invention relates to a protection circuit and method, and in particular, but not exclusively, to a protection circuit and method for protecting a light source, for example an LED illuminated in a RGB (Red, Blue, Green) LED array used for illuminating a target object, light from the target object being detected by a sensor, for example a CIS/CCD imaging sensor, as used in imaging apparatus such as optical imagers, e.g. scanners, and the like.
BACKGROUND
[0002] FIG. 1 shows a basic diagram of a state of the art LED driver circuit that is used, for example, in an image reading apparatus in conjunction with a CIS or CCD image sensor device. An LED array L 1 -L 3 is coupled to switches S 1 -S 3 and resistors R 1 -R 3 . The LED array L 1 -L 3 , switching circuit S 1 -S 3 , and resistors R 1 -R 3 are arranged separately from the analogue front end (AFE) circuitry that is used to process image data received from the sensor device, such as a Photo Diode Array (PDA) for example.
[0003] In a colour image scanner, the LED array typically comprises Red (L 1 ), Green (L 2 ) and Blue (L 3 ) LEDs. Light of each colour emitted from the respective LED illuminates a portion of a target object that is to be scanned, and the light reflected by the object is incident on a sensor device. Typically, the sensor device comprises an array of sensors arranged linearly as a line image sensor, each element of the sensor array comprising a photoelectric conversion element, such as a photodiode and a capacitor for each pixel, which converts incident light into a current which is accumulated as a charge on the capacitor. The respective charges accumulated on the respective capacitors are converted into respective voltages that are then output from the sensor array (PDA).
[0004] The voltages output from the PDA are converted by an Analogue to Digital Converter (ADC) into digital signals for subsequent processing during generation of the image of the target object being scanned.
[0005] The scanning of an image is usually performed using a line scanning operation. For colour images, each line is scanned by the Red, Green and Blue light sources. That is, the Red LED L 1 is turned on to read one line in a scanning direction, thereby obtaining the Red component of that line. The Green LED L 2 is then turned on to obtain the Green component of that line, followed by the Blue LED L 3 being turned on to obtain the Blue component of that line. The LED array and sensor array are then typically moved on a carriage mechanism to align with the next line on the target object. Each LED L 1 -L 3 is turned on by switching on the respective switch S 1 -S 3 , using respective switch control signals CS 1 -CS 3 received from a switch controller logic circuit SC.
[0006] While one line is being scanned, image data received from the sensor array (PDA) relating to a previous line scan is read out serially and processed by the ADC.
[0007] The current flowing through each LED is defined by the current-voltage characteristics of the LED, by the resistance of the series resistor and by the voltage applied from the power supply, PSU, (the on-resistance of the switch usually being negligible).
[0008] FIGS. 2 a - 2 d show the switch control signals CS 1 -CS 3 and the supply current IS drawn from the power supply PSU in a “constant current” mode. The ground current is substantially equal to the supply current.
[0009] In addition to each LED passing a respective constant current during illumination of the target object, it is also known to use Pulse Width Modulation (PWM) control signals for controlling the illumination of each LED, such that the illumination or intensity of the LED can be controlled by controlling the duty-cycle and/or frequency of the PWM control signals. The current though the LED may be subject to wide variation due to tolerances of the power supply voltage and the (temperature-dependent) I-V characteristic of the LEDs.
[0010] FIGS. 2 e - 2 h show the switch control signals CS 1 -CS 3 and the supply current IS drawn from the power supply in such a PWM mode.
[0011] It will be appreciated that, in both the constant current and PWM modes of operation, the quality of the image data received from the PDA 3 is related to the intensity at which each LED L 1 -L 3 is illuminated during respective scan periods. In addition, it is noted that the brighter the LED is illuminated, the less the sampling (i.e. integration), and hence scanning, time is required which means that the scanner can operate quicker. Therefore, it is desirable to operate the LEDs at or near their maximum current ratings without damaging the LEDs.
[0012] According to one known system, the illumination of an LED L 1 -L 3 is controlled by passing a predetermined current through the LED, the predetermined current being chosen according to known characteristics of the LED, power supply or switch resistance. However, due to the above mentioned variations caused by tolerances of the power supply voltage and the (temperature-dependent) I-V characteristic of the LEDs, setting a predetermined maximum current in this way does not enable an LED to be illuminated at its absolute maximum intensity, since some degree of safety margin must be incorporated to allow for such tolerances. If this safety margin in made small (i.e. in order to obtain the maximum possible current), then the possibility of damaging an LED is increased, i.e. due to an over-current being passed through the LED.
[0013] It is also known to illuminate an LED L 1 -L 3 by directly monitoring the amount of current flowing through the LED, and adjusting the current flow accordingly such that it operates near its maximum intensity. This involves monitoring the actual current flowing through LED. Operating an LED near its maximum intensity in this way can also result in the LED being damaged by an over-current, particularly when switching from one LED to another. In other words, when switching from one LED to another, if the initial current exceeds the maximum rating of the LED, then the LED will be damaged before the current monitor can detect and adjust the current flow.
[0014] It is therefore an aim of the present invention to provide a protection circuit and method for protecting a light source such as an LED, without having the disadvantages mentioned above.
SUMMARY OF THE INVENTION
[0015] According to a first aspect of the invention, there is provided a protection circuit for protecting a light source. The protection circuit comprises: a shunt path, the shunt path being selectively coupled in parallel with the light source; a detection circuit provided in the shunt path for determining the amount of current that will flow in the light source, prior to the light source being illuminated by a power supply; and a comparator for preventing or limiting the flow of current through the light source when the detection circuit determines that the amount of current will exceed a predetermined threshold.
[0016] Thus, according to the invention, a current detector is provided for monitoring the flow of current in a shunt path, the current detector being configured to disable or limit the flow of current through a light source when a predetermined threshold is reached. This aspect of the invention has the advantage of enabling the current flowing through a light source to be controlled by monitoring the current in the shunt path rather than the path having the light source, thus enabling the maximum current to be controlled without potentially damaging the light source.
[0017] According to another aspect of the present invention, there is provided a method of protecting a light source from over-current. The method comprises the steps of: selectively coupling a shunt path in parallel with the light source, such that current is diverted away from the light source and through the shunt path; detecting the amount of current flowing in the shunt path; and determining whether the amount of current flowing in the shunt path exceeds a predetermined threshold and, if so, preventing or limiting the flow of current in the light source when the shunt path is disconnected from being in parallel with the light source.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] For a better understanding of the invention, and to show more clearly how it may be carried into effect, reference will now be made, by way of example only, to the following drawings in which:
[0019] FIG. 1 shows a basic block diagram of a prior art system;
[0020] FIGS. 2 a - 2 h show the switch control signals and the current drawn in FIG. 1 when switching between LEDs in both constant current and PWM modes;
[0021] FIG. 3 shows a basic block conceptual diagram of a driver apparatus for driving an LED array, as described in co-pending application ID-06-021 by the same applicant;
[0022] FIG. 4 shows the current drawn in the circuit of FIG. 2 when switching between LEDs;
[0023] FIG. 5 shows a basic block conceptual diagram of a second arrangement for driving an LED array;
[0024] FIG. 6 shows a flow diagram relating to the switching sequence of switches S 1 -S 4 of FIG. 5 ;
[0025] FIGS. 7 a to 7 f are signal diagrams illustrating the switching sequence of switches S 1 -S 4 of FIG. 5 ;
[0026] FIG. 8 shows a basic block conceptual diagram of a third arrangement for driving an LED array;
[0027] FIGS. 9 a to 9 f are signal diagrams illustrating the switching sequence of switches S 1 -S 4 of FIG. 8 , when switching between LEDs in constant current mode;
[0028] FIGS. 10 a to 10 i are signal diagrams illustrating the switching sequence of switches S 1 -S 4 of FIG. 8 , when switching between LEDs in PWM mode;
[0029] FIG. 11 a provides a more detailed illustration of FIG. 8 , and in particular of the first current source IS 1 ;
[0030] FIG. 11 b shows a further optional improvement to FIG. 11 a;
[0031] FIG. 12( a ) illustrates a simplified example of the current source IS 2 used in FIG. 8 ;
[0032] FIG. 12( b ) illustrates an embodiment of an implementation of a protection circuit according to the present invention;
[0033] FIG. 12( c ) illustrates how the protection circuit of FIG. 12( b ) can be switched off; and, FIG. 12( d ) illustrates a more detailed example of the current source IS 2 described in FIGS. 8 and 12( a ).
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0034] In the following description of the preferred embodiments, reference is made to protecting a light source, the light source described in the context of an LED array comprising three LEDs, i.e. Red, Green and Blue. However, it will be appreciated that the invention is equally applicable to an LED array comprising two or more LEDs, or indeed any light source, including a single light source. Furthermore, any reference to LED is intended to cover any form of light source, not only visible light but non-visible light such as Ultra Violet (UV) and Infra Red (IR). Therefore, references to an LED or LED array in the preferred embodiments are intended to cover a light source or light source array more generally.
[0035] Prior to describing the protection circuit in detail with reference to FIGS. 12 b to 12 d , a description will first be given of the various arrangements for driving an LED array as illustrated in FIGS. 3 to 11 , corresponding to the subject matter claimed in co-pending application ID-06-021 by the present applicant.
[0036] FIG. 3 illustrates a basic block conceptual diagram of an arrangement for driving an LED array. The LED array comprises Red, Green and Blue LEDs L 1 , L 2 , L 3 . The LED switching circuitry S 1 , S 2 , S 3 is placed on the same monolithic structure, i.e. integrated circuit, as the analogue front end circuitry (AFE), i.e. the analogue processing circuitry that processes the image data received from a sensor device. To reduce the problems associated with LED switching transients interfering with the ADC process, a current source IS 1 is provided in the current path, preferably between the switches S 1 , S 2 , S 3 and ground. The current source IS 1 controls the flow of current through the LEDs L 1 , L 2 , or L 3 according to the states of switches S 1 , S 2 , S 3 .
[0037] The provision of the current source IS 1 enables the current flow through an LED (L 1 -L 3 ) to be controlled, rather than being merely switched on and off as found with the arrangement of FIG. 1 . The current through the LED is therefore defined by current source IS 1 , independently of the LED I-V characteristics or the supply voltage tolerance, so the LED current is as accurate as the accuracy of the current source. Adjustment of the current may be by direct adjustment of IS 1 or by PWM modulation of IS 1 and the switch signals.
[0038] The introduction of current source IS 1 also enables the rate of change of current (di/dt) through an LED to be controlled, for example by reducing the initial rate of change of current. FIG. 4 shows the supply current IS drawn by the circuit during the operation of the embodiment of FIG. 3 , when IS 1 is decreased in an S-shape fashion before each switch S 1 , S 2 , or S 3 is turned off, and increased in an S-shape fashion shortly after the next switch is turned on. As can be seen the current waveform IS has smoother S-shaped transitions than the current waveform IS of FIG. 2 , thereby reducing unwanted transient signals. The ground return current waveform is similar. Such S-shape waveforms may be generated by known techniques.
[0039] Thus, it can be seen that in the arrangement of FIG. 3 , the LED switches (S 1 -S 3 ) may be integrated on the same IC as the AFE processing circuitry, with the current source IS 1 being provided to reduce the generation of unwanted transient signals.
[0040] FIG. 5 shows a basic block diagram of a second arrangement for driving an LED array.
[0041] In a similar manner to FIG. 3 , an LED array comprises Red, Green and Blue LEDs L 1 , L 2 , L 3 . The LED switching circuitry S 1 , S 2 , S 3 is placed on the same monolithic circuit as the analogue front end circuitry (AFE) that drives the switching circuitry. A current source IS 1 is provided in the current path between the switches S 1 , S 2 , S 3 and ground, for controlling the flow of current through the LEDs L 1 , L 2 , L 3 .
[0042] According to this second arrangement a shunt path 50 is provided. The shunt path 50 comprises a switching device S 4 . The shunt path 50 having the switching device S 4 is provided in parallel with the LED array and switching circuitry. The problem relating to the LED switching transients interfering with the ADC is reduced because, as will be explained below, the shunt path 50 enables harmful transitions in the ground current flow to be reduced.
[0043] The following text describes the operation of the switching device S 4 in the shunt path 50 for reducing transient signals when switching from one LED to another.
[0044] The shunt path 50 is enabled when switching device S 4 is switched on. S 4 is switched on in sequence with the operation of the LED switches S 1 -S 3 as will be described in the following.
[0045] Referring to the flow chart of FIG. 6 , assume S 1 is switched on (i.e. S 1 is closed), step 61 , such that LED L 1 is passing a current I 1 from the positive supply VDD to ground GND via current source IS 1 .
[0046] During operation of a scanner, for example, once L 1 has achieved its task (e.g. used to illuminate the object while the red component of one line of its image is generated), L 1 has to be switched off by switching off S 1 (i.e. opening S 1 ), and S 2 has to be switched on (closed) so that L 2 passes its current I 2 (thus enabling L 2 to illuminate the object while the green component of one line of its image is generated).
[0047] According to this second arrangement, prior to switching off S 1 , switch S 4 is switched on, i.e. closed (step 63 ) such the Node A, on the high side of the current source IS 1 , is coupled to the supply voltage VDD.
[0048] Switching on S 4 has the effect of applying zero bias, or at least much reduced bias, to the LED L 1 . In other words, S 4 has the effect of steering the current away from the L 1 /S 1 current path. The current I 4 through S 4 is limited by the current source IS 1 , so the total supply or ground current is still IS 1 .
[0049] Even though the LED L 1 is effectively turned off, its associated switch S 1 is still however closed, i.e. switched-on.
[0050] S 1 can now be opened in step 65 , i.e. switched-off, thereby removing the LED L 1 from the circuit. The total supply or ground current is still IS 1 .
[0051] Switch S 2 is then closed, step 67 , thereby connecting LED L 2 to the circuit. Switch S 4 remains closed during this switching between L 1 and L 2 .
[0052] Once switch S 2 has been closed, S 4 can then be switched-off in step 69 , i.e. opened, thereby allowing LED L 2 to become forward biased such that a current I 2 passes from the positive supply VDD to ground GND via current source IS 1 .
[0053] This sequence is performed in a similar manner when changing from LED L 2 to another LED, for example L 3 , and so on.
[0054] It will therefore be realised that, rather than the power supply current IS having large switching current components being drawn in a disrupted, non-continuous manner from the power supply (i.e. corresponding to the currents I 1 , I 2 & I 3 being drawn by the respective LEDs during operation), the power supply current IS remains constant instead.
[0055] The circuit arrangement of FIG. 5 therefore performs differential current switching, such that current either flows through an LED (e.g. L 1 /S 1 ) and the current source IS 1 , or through the shunt path 50 and the current source IS 1 .
[0056] Thus, it will be appreciated that the circuit of FIG. 5 enables a substantially constant current IS to be drawn from the supply, and the same substantially constant current to flow in the ground return path, which reduces or substantially eliminates the ADC interference problem associated with the switching transients, such that it is possible that the ADC is capable of being integrated on the same IC as the LED switching array (S 1 -S 3 ). Integrating the switches on the same IC as the processing circuitry has the effect of minimising the cost associated with such an application.
[0057] FIGS. 7 a - 7 d provide a further illustration of the switching sequence of switches S 1 -S 4 of FIG. 5 . Prior to time t 1 the LED L 1 of FIG. 5 is being illuminated. In other words, switch S 1 is turned-on (i.e. due to the corresponding switch control signal CS 1 being high), while switches S 2 , S 3 and S 4 are turned-off (i.e. due to switch control signals CS 2 , CS 3 and CS 4 being low). The following operation is then performed in order to illuminate LED L 2 in place of LED L 1 . First, at time t, the switch S 4 is turned-on (i.e. by taking the switch control signal CS 4 high). This causes the shunt path 50 of FIG. 5 to become operational. Next, at time t 2 the LED L 1 is removed from the circuit by turning off switch S 1 (i.e. by taking the switch control signal CS 1 low). It will be appreciated that the current IS drawn from the supply remains constant despite LED L 1 being turned off, due to the effect of the shunt path 50 and current source IS 1 . At time t 3 switch S 2 is turned-on (i.e. by taking switch control signal CS 2 high) such that LED L 2 is connected to the circuit. Finally, at time t 4 the shunt path is removed by turning off switch S 4 (i.e. by taking the switch control signal CS 4 low).
[0058] A similar procedure is performed when switching from LED L 2 to LED L 3 , or from LED L 3 to LED L 1 .
[0059] FIG. 7 e illustrates the current IS drawn from the power supply of FIG. 5 when performing the switching operation described above. As can be seen, the current IS remains substantially constant.
[0060] In contrast, FIG. 7 f illustrates what power supply current IS would be drawn from a power supply (or the corresponding ground return current) when performing a switching operation in an arrangement as shown in FIG. 1 , i.e. if the shunt path 50 were absent.
[0061] Although not shown in FIGS. 7 a to 7 f , it will be appreciated that the arrangement of FIG. 5 can also be used in a PWM mode of operation, whereby the respective switches are controlled by altering the duty-cycle and/or frequency of their control signals, for example toggling CS 4 during a time when one of S 1 to S 3 are on.
[0062] It should be noted that it is preferable to switch Node A in a controlled manner so that the rate of change of voltage (dv/dt) at Node A is not excessive.
[0063] FIG. 8 shows a basic diagram of a third arrangement for driving an LED array.
[0064] As with FIGS. 3 and 5 , an LED array comprises Red, Green and Blue LEDs L 1 , L 2 , L 3 . The LED switching circuitry S 1 , S 2 , S 3 may form part of the same monolithic circuit as the analogue front end circuitry (AFE) that processes the image data received from the photo sensors. To reduce the problem associated with LED switching transients interfering with the ADC process, a current source IS 1 is provided in the current path between the switches S 1 , S 2 , S 3 and ground, for controlling the flow of current through the LEDs L 1 , L 2 , L 3 . A differential current path 50 (or shunt path) having a switching device S 4 is provided in parallel with the array of LEDs and corresponding switches S 1 -S 3 .
[0065] In addition, according to this arrangement, a second current source IS 2 is provided in the shunt path 50 . The second current source IS 2 enables the switching of the shunt path 50 to be performed in a more controlled manner. As will be described in greater detail below in relation to FIGS. 12 a to 12 d , there will be capacitance Cp associated with Node A, either parasitic capacitances or possibly an actual additional capacitor.
[0066] The second current source IS 2 is switched on by switching device S 4 in sequence with the LED switches S 1 -S 3 as was described above in connection with FIGS. 5 , 6 and 7 . The current drawn by the second current source IS 2 may be configured to be a predetermined amount greater than the current IS drawn through the LED L 1 , for example 5% greater. For example, it may be configured so that it can be switched between say 105% of IS 1 and 95% of IS 1 , for example by comprising a 95% current source and a 10% current source in parallel, separately switchable.
[0067] FIGS. 9 a - 9 d illustrate the switching sequence of switches S 1 -S 4 of FIG. 8 . Referring to FIGS. 9 a - d , just before switch S 1 is switched off at time t 2 , current source IS 2 is switched on via switch S 4 at time t, and draws a slightly larger current IS from the supply than the current IS previously drawn by LED L 1 from current source IS 1 . The difference in current between IS 2 and IS 1 serves to charge up the capacitance Cp on node A, until node A has risen to the voltage compliance limit of current source IS 2 and the output current of IS 2 reduces to equal IS 1 . In other words, a slightly larger current IS equal to IS 2 is drawn for a short time after time t 1 , as shown in FIG. 9 e . The modulation of the ground return current is substantially the same as that of the supply current IS. It is noted that the difference between IS 2 and IS 1 flows as a displacement current though Cp while node A is changing voltage.
[0068] When switching from using one LED, for example L 1 , to using another LED, for example L 2 , as before, S 1 can now be opened (switched off) at time t 2 so as to isolate LED L 1 , and S 2 can be closed at time t 3 to connect LED L 2 . During this switching operation switch S 4 remains closed.
[0069] Once switch S 2 is closed, current source IS 2 is reduced, to be less than IS 1 , and node A will decrease in voltage, at a rate determined by Cp and the difference between IS 1 and IS 2 . Node A will decrease in voltage until LED L 2 starts to take the difference current. Switch S 4 can then be switched off at time t 4 , i.e. opened, thereby stopping the current flow through IS 2 and fully forward biasing LED L 2 such that LED L 2 becomes illuminated and draws current from the supply driven by current source IS 1 .
[0070] This sequence is repeated when switching from LED L 2 to another LED.
[0071] Thus, it can be seen that, rather than the power supply having a large switching current IS being drawn from it as shown in FIG. 9 f (i.e. in a disrupted or non-continuous manner corresponding to the respective LED currents I 1 , I 2 , I 3 ), the power supply has a much smoother or continuous current IS drawn from it (as shown in FIG. 9 e ). The ground current will be equal to the constant current source IS 1 plus any brief transient currents charging Cp, so in this case the ground current will be IS 1 plus or minus 5%, for example. The supply current modulation will be the same. In contrast, FIG. 9 f illustrates what current IS PRIOR ART would be drawn in a prior art arrangement as shown in FIG. 1 , i.e. if IS 2 and S 4 were absent. As shown in FIG. 9 f , the current IS PRIOR ART drawn from the supply would switch between IS PRIOR ART and zero when switching from one LED to another.
[0072] The smaller switching current of the invention minimises the effect of switching transients such that the ADC is capable of being integrated on the same IC as the LED switching array and the IC can be placed on the scanner head. Such an integrated scheme has the effect of minimising the cost associated with such an application.
[0073] According to a further arrangement, the switches in the embodiment of FIG. 8 can be controlled using pulse width modulation (PWM) control signals. This could be achieved by toggling CS 1 etc, but to reduce supply and ground current ripple, CS 4 would need to be toggled in anti-phase. However, it is preferable to apply PWM to the shunt path. In other words, while switch S 2 say is closed, switch S 4 is controlled using a PWM control signal, thereby indirectly controlling the current I 2 passing through LED L 2 and therefore the average intensity of LED L 2 . FIGS. 10 a to 10 i show a PWM operation where L 1 is run at 100% duty cycle, L 2 at a small duty cycle and L 3 at an intermediate duty cycle.
[0074] According to a further embodiment, to allow variation of the LED currents without PWM switching, the current source IS 1 (and IS 2 ) can be varied in magnitude, by a common amount for all LEDs or differently for each LED. In other words, the current sources IS 1 and IS 2 can be fixed (i.e. set to operate in a predetermined mode of operation), or programmable, such that the operation of the current source is variable. Further discussion of this aspect of the invention will be provided after discussing the features of the current source IS 1 and the current source IS 2 in greater detail.
[0075] FIG. 11 a illustrates a more detailed example of a current source IS 1 that may be used in the arrangements of FIGS. 3 , 5 and 8 .
[0076] Referring to FIG. 11 a , a Current Reference Generator (CRG) basically sets the reference current Iref 1 for the whole circuit.
[0077] A reference voltage Vref supplied to an input of an amplifier in the CRG is preferably a bandgap reference voltage, thus being very accurate and stable.
[0078] In this particular example of the CRG, Vref is applied to the input of amplifier A 1 . Feedback around amplifier Al and transistor MN 0 forces the voltage on node Pin to equal Vref, and thus sets the current through the resistor Rext. This current passes through MN 0 to give the output current Iref 1 , equal to Vref/Rext.
[0079] “Pin” may represent an output pin on an IC. This allows a user to set the reference current Iref 1 to a desired value by altering the value of an external resistor, Rext. The ability of a user to set Iref 1 is preferable, since it relates to the type of LEDs (L 1 -L 3 ) that are used, with different LEDs having different characteristics. Alternatively Rext may be integrated with A 1 , possibly trimmable or digitally programmable to allow adjustment.
[0080] Current Source IS 1 comprises a series of controlled current sources MP 2 /MP 3 that define the currents Iref 2 and Iref 3 that are mirrored versions of Iref 1 .
[0081] Current source IS 1 comprises a variable current source, for example, a Current Digital-to-Analogue Converter (CDAC), which is made up of a series of 2 N−1 NMOS transistor and switch arrangements: where N is an integer greater than 1. It should be noted that Iref 2 & Iref 3 set up the current sinking capabilities of the CDAC as will be described below.
[0082] Within the CDAC, each individual switch is controlled so as to allow its associated NMOS transistor to connect to node A, the low-side of switches S 1 -S 4 . It should be noted that the CDAC NMOS transistors MLSB, . . . , MMSB have W/L ratios that are binary-weighted such that the each successive transistor, when switched on, is capable of sinking twice as much current as its predecessor. This is denoted by the labels 1 , 2 , . . . 2 N−1 close to each transistor MLSB, . . . , MMSB. Such an arrangement allows the current sunk by the CDAC to be accurately controlled over a wide range of current values.
[0083] As mentioned above, in operation the Red, Green and Blue LEDs L 1 -L 3 may require different current values to pass through them. This is in part due to the different characteristics of the LEDs, and also in part due to the required brightness of each LED during a scanning operation. The brighter the LED is made the less the sampling (i.e. integration), and hence scanning, time is required which means that the scanner can operate quicker. Therefore, it is desirable to operate the LEDs at or near their maximum current ratings without damaging the LEDs.
[0084] In the circuit of FIG. 11 a , the current Iref 2 through MN 1 is mirrored by MN 2 and MLSB, . . . , MMSB. To maintain accuracy despite variation in the voltage of node A, amplifier A 2 is introduced. The voltage on the inverting input of the A 2 is that of node A and varies during operation. Negative feedback from the non-inverting input of A 2 via the voltage inversion and gain introduced by MN 1 causes the gate voltage of MN 1 to settle out to that voltage necessary to sink the current Iref 2 output from MP 2 . MN 2 and MP 3 are not essential, but are introduced to maintain feedback in the case where all the CDAC NMOS transistors (MLSB-MMSB) are turned off (i.e. zero output current).
[0085] Modern electronic systems, and scanners in particular, now operate at low supply voltages to reduce power consumption, power dissipation, and active and passive component cost. For low voltage applications, such as where VDD=5v, the current source IS 1 is therefore selected and designed such that the maximum possible voltage drop exists across the LEDs L 1 -L 3 , while the minimum possible voltage drop exists across the current source IS 1 .
[0086] Assuming the CDAC comprises 8 bits (N=8), there are then 256 discrete levels (since 2 8 =256) from zero to Imax 3 in 255 steps, so each step (I LSB ) is Imax 3 /255, where Imax 3 is the maximum output current of the CDAC.
[0087] Assume that the maximum desired current through any one of the LEDs is Imax 1 (allowing for tolerances in the LEDs). Then, allowing some margin, Imax 3 <Imax 1 .
[0088] IS 2 , for correct operation, is configured to be capable of sourcing a current Imax 2 that is slightly greater, for reasons which will be apparent from the following description, than Imax 3 , such that:
Imax 2 >Imax 3
[0090] It is preferable to set the W/L ratio of MN 1 to be the same as that associated with the LSB NMOS transistor of the CDAC (as indicated by the number “1” just below the gate terminal). Therefore, MN 1 sinks a current Iref 2 that equals Imax 3 /255 which equals I LSB . It should be noted that Iref 2 can be scaled such that it is larger or smaller than Iref 1 , and this can be achieved by the sizing of the transistor W/L ratios of transistors MP 2 relative to transistor MP 1 . Also Iref 2 can be scaled with respect to Imax 3 by sizing MN 1 relative to the CDAC NMOS transistors MLSB, . . . , MMSB.
[0091] Transistor MN 2 is illustrated as having a parasitic Gate-Drain capacitance CGD. Such a capacitance exists in all of the NMOS transistors of the CDAC although they are not illustrated: such a parasitic capacitance is referred to as a Miller capacitance.
[0092] It should be noted that it is the combined Gate-Drain capacitance C GDTOT of all these capacitances (for MN 2 and those NMOS transistors switched on in the CDAC and possibly input transistors of A 2 ) that provides one mechanism for exacerbating the supply and ground current transients referred to earlier, giving rise to the requirement to render small the slew rates of node A as mentioned above in relation to FIG. 5 .
[0093] Referring to FIG. 5 , the effect C GDTOT has in the arrangement of FIG. 5 is that as the shunt path is enabled, i.e. as S 4 switches-on, and connects the supply voltage VDD to the high sides of MN 2 and the enabled CDAC NMOS transistors, there is a large dv/dt on node A. This is a.c. coupled through C GDTOT onto the gates of these transistors causing a spike in their currents, and these currents manifest as transients on the supply rails which will have an effect, to a greater or lesser effect depending on the value of C GDTOT , on the ADC.
[0094] A second effect, for example when using a current source IS 1 as shown in FIG. 11 a , is that the transient kick on the gates of MN 2 and the other parallel NMOS transistors MLSB, . . . , MMSB disturbs the bias point set by amplifier A 2 . A 2 will have only a finite bandwidth, so may take some time to settle out and re-establish the steady-state bias point. During this time the current output from the CDAC will deviate from the nominal. Hence, there is the need to control the slew rate of the voltage at Node A.
[0095] It should be noted that S 4 illustrated in FIG. 5 may be, in a very basic version of the invention, implemented as a variable resistor, resistive controlled switch etc., such that it is switched on in a controlled manner so as to avoid these high rates of change of voltage dv/dt on Node A. Similarly for IS 2 in the arrangement of FIG. 8 .
[0096] Due to the requirement of having the maximum possible voltage drop across the LEDs, and the minimum voltage drop across the current source IS 1 , the circuit of FIG. 11 a is susceptible to damage due to the high voltage at Node A of FIG. 5 . This is because the high voltage of Node A causes the voltage on the gate of MN 2 to rise due to Miller Capacitance effects, thus causing MN 2 to turn on.
[0097] In view of this possibility, FIG. 11 b shows an improvement in which a cascode transistor is connected to the drain of MN 2 , thereby shielding MN 2 from the voltage at Node A in FIG. 5 . The cascode transistor is biased by a reference voltage Vbias that may, for example, be supplied by a current source arrangement as shown.
[0098] The cascode transistor illustrated in FIG. 11 b and associated with MN 2 is preferably used as the basis for the respective switches associated with each of the CDAC NMOS transistors (not illustrated). Each “cascode” switch in the CDAC is controlled independently by a control signal that biases its respective cascode switch. The advantage of utilising the cascode switches in the CDAC is that it helps to isolate the CDAC and the ground supply rail from transients.
[0099] As mentioned above, in low voltage applications, it is preferable to have the maximum possible voltage drop across each of the LEDs so as to maximise the current through the LEDs, which implies the minimum possible voltage drop across each of the switches S 1 -S 3 and the current source IS 1 . It is noted that the on-resistance of the switches is substantially negligible hence the voltage drop is low in comparison to that associated with the current source IS 1 .
[0100] In order to minimise the voltage drop across current source IS 1 , there needs to be a low Drain-Source voltage drop across MN 1 and as well as MN 2 and the CDAC transistor and switch elements. However, to keep MN 2 in its saturation region, thereby providing a good current source, the V DSsat of these transistors must be kept low. The transconductance (gm) of an NMOS transistor is given approximately by:
[0000] gm= 2. IDS/V DSsat
[0101] Therefore, gm is inversely proportional to V DSsat and is therefore high for a low V DSsat .
[0102] Any mismatch in transistors MN 1 & MN 2 will result in an effective offset voltage at the gate terminal of MN 2 . Such an offset will, because of the high gain (gm) of MN 2 , result in errors. From the above formula, an effective gate voltage offset ΔV will give a fractional error ΔI in output current Iref 3 compared to Iref 2 where
[0000] Δ I/IDS=gm.ΔV/IDS= 2 .ΔV/V DSsat
[0103] This is especially true when the transistors within the CDAC are switched in as they too have high transconductances like MN 2 plus, they are binary-weighted and driven by the effective offset voltages of similar magnitude.
[0104] To achieve say 8-bit accuracy for say a 100 mV VDSsat of MN 1 requires sub-millivolt offsets. The random manufacturing offset voltage of a MOS transistor may be reduced by increasing its gate area. But since the offset is only inversely proportional to the square root of its gate area: this leads to impractically large devices for MN 1 and the CDAC devices. To overcome this, there may be provided a second, more accurate, current source, whereby the output of the first current source is calibrated against this second current source. In this arrangement, IS 2 comprises this second current source. IS 2 has much more headroom, almost all of VDD, so can include devices with much greater V DSsat and hence much smaller area for the required accuracy.
[0105] To provide a more detailed explanation of the current source IS 2 , reference will now be made to FIGS. 12 a to 12 d in which:
[0106] FIG. 12 a illustrates a simplified example of the current source IS 2 used in FIG. 8 ,
[0107] FIG. 12 b illustrates an implementation of a protection circuit for detecting a maximum current (Imax) according to the present invention,
[0108] FIG. 12 c illustrates how the protection circuit of FIG. 12 b can be disabled, and
[0109] FIG. 12 d illustrates a more detailed example of the current source IS 2 described in FIGS. 8 and 12 a.
[0110] Referring to FIGS. 12 b and 12 d , and explanation will now be given concerning how the shunt path 50 comprises a protection circuit 120 for preventing an over current from passing through an LED L 1 -L 3 . In FIG. 12 d : transistors MP 5 , MN 4 and MN 5 constitute the current source IS 3 in FIG. 12 b ; transistors MP 4 , MN 3 and MN 6 constitute the current source IS 5 in FIG. 12 b ; and transistors MP 10 , MP 11 and MN 7 constitute the current source IS 4 in FIG. 12 b.
[0111] Referring to FIG. 12 d , transistor MP 4 is driven from a suitable voltage, for example Node X of FIG. 11 a , to deliver a current Iref 4 , another replica of Iref 1 . This is mirrored by transistors MN 3 and MN 6 and then mirrored again by transistors MP 9 and MP 8 . Most of MP 8 's output current is then output via MP 6 of the protection circuit 120 to provide an output current I 4 to deliver the current Imax 2 when the LEDs are shunted by current source IS 2 .
[0112] MP 7 of the protection circuit 120 mirrors the current Imax 2 flowing through transistor MP 6 . The W/L ratio of MP 7 may be, for example, 1/1000 of that of MP 6 . This means that the protection circuit 120 diverts only a small fraction of MP 8 's output current, and only consumes minimal power when performing its current detection function.
[0113] MP 5 is driven with the same gate voltage as MP 4 to give another replica current Iref 5 , which is then mirrored via MN 4 and MN 5 . MN 5 is connected to MP 7 : the voltage at their common drain node will go high if MP 7 carries more current than MN 5 and low if MP 7 carries less current than MN 5 . Since I(MP 7 ) is a known fraction (say 1/1000) of I(MP 8 ), this flags whether I(MP 8 ) is less than or greater than some predetermined threshold, this predetermined threshold being determined mainly by the transistor size ratios of mirrors MP 6 :MP 7 , MN 5 :MN 4 , and the ratio of MP 4 , MP 5 to say MP 1 of FIG. 11 a.
[0114] The comparator Ca compares the voltage at this common drain node of transistors MP 7 and MN 5 with a reference voltage Vref. Thus if the maximum current flowing through MP 8 exceeds the predetermined threshold then the comparator output signal I LEDmax is set so as to indicate this condition.
[0115] In operation, the output of MP 6 is connected to the output of IS 1 as shown and conducts the current I 4 . If IS 1 is less than 14 (i.e. IMP 6 ) then node A will rise, until the source voltage of MP 6 , i.e. the drain voltage of MP 8 has risen enough to take MP 8 out of saturation into triode operation, i.e. past the output voltage compliance of MP 8 regarded as a current source. MP 7 will still output the same fraction of 14 (IMP 6 ), so the comparator flags whether I(IS 1 ) is less than or greater than the predetermined threshold of 14 (IMP 6 ).
[0116] If however IS 1 is greater than I 4 (IMP 6 ) then node A will fall until node A reaches the voltage compliance of IS 1 when delivering 14 defined by MP 8 . The current through MP 7 will then be high, so the comparator Ca will flag this. This “flag” signal I LEDmax can then be used to inhibit the turn-on of switches S 1 , . . . , S 3 to prevent the IS 1 current being steered to the LEDs, at least until the digital control to IS 1 CDAC has been adjusted to decrease to a desired safe level, thereby protecting the LED.
[0117] Thus, according to the invention, the protection circuit 120 enables the LEDs to be illuminated at their maximum intensity, while preventing an over-current from flowing through any of the LEDs L 1 -L 3 .
[0118] In this implementation of IS 2 , its output current I 4 is switched on and off by controlling the gate of MP 8 using a switch S 4 *. (Note that S 4 * open corresponds to S 4 being closed in previous diagrams, and vice versa.)
[0119] As discussed above, it is desirable to limit the voltage slew rate on node A. This is implemented with the aid of capacitor C and controlled charging currents from MN 6 and MP 11 . Referring to FIG. 12 b , it should be noted that the current IIS 4 sourced by current source IS 4 (MP 11 ) is twice that of the current IIS 5 sourced by current source IS 5 (MN 6 ) such that: when S 4 * is open, current source IS 5 is sinking a current which pulls the gates of transistors MP 8 and MP 9 , as well as the low-side of capacitor C towards ground. Transistors MP 8 and MP 9 turn on, at a rate influenced by the capacitor C, and MP 8 mirrors a magnified version of the current flowing through transistor MP 9 . When S 4 * is closed current source IS 4 effectively pulls the gates of transistors MP 8 and MP 9 , as well as the low-side of capacitor C towards the supply VDD and transistors MP 8 and MP 9 turn off, at a rate influenced by the capacitor C, thereby gradually stopping the current ( 14 ) flowing to current source IS 1 .
[0120] The capacitor C, which is a relatively large capacitor, connected between the common gate terminals of transistors MP 8 and MP 9 acts to delay the rise in the gate voltages of transistors MP 8 and MP 9 such that rather than these two transistors turning hard on in a relatively short period, the turn-on time of these transistors is relatively slower. This has the effect of reducing the rate of change of voltage dv/dt at Node A. It will be appreciated that the sizes of transistors employed and the value of the capacitor, together with the LED current values can be altered so as to produce the desired effect, i.e. a reduced dv/dt at Node A, accordingly.
[0121] Referring to FIG. 12( c ), it is preferable to insert a switching mechanism, as illustrated by switches S 5 and S 6 into the protection circuit 120 (Imax Det.). By inserting these switches, the current that initially flows through the LED is indicative of the current flowing through the LED for the duration that it is conducting current such that the LED current monitoring can be disabled. S 5 and S 6 are driven by inverse signals such that when S 5 is closed, S 6 is open and vice-versa.
[0122] From the above it can be seen that the arrangement of the preferred current source shown in FIGS. 12 b , 12 c and 12 d allows the current set for each of the LEDs to be measured: if it exceeds a maximum then the LED is not connected, so the LED is protected. This is active whenever the shunt current path is enabled, either when switching between LEDs or in the “off” time between pulses in PWM mode. This has the advantage of enabling the current to be monitored and controlled in the shunt path, rather than in the path actually containing an LED.
[0123] It should be noted that the W/L ratio of MP 8 may be scaled if desired. For instance W/L for MP 8 may be scaled to be 2 N* 1.2 times (i.e. for an 8 bit=256*1.2 times) that of MP 9 , to give a nominal IS 2 scaled by 1.2 over IS 1 . Similarly W/L of say MN 5 may be scaled to adjust the limit threshold.
[0124] In a further embodiment, rather than MP 8 being a fixed size, it can be broken into a number, say 256 segments, and controlled digitally to act as a current DAC. Since it has more available headroom, it can be physically small. With MP 8 CDAC set to the desired current, IS 1 can be iterated until it is within an LSB of I(MP 8 ) (strictly I(MP 6 )). In this way the accuracy requirements and hence the physical size of the CDAC in IS 1 can be kept within reasonable limits.
[0125] It will be appreciated that the embodiments described above offer the choice of PWM or absolute control of the LED current control. To control the brightness of illumination and so the imaging period, two techniques are therefore available, i.e. adjusting the absolute current or varying the on-time of a PWM control.
[0126] The protection circuit 120 for detecting a maximum LED current, enables scan time to be minimised, by maximising LED brightness. This is achieved by running the LED near it maximum current rating. To prevent damage to the LED, the LED current is checked to be within the maximum current rating of the LED, prior to connecting the LED to the power supply.
[0127] It is noted that, in the description of the above mentioned arrangements, it is assumed in FIG. 9 e , for example, that LED L 2 and LED L 3 draw the same current as LED 1 , i.e. I 1 =I 2 =I 3 . It will be appreciated however that, in practice, the optimum operational current of each LED might be different. Also the operational currents may be required to be adjustable, perhaps to adjust the illumination of the object to match the sensitivity of a particular sensor or reflectance of the object.
[0128] It will also be appreciated that the current source IS 1 in each of the arrangements can be configured to provide a predetermined current profile, and/or configured such that the current profile is variable (for example depending upon which of the LEDs L 1 -L 3 is being switched). In other words, the current source IS 1 can be fixed (i.e. set to operate in a predetermined mode of operation), or programmable, such that the operation of the current source is variable.
[0129] It will also be appreciated that, while the preferred embodiment of the invention relates to providing a protection circuit when switching between LEDs in an LED array, the invention is equally applicable to providing a protection circuit for a single LED or light source, such that the single LED or light source is not damaged by an over-current.
[0130] It should be noted that the above-mentioned embodiments illustrate rather than limit the invention, and that those skilled in the art will be able to design many alternative embodiments without departing from the scope of the appended claims or drawings. The word “comprising” does not exclude the presence of elements or steps other than those listed in a claim, “a” or “an” does not exclude a plurality, and a single element or other unit may fulfil the functions of several units recited in the claims. Any reference signs in the claims shall not be construed so as to limit their scope. | A light source is protected by selectively coupling a shunt path in parallel with the light source, such that current is diverted away from the light source and through the shunt path. A detection circuit detects the current flowing in the shunt path when the shunt path is connected in parallel with the light source. A comparator determines whether the current flowing in the shunt path exceeds a predetermined threshold and, if so, prevents or limits the flow of current when the shunt path is disconnected from being in parallel with the light source. In this way, a current detector is provided for monitoring the flow of current in a shunt path, the current detector being configured to disable or limit the flow of current through a light source when a predetermined threshold is reached. This aspect of the invention has the advantage of enabling the current flowing through a light source to be controlled by monitoring the current in the shunt path rather than the path having the light source, thus enabling the maximum current to be controlled without potentially damaging the light source. | 8 |
BACKGROUND OF THE INVENTION
The present invention relates to a reversible refrigeration system or heat pump. Many current heat pump systems use a four-way, two-position valve which is reversed in order to defrost the system. Such conventional hot gas defrost causes undesirable strong pressure changes and associated oil forming at the compressor. In addition, the four-way, two position valves used in such systems are complex and expensive and have several disadvantages.
One disadvantage of a four-way, two-position or reversing valve is that heat is lost by condition and leakage from the hot and the cold refrigerant lines within the valve. U.S. Pat. No. 2,991,631 recognizes this problem. For example, in column 1, at lines 34-40, the patent notes that "Another important feature of the present invention is that there is a minimum amount of heat transfer between various conduits in the four-way valve to minimize that heat transfer which otherwise would be a dead load on the refrigeration compression system . . .". This heat loss or "dead load" problem can significantly decrease the efficiency of a heat pump system. The present invention substantially eliminates this problem by eliminating the four-way, two-position reversing valve.
Another long standing problem with four-way, two-position valves is leakage of working fluid from the high to low pressure side of the valve. U.S. Pat. No. 2,741,264, line 32 et seq. documents this problem. The present invention employs simpler valves which are more likely to provide leak-free operation.
Four-way, two-position reversing valves also typically have problems associated with unequal thermal expansion of metal parts within the valve, a problem related to the first two problems discussed above. The temperature differential between the suction and discharge lines of the system compressor causes thermal stresses in the four-way valve. That is, the cold portions of the valve tend to expand less (or contract more) than the hot portions. This unequal expansion causes sealing problems and contributes to binding of the moving parts within the valve. U.S. Pat. No. 4,055,056, column 1, line 27, discusses this problem. The valves of the present system do not simultaneously have cold and hot gasses flowing through them and, accordingly, do not undergo thermal straining to as large a degree as the four-way, two-position valves typically used in current systems.
In addition to the above advantages, the present invention provides for a condensor bypass defrost, again without the use of a four-way, two-position reversing valve. Condensor bypass defrost is more reliable than full reverse defrost typically used in four-way valve systems since compressor operating conditions change less abruptly during condensor bypass defrost. Further, in condensor bypass defrost, the first in-rush of hot refrigerant is used to defrost the evaporator rather than to warm up the accumulator, thus increasing defrost efficiency (the accumulator, not shown in FIG. 1, is located at the compressor suction port).
The present invention also provides a stop mode of operation which increases system efficiency by preventing hot, liquid refrigerant from escaping from the evaporator immediately following compressor shut down at the end of a cycle.
SUMMARY OF THE INVENTION
The present invention is a reversible refrigeration system comprising a compressor, first and second heat exchangers, an expansion valve, three three-way valves, and apparatus for connecting the elements of the system so that the system will operate in a heating mode with the three three-way valves adjusted for heating operation, in a cooling mode with the three three-way valves adjusted for cooling operation, and in a defrost mode with the three three-way valves adjusted for defrost operation.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates a preferred embodiment of the present invention.
FIG. 2 illustrates the location of an optional valve in an alternate preferred embodiment of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
As schematically illustrated in FIG. 1, a preferred embodiment of the present invention comprises first and second heat exchangers 10 and 20 which may be, and typically are, identical. Each heat exchanger 10 and 20 operate either as a condensor or as an evaporator, and each comprises first and second ports labeled 1 and 2.
The system further comprises a compressor 30 having a suction port S for intaking refrigerant and a discharge port D for discharging refrigerant at a higher pressure.
The system further comprises an expansion valve 40 for reducing the pressure of the refrigerant, the expansion valve having first and second ports labeled 1 and 2 respectively.
The system as illustrated in FIG. 1 further comprises first, second and third three-way valves labeled 100, 200 and 300 respectively. Each three-way valve has first, second and third ports labeled 1, 2 and 3 respectively.
Although the various ports of the various components are typically interconnected by piping, at least some of these ports may be directly connected without piping in appropriate circumstances. As illustrated in FIG. 1, the first port 1 of first three-way valve 100 is connected to the first port 1 of first heat exchanger 10 via piping. The second port 2 of first three-way valve 100 is connected via piping to the discharge port D of compressor 30, and third port 3 of first three-way valve 100 is connected via piping to first port 1 of expansion valve 40.
Second three-way valve 200 has its first port 1 connected via piping to second port 2 of first heat exchanger 10. The second port 2 of second three-way valve 200 is connected via piping to first port 1 of expansion valve 40, and the third port 3 of second three-way valve 200 is connected to suction port S of compressor 30.
The first port 1 of third three-way valve 300 is connected to the first port 1 of second heat exchanger 20. The second port 2 of third three-way valve 300 is connected via piping to suction port S of compressor 30, and the third port 3 of third three-way valve 300 is connected to discharge port D of compressor 30.
The second port 2 of second heat exchanger 20 is connected to the second port 2 of expansion valve 40.
Each three-way valve 100, 200 and 300 has a first position for permitting refrigerant flow between its first and third ports 1 and 3 respectively, and a second position for permitting refrigerant flow between its first and second ports 1 and 2 respectively.
As more fully explained below, the present system will operate in a heating mode with each of the three-way valves 100, 200 and 300 in the first position. The system will operate in a cooling mode with all three three-way valves 100, 200 and 300 in the second position. The system will operate in a defrost mode with the first three-way valve 100 in the second position and the second and third three-way valves 200 and 300 in the first position.
As previously indicated, in the heating mode of operation, each of the three three-way valves 100, 200 and 300 are in the first position, that is, with refrigerant flowing between the first and third ports 1 and 3 of each of the three valves.
In the heating mode of operation, pressurized refrigerant in its vapor state is discharged by discharge port D of compressor 30. The pressurized refrigerant flows through third three-way valve 300 and into second heat exchanger 20 which would normally be indoors and giving off heat of condensation as the refrigerant is condensed from vapor to liquid form. After the refrigerant is condensed to liquid form in heat exchanger 20, the liquid refrigerant flows out of heat exchanger 20, through expansion valve 40, through first three-way valve 100, and into first heat exchanger 10 which would typically be outdoors and absorbing heat of vaporization to turn the liquid refrigerant into vaporized refrigerant. After vaporizing, refrigerant flows out of heat exchanger 10, through second three-way valve 200, and into suction port S of compressor 30.
Thus, in operating the present system in its heating mode, first heat exchanger 10 operates as an evaporator while second heat exchanger 20 operates as a condensor.
For optimum performance, lines or piping carrying the refrigerant between components are kept well insulated and/or separated, thus minimizing heat transfer from hot to cold lines. As previously mentioned, this is in contrast to prior art systems using four-way, two-position reversing valves in which considerable heat is typically lost between components of the valve.
In using the present system in its cooling mode, all three three-way valves 100, 200 and 300 are in the second position, the second position permitting refrigerant flow between the first and second ports 1 and 2 of the three valves.
In the cooling mode of operation, pressurized refrigerant leaves discharge port D of compressor 30, flows through first three-way valve 100, and enters first heat exchanger 10 which is normally outdoors and looses heat of condensation to the environment as the refrigerant is turned from vapor to liquid. After condensing in heat exchanger 10, the refrigerant flows through second three-way valve 200, through expansion valve 40, and into second heat exchanger 20 which is normally indoors and absorbing heat of vaporization as the liquid refrigerant is vaporized. After vaporizing, the refrigerant flows out of second heat exchanger 20, through third three-way valve 300, and into suction port S of compressor 30.
Thus, in its cooling mode of operation, first heat exchanger 10 operates as a condensor and second heat exchanger 20 operates as an evaporator. Note again that, for optimum performance, lines or piping carrying the refrigerant are kept well insulated and/or separated, thus minimizing heat transfer from hot to cold lines.
As previously mentioned, the present system may be defrosted in a condensor bypass defrost mode. This mode is made operational by placing first three-way valve 100 in the second position (for flow between the first and second ports 1 and 2) and the second and third three-way valves 200 and 300 in the first position (for flow between the first and third ports 1 and 3).
In the condensor bypass defrost mode, compressed vaporized refrigerant is discharged from discharge port D of compressor 30. The refrigerant then passes through first three-way valve 100, through first heat exchanger 10, through second three-way valve 200 and into suction port S of compressor 30. This continuous flow of hot vaporized refrigerant through first heat exchanger 10 melts the frost from the outside of heat exchanger 10, the exchanger that is prone to frost problems when its temperature of operation is lower than water freezing temperature.
Such a method of defrosting condensor 10 has advantages over more typical systems that use a four-way, two-position reversing valve; such systems defrost the condensor by reversing the four-way valve so that the condensor becomes the evaporator and the frost melts away. Such prior art defrosting techniques cause considerable undesirable pressure changes and associated oil foaming in the compressor, and subsequent oil removal by being carried with the refrigerant stream. In addition, such defrost techniques also necessitate the tempering or heating of air flowing past the indoor heat exchanger since otherwise the heat pump will cool the indoor air.
Thus, through the present invention, the defrost mode does not require tempering of indoor air during the defrost mode since the indoor heat exchanger is not functioning as an evaporator. In addition, since third three-way valve 300 is in its first position during defrost (thus permitting refrigerant flow between ports 1 and 3), its hot refrigerant content is also available to defrost evaporator or heat exchanger 10.
The present invention is also capable of being used in a stop mode, which is effected when compressor 30 is turned off. The objective of a stop mode is to substantially prevent hot refrigerant from escaping from heat exchanger 20 so that the indoor/outdoor temperature differential (the temperature differential between heat exchangers 10 and 20) can be maintained for as long as possible without turning on the compressor. In providing a stop mode within the present system, two alternatives described below are available.
In the system thus far described, three-way valves 100, 200 and 300 each required only two positions, a first position for providing fluid flow between first and third ports 1 and 3 and a second position for providing fluid flow between first and second ports 1 and 2. By providing first and second three-way valves 100 and 200 with a third closed position for preventing refrigerant flow through these valves, a stop mode of operation may be obtained by closing valves 100 and 200. This prevents refrigerant flow between heat exchangers 10 and 20 and maximizes stop mode temperature differential between heat exchangers 10 and 20 over a period of time without operating compressor 30 (as previously noted, compressor 30 is shut off during a stop mode). For the stop mode of operation using closable valves 100 and 200, third three-way valve 300 may be left in either of its first or second positions (it would normally be easiest to leave three-way valve 300 in the same position as it was in prior to selecting the stop mode).
In an alternate approach to obtaining a stop mode of operation with the present system, all three three-way valves may remain as two position valves as previously described provided that a two-way valve 400 is inserted in the system. Two-way valve 400 may be added in either of two locations. In FIG. 2, two-way valve 400 is shown inserted between three-way valve 100 and expansion valve 40, a first port 1 of two-way valve 400 being connected to a third port 3 of first three-way valve 100, and a second port 2 of two-way valve 400 connected to the first port 1 of expansion valve 40. Alternately, two-way valve 400 may be connected between expansion valve 40 and second heat exchanger 20. Although this arrangement is not illustrated, it could be implemented by connecting first port 1 of two-way valve 400 to second port 2 of expansion valve 40 and by connecting second port 2 of valve 400 to second port 2 of second heat exchanger 20.
Two-way valve 400 has an open position for permitting refrigerant to flow between its first port 1 and its second port 2 and a second position for preventing refrigerant flow through the valve. By having two-way valve 400 in its open position, one of the heating, cooling or defrosting modes of operation may be selected as previously described. By having the two-way valve in its closed position, a stop mode of operation is obtained, thereby preventing refrigerant flow between heat exchangers 10 and 20 and maximizing stop mode temperature differential between heat exchangers 10 and 20 over a period of time without operating compressor 30, thus reducing heat pump cycling energy losses.
Accordingly, either approach to obtaining stop modes of operation into the present system may be easily implemented in order to maximize the temperature differential between the heat exchangers without operating the compressor, thus increasing system efficiency. As previously described, if no stop mode of operation is available, refrigerant can communicate between the two heat exchangers with a resultant loss of heat.
The present invention is to be limited solely in accordance with the scope of the appended claims since others skilled in the art may devise other embodiments still within the limits of the claims. | Disclosed is a reversible refrigeration system comprising a compressor, first and second heat exchangers, an expansion valve, three three-way valves, and apparatus for connecting the elements of the system so that the system will operate in a heating mode with the three-way valves adjusted for heating operation, in a cooling mode with the three three-way valves adjusted for cooling operation and in a defrost mode with the three three-way valves adjusted for defrost operation. | 5 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application is the U.S. National Stage of PCT/CN2013/088935 filed Dec. 10, 2013, the entire contents of which is incorporated herein by reference in its entirety.
TECHNICAL FIELD
The present invention relates to a method for preparing tantalum powder of capacitor grade with high nitrogen content, tantalum powder of capacitor grade prepared thereby, and anode and capacitor prepared from tantalum powder.
BACKGROUND
Metal tantalum is a valve metal. It can form a layer of dense oxide film on its surface to have a property of unilateral conduction. An anode film made of tantalum has chemical stability (especially in acidic electrolyte), high resistivity (7.5×10 10 Ω·cm), high dielectric constant (27.6) and small leakage current. Furthermore, the anode film has advantages including a broad range of working temperature (−80 to 200° C.), high reliability, anti-vibration and long service life. It is an ideal material for preparing tantalum capacitor with small volume and high reliability.
Tantalum capacitor is an electronic device with tantalum as metal anode, having a dielectric oxide film which is directly formed on the surface of tantalum through the oxidation of the anode. Tantalum powder has a very high specific surface area. The specific surface area remains high even after pressing and sintering due to its characteristic pore structure, and thereby the resulting capacitor has high specific capacitance.
Among the methods for preparing tantalum powder, the reduction method of potassium fluotantalate with sodium is the most widely used and the most maturely developed preparation method worldwide.
The reduction method of potassium fluotantalate with sodium is a method in which tantalum powder of capacitor grade is prepared, using K 2 TaF 7 and Na as main feedstocks, and using a halide salt such as NaCl, KCl or a mixture of halide salts as diluent, with the following main reaction mechanism:
K 2 TaF 7 +5Na=Ta+5NaF+2KF (1)
The above reaction occurs between K 2 TaF 7 and liquid sodium, in the nitrogen atmosphere and at certain temperature. The tantalum powder resulting from the reduction is water washed and acid washed, and is then heat-treated. Subsequently the powder is reduced and deoxidized with magnesium, and the final tantalum powder with high purity is obtained.
Currently tantalum powder of capacitor grade is developing in a direction of high specific capacitance and high purity. It is well known that the specific capacitance of tantalum powder is in proportion to its specific surface area. In other words, the smaller the mean particle diameter of tantalum powder is, the higher the specific surface area is, and the higher the specific capacitance is. The key technology to achieve high specific capacitance of tantalum powder is the preparation of tantalum powder with smaller mean particle diameter. In respect to the reduction method of potassium fluotantalate with sodium, the core of the development is to control the formation, the distribution and the growth of the crystal nucleus during the reduction with sodium by controlling the reduction conditions including the compositions of potassium fluotantalate and diluent dissolving salts, the reduction temperature, the rate of injection of sodium etc., in order to prepare the tantalum powder having certain specific surface area and particle diameter. A mechanical method is to obtain tantalum powder with finer particles by controlling the conditions of hydrogenation milling or ball milling. The reduction of halide with hydrogen uses preparation technology of nanoscale powder, and the particle size of the resulting tantalum powder is in nanoscale with very high specific surface area.
Doping is an important technical means to achieve high specific capacitance of tantalum powder, and thus is generally used in the production and the development of tantalum powder with high specific capacitance. The main purposes of doping during the preparation method of tantalum powder are: 1) to refine the tantalum powder; and 2) to inhibit the growth of grains of the tantalum powder, to the most possibly maintain higher specific surface area of the tantalum powder, and to reduce loss of specific capacitance of the tantalum powder. Doping can be conducted during various methods. Doped elements commonly used include N, Si, P, B, C, S, Al, O etc. and compounds thereof. Doped elements generally segregate at the surfaces of grain-boundaries, reacting with tantalum at high temperature to form various compounds of tantalum. Doping comprises not only incorporating one element in one step, but also doping multiple elements in multiple steps. By this way, tantalum powder can be refined, and at the same time loss of specific capacitance of tantalum powder can be reduced.
It is a widespread operation to dope nitrogen in tantalum powder in the tantalum powder industry, especially in the production of tantalum powder with high specific capacitance.
U.S. Pat. No. 6,876,542 provides a production method of nitrogen-containing metal powder, and porous sintered body and solid electrolytic capacitor using the metal powder. The nitrogen containing metal powder has a ratio W/S between the nitrogen content W (ppm) and the specific surface area S (m 2 /g) as measured by a BET method, that falls within a range from 500 to 3000. The patent further provides a method in which nitrogen is introduced during the reduction to increase nitrogen content in tantalum powder.
U.S. Pat. No. 7,066,975 provides nitrogen-containing metal powder, production method thereof, and porous sintered body and solid electrolytic capacitor using the metal powder. The patent provides nitrogen-containing metal powder which is a solid solution containing 50-20,000 ppm nitrogen, in which the metal is particularly tantalum, preferably containing P, B, O or a combination thereof. It is characterized that nitrogen is in solid solution form, and the mean particle diameter of the nitrogen-containing metal powder is in a range of 80 to 360 nm.
U.S. Pat. No. 7,473,294 provides nitrogen-containing metal powder, production method thereof, and porous sintered body and solid electrolytic capacitor using the metal powder. The patent provides nitrogen-containing metal powder (having surface layer and inner layer) which is a solid solution containing 50-20,000 ppm nitrogen. The nitrogen is in solid solution form. The metal is tantalum. The nitrogen uniformly permeates from the surface layer of the metal to the inner layer. And the particle diameter of the metal powder is ≦250 nm.
U.S. Pat. No. 6,432,161 provides another nitrogen-containing metal powder, production method thereof, and porous sintered body and solid electrolytic capacitor using the metal powder. The patent provides a production method of nitrogen-containing metal powder, comprising a compound of niobium or tantalum is reduced with a reducing agent, and nitrogen is simultaneously incorporated into the reaction system, and nitrogen-containing niobium or tantalum powder in solid solution form is formed, wherein the nitrogen is simultaneously incorporated in niobium or tantalum powder. The patent is an alternative to the reduction method of potassium fluotantalate with sodium, which is suitable for the reduction doping nitrogen of other compounds of niobium or tantalum.
Chinese patent application CN1498144A relates to a preparation method of sintered particles. The particles is made of a mixture of refractory metals and refractory metal nitrides. It is found that the particles have higher proportion of intra-aggregate pores as than those singly made of refractory metals or nitrides of refractory metals. There is provided improved powder of capacitor grade, anode and capacitor made thereby. Where the mixture contains 50 to 75 w/w % of refractory metal nitrides, the porosity and the total intrusion volume of the particles are maximized. The total pore surface area of the particles is 50% higher than that of single refractory metal nitrides. A substrate consisting of a powder mixture of 50/50 or 25/75 w/w % refractory metals/refractory metal nitrides generates solid capacitor with higher recovery rate of capacitor and lower ESR. To be brief, tantalum and tantalum nitride or niobium and niobium nitride are directly mixed, and are shaped by pressing, to form anode of capacitor.
Accordingly, the methods for doping nitrogen in tantalum powder used in prior art focus on the incorporation of nitrogen-containing gas into the reaction system. The nitrogen is present in tantalum powder in solid solution form. However, such methods for doping nitrogen is less effective, and tantalum powder with high nitrogen content cannot be obtain, and the amount of doped nitrogen cannot be accurately controlled. Therefore, there is still need for a method for doping nitrogen in tantalum powder having good effectiveness and controllability.
SUMMARY OF THE INVENTION
In a first aspect of the present invention, there is provided a method for preparing tantalum powder of capacitor grade, comprising the steps of:
(1) KCl and KF are fed into a reactor, and temperature is increased;
(2) K 2 TaF 7 is fed to the reactor, and tantalum nitride powder is simultaneously fed hereto depending on desired amount of doped nitrogen;
(3) the reactor is heated to 880 to 930° C., and the temperature is kept;
(4) the reactor is cooled to 800 to 880° C., and sodium is fed hereto;
(5) the temperature is kept at 880 to 930° C. until the reaction temperature drops rapidly; and
(6) the tantalum powder resulted from step (5) is after-treated, and nitrogen-doped tantalum powder product is obtained.
The present invention achieves tantalum powder with higher nitrogen content than those in prior art. And the amount of doped nitrogen in the tantalum powder can be accurately controlled, allowing desired amount of nitrogen to incorporate into the tantalum powder, providing the tantalum powder product with corresponding electrical performance. Therefore, the electrical performance of the resulting product precedes those of the tantalum powder made by traditional methods for doping nitrogen.
In one embodiment, the tantalum powder for preparing the tantalum nitride powder which is fed in step (2) has essentially the same mean particle diameter as the tantalum powder product resulted from step (6), and thus the final tantalum powder has uniform particle size.
In one embodiment, the amount of doped nitrogen is 1000 to 3000 ppm, allowing the product to have lower leakage current and the tantalum powder to have preferred electrical performance.
In one embodiment, the weight ratio between the sodium which is fed in step (4) and the K 2 TaF 7 which is fed in step (2) is in a range of 30 to 32:100. In one embodiment, step (2) is performed at 900 to 950° C. In one embodiment, steps (3) to (5) are performed under agitation. In some embodiments, agitator blades are used, and are elevated in step (4). In one embodiment, the time for keeping the temperature in step (3) is at least 1 hour. In one embodiment, the after-treatment in step (6) includes crushing, water washing, acid washing, pelletizing or a combination thereof.
In a second aspect of the present invention, there is provided tantalum powder prepared by the preparation method according to the first aspect of the present invention.
In a third aspect of the present invention, there is provided a tantalum anode made of the tantalum powder according to the second aspect of the present invention.
In a fourth aspect of the present invention, there is provided a tantalum capacitor comprising the tantalum anode according to the third aspect of the present invention.
The tantalum powder and the tantalum anode and the tantalum capacitor made thereof according to the present invention have high nitrogen content and accurately controllable amount of doped nitrogen, and thus have preferred electrical performance than the tantalum powder, the tantalum anode and the tantalum capacitor in prior art.
Above embodiments can be combined as required, and the resulting technical solutions are still within the scope of the present invention.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 shows a curve graph in which the electrical performance of the products of the Examples according to the present invention and the Comparative Example change with nitrogen content.
In the FIGURE, DCL represents leakage current K×10 −4 (μA/μFV), and LOT represents series numbers of the samples.
DETAILED DESCRIPTION
The present invention provides a method for doping nitrogen in tantalum powder, comprising the steps of:
Firstly, KCl and KF are charged into a reducing furnace, and temperature is increased according to predetermined program. When the temperature reaches 900 to 950° C., K 2 TaF 7 is added through feeding inlet, and tantalum nitride powder made of tantalum powder of the same grade is added simultaneously. At this time the temperature is cooled to about 800° C. Agitation is started after the charging, and the reducing furnace is heated to 880 to 930° C. The temperature is kept, and the time for keeping temperature is recorded. After a period of time, the agitator blade is elevated, and the agitation continues, leading to uniform temperature and composition of the molten salt system. The temperature is decreased to 800 to 880° C., and sodium is added smoothly. Agitation is kept as the sodium is added, to timely spread the resulting heat and keep uniform temperature of the whole molten salt system, and at the same time to timely transfer particles of the formed tantalum powder outside of the reaction zone and avoid rapid growth of the particles which results in poor uniformity. The temperature is kept at a relatively stable level in a range of 880 to 930° C. The weight ratio between sodium and K 2 TaF 7 added in the reduction reaction is in a range of 30 to 31:100. When the reaction temperature drops rapidly, it can be determined that the reduction reaction is over. Raw tantalum powder with uniformly doped nitrogen is obtained.
During the above reaction, the raw tantalum powder is collided and contacted with the added tantalum nitride powder, allowing the nitrogen in the tantalum nitride to spread between the particles, resulting in primary particles of the tantalum powder with high nitrogen content and relatively uniform doping.
The tantalum powder with relatively uniform nitrogen content agglomerates, resulting in a bulk material. The material is subject to steps including crushing, water washing, acid washing, pelletizing etc., resulting in tantalum powder product with high nitrogen content.
The tantalum powder with high nitrogen content can be used to produce tantalum anode and tantalum capacitor by the methods in prior art.
In this context, the term “tantalum powder of the same grade” is referred that the tantalum powder for preparing the tantalum nitride powder which is added in the reaction has essentially the same mean particle diameter as the tantalum powder product, and thus the final tantalum powder has uniform particle size.
EXAMPLES
In order to further illustrate the present invention, embodiments according to the present invention are described with reference to the Examples. However, it is understood that the description is for further illustration of the characteristics and advantages of the present invention, rather than limitation to the scope of the claims of the present application.
The Fisher particle diameter referred in the Examples the particle diameter measured with Fisher Sub-sieve sizer, also known as Fisher transmitter. The specific surface area of the particles is obtained according to the height difference (h) between the liquid levels in the two tubes of differential pressure gauge that is caused by the pressure difference generated by the atmosphere passing through the bed of powder. And then he mean particle size is calculated according to the equation: the mean particle size (in micron)=6000/volume specific surface area (in square centimeter/gram).
Example 1
120 kg of KCl and 100 kg of KF were charged into a reducing furnace, and temperature was increased according to predetermined program. When the temperature reached 920° C., 60 kg of K 2 TaF 7 was added through feeding inlet, and 1500 g of tantalum nitride powder made of raw tantalum powder of Fisher particle diameter in a range of 0.3 to 0.45 μm was added simultaneously as seed crystal. After the charging, the temperature was elevated to 930° C., and the time for keeping temperature was recorded. After holding 1 hour at 930° C., the agitator blade was elevated, and the agitation continued. The temperature was decreased to 820° C. with a blower, and sodium was added smoothly. Agitation was kept as the sodium was added. The temperature was kept at about 900° C. The amount of sodium added in the reduction reaction was 18.5 kg. When the reaction temperature dropped rapidly, it was determined that the reduction reaction was over and the reduced material was obtained. Then the reduced material was subject to steps including crushing, water washing, acid washing, pelletizing etc., resulting in nitrogen-doped tantalum powder product.
Example 2
120 kg of KCl and 100 kg of KF were charged into a reducing furnace, and temperature was increased according to predetermined program. When the temperature reached 930° C., 60 kg of K 2 TaF 7 was added through feeding inlet, and 1000 g of tantalum nitride powder made of raw tantalum powder of Fisher particle diameter in a range of 0.3 to 0.45 μm was added simultaneously as seed crystal. After the charging, the temperature was elevated to 930° C., and the time for keeping temperature was recorded. After holding 1 hour at 930° C., the agitator blade was elevated, and the agitation continued. The temperature was decreased to 820° C. with a blower, and sodium was added smoothly. Agitation was kept as the sodium was added. The temperature was kept at about 900° C. The amount of sodium added in the reduction reaction was 18.5 kg. When the reaction temperature dropped rapidly, it was determined that the reduction reaction was over and the reduced material was obtained. Then the reduced material was subject to steps including crushing, water washing, acid washing, pelletizing etc., resulting in nitrogen-doped tantalum powder product.
Example 3
120 kg of KCl and 100 kg of KF were charged into a reducing furnace, and temperature was increased according to predetermined program. When the temperature reached 930° C., 60 kg of K 2 TaF 7 was added through feeding inlet, and 800 g of tantalum nitride powder made of raw tantalum powder of Fisher particle diameter in a range of 0.3 to 0.45 μm was added simultaneously as seed crystal. After the charging, the temperature was elevated to 930° C., and the time for keeping temperature was recorded. After holding 1 hour at 930° C., the agitator blade was elevated, and the agitation continued. The temperature was decreased to 820° C. with a blower, and sodium was added smoothly. Agitation was kept as the sodium was added. The temperature was kept at about 900° C. The amount of sodium added in the reduction reaction was 18.5 kg. When the reaction temperature dropped rapidly, it was determined that the reduction reaction was over and the reduced material was obtained. Then the reduced material was subject to steps including crushing, water washing, acid washing, pelletizing etc., resulting in nitrogen-doped tantalum powder product.
Example 4
120 kg of KCl and 100 kg of KF were charged into a reducing furnace, and temperature was increased according to predetermined program. When the temperature reached 910° C., 60 kg of K 2 TaF 7 was added through feeding inlet, and 600 g of tantalum nitride powder made of raw tantalum powder of Fisher particle diameter in a range of 0.3 to 0.45 μm was added simultaneously as seed crystal. After the charging, the temperature was elevated to 930° C., and the time for keeping temperature was recorded. After holding 1 hour at 930° C., the agitator blade was elevated, and the agitation continued. The temperature was decreased to 820° C. with a blower, and sodium was added smoothly. Agitation was kept as the sodium was added. The temperature was kept at about 900° C. The amount of sodium added in the reduction reaction was 18.5 kg. When the reaction temperature dropped rapidly, it was determined that the reduction reaction was over and the reduced material was obtained. Then the reduced material was subject to steps including crushing, water washing, acid washing, pelletizing etc., resulting in nitrogen-doped tantalum powder product.
Example 5
120 kg of KCl and 100 kg of KF were charged into a reducing furnace, and temperature was increased according to predetermined program. When the temperature reached 900° C., 60 kg of K 2 TaF 7 was added through feeding inlet, and 300 g of tantalum nitride powder made of raw tantalum powder of Fisher particle diameter in a range of 0.3 to 0.45 μm was added simultaneously as seed crystal. After the charging, the temperature was elevated to 930° C., and the time for keeping temperature was recorded. After holding 1 hour at 930° C., the agitator blade was elevated, and the agitation continued. The temperature was decreased to 820° C. with a blower, and sodium was added smoothly. Agitation was kept as the sodium was added. The temperature was kept at about 900° C. The amount of sodium added in the reduction reaction was 18.5 kg. When the reaction temperature dropped rapidly, it was determined that the reduction reaction was over and the reduced material was obtained. Then the reduced material was subject to steps including crushing, water washing, acid washing, pelletizing etc., resulting in nitrogen-doped tantalum powder product.
Comparative Example 6
120 kg of KCl and 100 kg of KF were charged into a reducing furnace, and temperature was increased according to predetermined program. When the temperature reached 930° C., 60 kg of K 2 TaF 7 was added through feeding inlet. After the charging, the temperature was elevated to 930° C., and the time for keeping temperature was recorded. After holding 1 hour at 930° C., the agitator blade was elevated, and the agitation continued. The temperature was decreased to 820° C. with a blower, and sodium was added smoothly. Agitation was kept as the sodium was added. The temperature was kept at about 900° C. The amount of sodium added in the reduction reaction was 18.5 kg. When the reaction temperature dropped rapidly, it was determined that the reduction reaction was over and the reduced material was obtained. Then the reduced material was subject to steps including crushing, water washing, acid washing, pelletizing etc., resulting in a product which we needed.
Nitrogen was not purposely doped in this Comparative Example. The nitrogen in the sample was brought in when the tantalum powder formed oxide film in the air.
The resulting six samples were analyzed. The comparison results of the properties are shown in Table 1.
TABLE 1
Element contents in the tantalum powder (in ppm)
Smaple
O
C
N
Fe
Si
P
K
Ex. 1
3260
28
3420
10
12
130
30
Ex. 2
3780
35
2300
12
15
120
30
Ex. 3
3920
36
1820
15
16
130
32
Ex. 4
4030
30
1400
13
14
120
33
Ex. 5
4150
28
810
16
12
130
34
Com. Ex. 6
4220
28
520
12
14
126
31
All of the test methods of the element in the tantalum powder are according to Chinese national standards such as GB/T 15076.8-2008, GB/T 15076.9-2008, GB/T 15076.12-2008, GB/T 15076.14-2008, GB/T 15076.15-2008, GB/T 15076.16-2008, and Chemical Analytic Technique for Tantalum and Niobium.
As seen from Table 1, the amounts of doped nitrogen in Examples 1 to 5 are higher than that in Comparative Example 6. It means that nitrogen-doping effect through tantalum nitride powder is better than that of traditional nitrogen-doping method. Tantalum powder with high nitrogen content can be obtained by the method according to the present invention.
TABLE 2
Physical Properties of the Tantalum Powder
Smaple
Fsss (μm)
SBD (g/cc)
+80 (%)
−400 (%)
Ex. 1
1.60
1.50
0.10
30.16
Ex. 2
1.54
1.52
0.02
36.80
Ex. 3
1.56
1.50
0.06
25.96
Ex. 4
1.50
1.45
0.00
28.92
Ex. 5
1.64
1.56
0.10
30.52
Com. Ex. 6
1.62
1.52
0.12
28.68.
In Table 2:
FSSS represents Fisher particle diameter of tantalum particles.
SBD represents apparent density of powder, referring to tap density measured after the powder freely fills a standard vessel under specified conditions, i.e. mass of the powder per unit volume when packed loosely, expressed in g/cm 3 . It is a method property of powder. The measuring method used herein is funnel method in which powder freely drops from a funnel hole at a certain height to fill a vessel.
+80(%) represents the proportion of particles larger than 80 mesh in all particles, and −400(%) represents the proportion of particles smaller than 400 mesh. The mesh refers to mesh number per inch (25.4 mm) on a screen.
TABLE 3
Comparison of Electrical Performance (sintering condition:
1250° C./20 min, Vf: 20 V, pressed density: 5.0 g/cc)
I
K × 10 −4
CV
tgδ
SHV
Sample
(μA/g)
(μA/μFV)
(μFV/g)
(%)
(%)
Ex. 1
35.0
3.6
97815
45.7
1.8
Ex. 2
22.0
2.2
101520
40.7
1.2
Ex. 3
24.4
2.4
100108
41.6
1.5
Ex. 4
34.0
3.5
98763
44.0
1.9
Ex. 5
36.0
3.7
96600
43.1
1.3
Com. Ex. 6
44.5
4.7
95060
40.5
2.1
All of the test method and device of the electrical performance of tantalum powder are according to Chinese national standards GB/T 3137-2007, Experiment Technique for Electrical Performance of Tantalum Powder.
In Table 3:
Sintering condition: 1250° C./20 min means that the tantalum powder is sintered at 1250° C. for 20 minutes to obtain anode block.
Vf: 20V means energization at voltage of 20V.
Pressed density: 5.0 g/cc means that the pressed density of the anode block is 5.0 g/cc.
K×10 −4 (μA/μV) represents leakage current, hereinafter referred to as K value. Capacitance media cannot be absolutely non-conducting, so when direct voltage is applied to capacitance, the capacitor may generate leakage current. If the leakage current is too high, the capacitor may heat up and fail. When specified direct working voltage is applied to the capacitor, it will be observed that the change of charging current is initially great, and decreases over time, and reaches a relatively stable state until a final value. This final value is called as leakage current.
CV (μFV/g) represents specific capacity, i.e. electric quantity that can be released by unit weight of cell or active substrate.
tgδ (%) represent capacitor loss. Capacitor loss is actually reactive power consumed by a capacitor. Thus it can be defined as that capacitor loss also refers to the ratio between reactive power consumed under electric field and total consumed power, expressed as: tangent of capacitor loss angle=reactive power/total power, or tangent of capacitor loss angle=reactive power×100/total power (resulting value is a percentage)
SHV (%) represents volume shrinkage of capacitor anode block.
TABLE 4
Comparison of Electrical Performance (sintering condition:
1300° C./20 min Vf: 20 V, pressed density: 5.0 g/cc)
I
K × 10 −4
CV
tgδ
SHV
Sample
(μA/g)
(μA/μFV)
(μFV/g)
(%)
(%)
Ex. 1
33.0
3.5
93500
43.0
2.7
Ex. 2
20.0
2.1
96921
38.6
1.6
Ex. 3
28.6
3.0
95169
40.1
1.8
Ex. 4
33.1
3.4
96096
42.8
2.1
Ex. 5
33.2
3.4
96491
43.0
2.2
Com. Ex. 6
33.0
3.5
92500
45.0
2.7
The data in the above tables (especially in Table 3) show that with regard tantalum powder of capacitor grade, specific capacitance (CV value) of the tantalum powder increases, leakage current (K value) decreases, and loss (tgδ%) decreases as the amount of doped nitrogen increases. However, when nitrogen content is more than 3000 ppm (Example 1), specific capacitance (CV value) of the tantalum powder decreases, leakage current (K value) and loss (tgδ%) begin to increase, and the electrical performance degrades.
If the amount of doped nitrogen is relatively low (Example 5), there is problems such as too low specific capacitance (CV value) of the tantalum powder, too high leakage current (K value) and loss (tgδ%), which is not preferred.
FIG. 1 shows a curve graph in which K values of the products of Examples 1 to 5 and Comparative Example 6 change with nitrogen content.
Therefore, with regard to the tantalum powder with high specific capacitance according to the present invention, when nitrogen content is controlled in a range of 1000 to 3000 ppm, leakage current of the sample is relatively low, and electrical performance of the tantalum powder is preferred.
The present invention enable effective control of nitrogen content in tantalum powder by adding TaN with high nitrogen content as seed crystal during the reduction. Also, the tantalum prepared by this method has uniform nitrogen content and relatively small particle diameter of primary particles. The greatest characteristic of this method is that the nitrogen in tantalum nitride diffuses between particles of the tantalum powder, with substantially no loss, and thus the nitrogen content can be accurately controlled.
The description and the Examples according to the present invention disclosed herein are illustrative. It is apparent to a person skilled in the art that the present invention includes other more embodiments, and the actual scope and spirit of the present invention is defined by the claims. | A method for preparing a tantalum power of capacitor grade, comprising: solid tantalum nitride is added when potassium fluotantalate is reduced by sodium. The method increases the nitrogen content in the tantalum powder, and at the same time improves the electrical performance of the tantalum powder. The specific capacitance is increased, and the leakage current and loss is improved. The qualification rate of the anode and the capacitor product is also improved. The method is characterized in that the nitrogen in the tantalum nitride diffuses between the particles of the tantalum powder, with substantially no loss, and thus the nitrogen content is accurate and controllable. | 2 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority from U.S. Provisional Patent Application No. 60/864,796, filed on Nov. 8, 2006, the entirety of which is incorporated herein.
TECHNICAL FIELD
[0002] The technical field of the invention relates to an apparatus and method for reducing energy consumption in both domestic and professional clothes dryers by reducing drying time of clothes being dried. This result is obtained by using an absorbent, quick drying and/or negatively charged fabric that is mounted to the drum of the clothes dryer.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0003] Not Applicable
REFERENCE TO SEQUENCE LISTING, A TABLE, OR A COMPUTER PROGRAM LISTING COMPACT DISC APPENDIX
[0004] Not Applicable
BACKGROUND OF THE INVENTION
[0005] As is well known, a typical clothes dryer is a large appliance for drying clothes, bedding, towels, and other linens. Moisture is removed from clothes by a combination of air, heat, and motion. Gas and electric dyers differ mainly in the heat source. Both gas and electric models use a motor to turn a drive belt. The drive belt revolves the drum which holds the clothing. A blower directs air past the heat source and into the drum where it draws lint and moisture from the fabrics through a lint screen and out an exhaust duct. Appliance controls regulate the options, such as temperature and drying time. Some machines use mechanical timers while others rely on digital electronics. Clothes dryers constitute one of the most energy intensive appliances. However, even with the advancement of technology, clothes dryers are one of the few appliances that have not demonstrated significant reduction of energy consumption.
[0006] According to the report on “Residential Consumption of Electricity by End Use, 2001” produced by the Energy Information Administration, clothes dryers in the United States used 65.9 billion kWh. Note that this number does not take into account the energy used by commercial clothes dryers (e.g., Laundromats, Hotels, Prisons, Hospitals, etc.). According to one source, as compared to clothes washers, “energy consumption does not vary significantly among comparable models of clothes dryers.” See Worldwise, at the web page: http://www.worldwise.com/clothesdryers.html. Consequently, “ENERGY STAR does not label Clothes Dryers because most Clothes Dryers use similar amounts of energy.” See Energy Star, at the web page: http://www.energystar.gov/index.cfm?c=clotheswash.pr_clothes_washers. Given the need to reduce energy consumption in clothes dryers and the fact that technology has reached a limitation in making cloths dryers more efficient, this invention, Quick Time Drying Apparatus and Method for Clothes Dryers is being proposed and has been developed.
[0007] This invention is believed to be useful in meeting the growing demand by both power companies and government agencies to reduce energy use. Further, it should be noted that the effectiveness of Quick Time Drying Apparatus and Method for Clothes Dryers is not limited to electric powered clothes dryers, but is also applicable to clothes dryers operated by either natural gas or propane gas.
[0008] Below is a list of several government agencies and nongovernmental organizations (NGOs) that would likely value the benefits of Quick Time Drying Apparatus and Method for Clothes Dryers: This list is not exhaustive.
[0009] a. U.S. Department of Energy
[0010] b. American Council for an Energy-Efficient Economy
[0011] c. Appliance Standards Awareness Project
[0012] d. International Energy Agency
[0013] e. Energy Efficient Strategies
[0014] f. Energy Federation Incorporated
[0015] g. Energy Start
[0016] h. Energy Efficiency Form
[0017] i. Natural Resources Defense Council
[0018] j. International Electrotechnical Commission
[0019] k. Alliance to Save Energy
[0020] l. American Council for an Energy Efficient Economy
[0021] m. California Institute for Energy Efficiency
[0022] n. Office of Energy Efficiency and Renewable Energy
BRIEF SUMMARY OF THE INVENTION
[0023] In one general aspect, there is provided a drying apparatus for placing inside of a clothes dryer to increase the efficiency of drying clothes in the clothes dryer. The drying apparatus includes a fabric material (that may be perforated) mounted to a surface, the fabric material being configured to absorb moisture from moist clothes in the dryer and being characterized by being one or both of fast drying and highly absorbent of moisture.
[0024] Embodiments of the drying apparatus may include one or more of the following features. For example, the surface may be an attachment means for mounting to the inside of the dryer. The attachment means may include at least one magnetic strip, whereby the magnetic strip can be magnetically attached to the drum of the clothes dryer. The attachment means may include at least one Velcro® strip to attach the fabric material to the inside of the dryer. The attachment means may include at least one Velcro® strip affixed to at least one magnetic strip, whereby the magnetic strip is configured to be attached to the inside of the dryer and the Velcro® strip is configured to be attached to the fabric material.
[0025] The drying apparatus may be placed inside of the dryer drum on a surface on one or more of the drum, the door or a fin or baffle extending from the drum.
[0026] The surface may be a surface of an object that is configured to be placed within the inside of the dryer. The surface may have openings into the object. The object may be hollow and perforated. The object may have one or more of a round shape, an elongated shaped, and a disc shape.
[0027] The fabric material may be nylon. The fabric material may be a sheet of nylon. The drying material may be further characterized by being one or more of odor resistant; durable; mildew resistant; heat resistant, and having a negative or positive charge.
[0028] Use of the drying apparatus may reduce the amount of time it would take for clothes to dry in the dryer relative to drying clothes in the absence of the drying apparatus. The drying apparatus may be reusable and not limited to a one time use.
[0029] In another general aspect there is provided a method for removing moisture from clothes in a clothing dryer. The method includes providing a drying apparatus for placing inside of a clothes dryer to increase the efficiency of drying clothes in the clothes dryer. The drying apparatus includes a fabric material mounted to a surface, the fabric material being configured to absorb moisture from moist clothes in the dryer and being characterized by being one or both of fast drying and highly absorbent of moisture.
[0030] Embodiments of the method may include one or more of the following features or those described above. For example, the method may further include placing the drying apparatus in the clothes dryer with moist clothes and operating the dryer.
[0031] The surface may include an attachment means for mounting to the inside of the dryer. The attachment means may include at least one Velcro® strip affixed to at least one magnetic strip, whereby the magnetic strip is configured to be attached to the inside of the dryer and the Velcro® strip is configured to be attached to the fabric material. The fabric material may be nylon.
[0032] Other embodiments of Quick Time Drying Apparatus and Method for Clothes Dryers may include one or more of the following features. For example, the method may include the use of one or more balls covered with the fabric material to maximize contact between the clothes and the fabric material as a means to reduce drying time even further. The ball may be hollow and perforated to allow the fabric to dry quicker.
[0033] The details of various embodiments of the invention are set forth in the accompanying drawings and the description below. Other features and advantages of the invention will be apparent from the description, the drawings, and the claims. For example, the invention may provide one or more of the following advantages: (a) reusable (i.e., depending on further testing of the product, e.g., it could be used up to 2,000 drying cycles); (b) portable (i.e., the product can be easily removed and placed in another clothes dryer, which is especially helpful for Laundromat users); (c) versatile (i.e., can be used in most clothes dryer); (d) inexpensive to make, buy and use; (e) saves wear-and-tear on clothes dryers due to less drying time; (f less wear-and-tear on clothes due to reduced drying time; (g) reduction in greenhouse gas emissions, as less drying time means less energy required; and (h) resilient (i.e., due to the fact that the special material dries extremely fast there is no need to wait in-between dryer loads).
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0034] FIG. 1 is a perspective view of a drum of a conventional clothes dryer the without the fabric material used.
[0035] FIG. 2 is a perspective view of a sheet of fabric material (24×17 inch) with Velcro® strips mounted underneath.
[0036] FIG. 3 is a perspective view of magnetic strips with Velcro® attached underneath the magnetic strips.
[0037] FIG. 4 is a perspective view of magnetic strips attached to the sheet of fabric material of FIG. 2 .
[0038] FIG. 5 is a perspective view of the sheet of fabric material magnetically attached to each section of the clothes dryer drum.
[0039] FIG. 6 is a perspective view of a prior art clothes dryer.
DETAILED DESCRIPTION OF THE INVENTION
[0040] Referring to FIGS. 1 and 6 , conventional clothes dryers include a drum rear wall 5 , a drum 6 , a dryer drum opening 7 , one or more drum seals 10 , a drum belt 15 , a drum roller 20 , a motor 25 , a pulley 30 , an adjustable foot 35 , a door interlock switch 40 , a door 45 , a lint screen 50 , a timer 55 , a temperature control switch 60 , a start switch 65 , and an electrical plug 70 , a drum 6 , a drum rear wall 5 , and a dryer drum opening 7 to receive moist clothes into the chamber created by the drum 6 , drum rear wall 5 and dryer drum opening 7 . The conventional dryer receives the moist clothes and tumbles the clothes in the drum chamber while passing heated air through the drum chamber. The heated air heats the moisture in the clothes and thereby evaporates the moisture from the clothes to dry the clothes.
[0041] The inventor believes that the uniqueness of the inventions described herein resides in how the invention functions and what it is able to accomplish while drying clothes. In particular, the inventor is not aware of any product that absorbs moisture from wet clothes inside a clothes dryer to reduce the time required for drying the clothes. The invention does this by using a drying apparatus to physically transfer moisture from wet clothes in the dryer to a fabric material component of the dryer apparatus in the dryer that readily absorbs moisture but also easily gives up moisture.
[0042] Referring to FIG. 2 , in one embodiment of the dryer apparatus, a sheet of fabric material 1 is mounted within the dryer to contact moist clothes, absorb moisture from the clothes, and then allow the moisture to evaporate from the sheet of fabric material 1 . In one implementation of the sheet, the size of the sheet of fabric material 1 is 24×17 inches, although the dimensions can be varied as necessary to customize the apparatus to any dryer or for other needs. Underneath the longer side of the sheet of fabric material 1 is placed a 2 inch wide Velcro® strip 2 , “loop” part (see FIG. 2 ). In order to secure the fabric material 1 to the drum of the clothes dryer a 2 inch wide magnetic strip 3 (24 inches) is attached to the fabric material 2 (see FIG. 4 ). This is done by using a layer of glue 4 to glue the 24 inch long and 2 inch wide Velcro® strip 3 to the magnetic strip (see FIG. 3 ). Referring to FIG. 5 , if the drum of the clothes dryers is divided into three sections one 24×17 sheet can be placed in one section or each section. Optionally or alternatively, the sheet of fabric may also be attached to each fin on the tumbler.
[0043] It should be readily understood that the dimensions of the sheet, magnetic strips and Velcro® strips, as well as the structure of the combined sheet of fabric material, magnetic strips, and Velcro® strips, can be varied so long as the concept is followed of placing a fabric material within the dryer drum to absorb moisture from moist clothes upon contact with the moist clothes. Thus, the fabric material can be used in different shapes and configurations to allow them to be strategically placed on and in the dryer drum and other components to more efficiently absorb the moisture or release the moisture.
[0044] For example, in a second embodiment of the dryer apparatus, or for use as a separate component of the invention, the fabric material may be applied to a ball such that the ball is partially or completely covered with the same fabric material as in the implementation above. The ball may be solid or hollow with perforated holes. Further, the ball may have openings such that the fabric is affixed or otherwise attached to solid material surrounding opening but also covers the openings. In this manner, the inside of the ball also can be used to accept moisture from the fabric material. One or more dryer balls may be used along with or separately from the sheet of fabric material 1 described above. The balls may be made in a variety of sizes; in one implementation the balls are approximately half the size of a basketball. In others they are the size of a tennis ball, a ping pong ball, a volley ball, etc. Of course, in this embodiment the balls may be shaped in a variety of configurations, such as a rod, an elongated object, a disc, etc. that can tumble within the dryer with the clothes to absorb moisture from the moist clothes. This implementation will further enhance the effectiveness of the sheet of fabric material 1 by increasing contact between the wet clothes and the fabric.
[0045] What enables the invention to reduce drying time will now be described. The invention uses a fabric material that absorbs moisture from wet clothes; however, this same material dries extremely fast. In one embodiment, the fabric material is comprised of a hydrophilic nylon, although any hydrophilic, fast drying material may be used. This fabric material relies upon physical contact with the moist clothes to transfer the moisture from the moister clothes to the less moist fabric material. As a potential second mechanism that relies upon the polarity of water, the fabric material optionally may be negatively or positively charged in order to further draw moisture from the wet clothes using this second mechanism. When the clothes dryer is in operation, the drum rotates, and as it rotates the clothes are forced to be in contact with the fabric material. Each time the clothes touch the fabric material, the material absorbs some moisture from the clothes; however, due to the nature of the fabric, the fabric dries extremely fast and thereby allowing it to continually absorb moisture. In particular, during a portion of the rotational cycle of the drum, the fabric material will be in contact with the moist clothes and thus will absorb moisture from the moist clothes. However, in a remainder portion of the rotational cycle of the drum, the moist clothes will be falling away from the drum and therefore the fabric material will be exposed only to the heated air in the dryer. During this portion of the rotational cycle, the fabric material will be able to evaporate off some of the moisture. Further, because the fabric material is expected to have at least a portion in contact with the hot dryer drum, the fabric material will be maintained at an elevated temperature, thereby providing additional energy to evaporate off the moisture before contacting wet clothes again in the next rotational cycle of the drum.
[0046] Although the above embodiment uses a hydrophilic nylon for the fabric material, other materials may be used instead or along with the hydrophilic nylon. In general, the fabric material, which may be a material such as a polymer or natural fiber, should have one or more of the following characteristics: (a) hydrophilic (highly absorbent), (b) ability to dry extremely fast, and (c) negatively or positively charged. In addition, the following characteristics may add additional benefits if the fabric material has these properties: (a) odor resistant, (b) durable, (c) mildew resistant, and (d) heat resistant.
[0047] The inventor has tested a working prototype of the sheet of fabric material 1 . The prototype has proven successful in reducing drying time. A test was completed using a 10 year old residential clothes washer and clothes dryer. As a means to test the viability of the invention four large towels were washed on a normal cycle. The towels were then weighed (15 lbs) and then placed in the clothes dryer without the sheet of fabric material. After 22 minutes the weight of the four towels were recorded. The same four towels were then placed in the washing machine in the same manner as before. When finished they were once again weighed to ensure the weight was the same as the previous test. The prototype was inserted into the clothes dryer, the four towels were then placed in the same dryer and the four towels dried for the same amount of time. After 22 minutes, the towels were weighed again. There was a difference of 1 lbs between the towels when dried with the sheet of fabric material and when dried without the sheet of fabric material. This shows that the sheet of fabric material increases the rate at which moisture is removed from the towels, thereby reducing the drying time.
[0048] While several particular forms of the invention have been illustrated and described, it will be apparent that various modifications and combinations of the invention detailed in the text and drawings can be made without departing from the spirit and scope of the invention. For example, references to materials of construction, methods of construction, specific dimensions, shapes, utilities or applications are also not intended to be limiting in any manner and other materials and dimensions could be substituted and remain within the spirit and scope of the invention. Accordingly, it is not intended that the invention be limited, except as by the appended claims. | The invention relates to an apparatus and methods for reducing energy consumption in both domestic and professional clothes dryers by reducing drying time of clothes being dried. This is result is obtained by using an absorbent, quick drying and/or negatively charged fabric material that is mounted to the drum of the clothes dryer or allowed to circulate with the drying clothes. The drying apparatus is placed inside of a clothes dryer to increase the efficiency of drying clothes in the clothes dryer. The drying apparatus includes a fabric material mounted to a surface, the fabric material being configured to absorb moisture from moist clothes in the dryer and being characterized by being one or both of fast drying and highly absorbent of moisture. | 3 |
FIELD OF THE INVENTION
[0001] The present invention relates generally to medical devices, and particularly relates to implantable devices for treating narrowing of coronary or peripheral vessels in humans.
BACKGROUND OF THE INVENTION
[0002] Cardiovascular disease, including atherosclerosis, is the leading cause of death in the U.S. The medical community has developed a number of methods for treating coronary heart disease, some of which are specifically designed to treat the complications resulting from atherosclerosis and other forms of coronary arterial narrowing.
[0003] The most impelling development in the past decade for treating atherosclerosis and other forms of coronary narrowing is percutaneous transluminal coronary angioplasty, hereinafter referred to simply as “angioplasty” or “PTCA”. The objective in angioplasty is to enlarge the lumen of the affected coronary artery by radial hydraulic expansion. The procedure is accomplished by inflating a balloon within the narrowed lumen of the coronary artery. Radial expansion of the coronary artery occurs in several different dimensions and is related to the nature of the plaque. Soft, fatty plaque deposits are flattened by the balloon and hardened deposits are cracked and split to enlarge the lumen. The wall of the artery itself is also stretched when the balloon is inflated.
[0004] PTCA is performed as follows: A thin-walled, hollow guiding catheter is typically introduced into the body via a relatively large vessel, such as the femoral artery in the groin area or the brachial artery in the arm. Access to the femoral artery is achieved by introducing a large bore needle directly into the femoral artery, a procedure known as the Seldinger Technique. Once access to the femoral artery is achieved, a short hollow sheath is inserted to maintain a passageway during PTCA. The flexible guiding catheter, which is typically polymer coated, and lined with Teflon, is inserted through the sheath into the femoral artery. The guiding catheter is advanced through the femoral artery into the iliac artery and into the ascending aorta. Further advancement of the flexible catheter involves the negotiation of an approximately 180 degree turn through the aortic arch to allow the guiding catheter to descend into the aortic cusp where entry may be gained to either the left or the right coronary artery, as desired.
[0005] After the guiding catheter is advanced to the ostium of the coronary artery to be treated by PTCA, a flexible guidewire is inserted into the guiding catheter through a balloon and advanced to the area to be treated. The guidewire provides the necessary steerability for lesion passage. The guidewire is advanced across the lesion, or “wires” the lesion, in preparation for the advancement of a polyethylene, polyvinyl chloride, polyolefin, or other suitable substance balloon catheter across the guide wire. The balloon, or dilatation, catheter is placed into position by sliding it along the guide wire. The use of the relatively rigid guide wire is necessary to advance the catheter through the narrowed lumen of the artery and to direct the balloon, which is typically quite flexible, across the lesion. Radiopaque markers in the balloon segment of the catheter facilitate positioning across the lesion. The balloon catheter is then inflated with contrast material to permit fluoroscopic viewing during treatment. The balloon is alternately inflated and deflated until the lumen of the artery is satisfactorily enlarged.
[0006] Unfortunately, while the affected artery can be enlarged, in some instances the vessel restenoses chronically, or closes down acutely, negating the positive effect of the angioplasty procedure. In the past, such restenosis has frequently necessitated repeat PTCA or open heart surgery. While such restenosis does not occur in the majority of cases, it occurs frequently enough that such complications comprise a significant percentage of the overall failures of the PTCA procedure, for example, twenty-five to thirty-five percent of such failures.
[0007] To lessen the risk of restenosis, various devices have been proposed for mechanically keeping the affected vessel open after completion of the angioplasty procedure. Such mechanical endoprosthetic devices, which are generally referred to as stents, are typically inserted into the vessel, positioned across the lesion, and then expanded to keep the passageway clear. Effectively, the stent overcomes the natural tendency of the vessel walls of some patients to close back down, thereby maintaining a more normal flow of blood through that vessel than would be possible if the stent were not in place.
[0008] Various types of stents have been proposed, although to date none has proven satisfactory. One proposed stent involves a tube of stainless wire braid. During insertion, the tube is positioned along a delivery device, such as a catheter, in extended form, making the tube diameter as small as possible. When the stent is positioned across the lesion, it is expanded, causing the length of the tube to contract and the diameter to expand. Depending on the materials used in construction of the stent, the tube maintains the new shape either through mechanical force or otherwise. For example, one such stent is a self-expanding stainless steel wire braid. Other forms of stents include various types tubular metallic cylinders expanded by balloon dilatation. One such device is referred to as the Palmaz stent, discussed further below.
[0009] Another form of stent is a heat expandable device. This device, originally designed using NITINOL by Dotter has recently been modified to a new tin-coated, heat expandable coil by Regan. The stent is delivered to the affected area on a catheter capable of receiving heated fluids. Once properly positioned, heated saline is passed through the portion of the catheter on which the stent is located, causing the stent to expand. Numerous difficulties have been encountered with this device, including difficulty in obtaining reliable expansion, and difficulties in maintaining the stent in its expanded state.
[0010] Perhaps the most popular stent presently under investigation in the United States is referred to as the Palmaz stent. The Palmaz stent involves what may be thought of as a stainless steel cylinder having a number of slits in its circumference, resulting in a mesh when expanded. The stainless steel cylinder is delivered to the affected area by means of a balloon catheter, and is then expanded to the proper size by inflating the balloon.
[0011] Significant difficulties have been encountered with all prior art stents. Each has its percentage of thrombosis, restenosis and tissue in-growth, as well as varying degrees of difficulty in deployment. Another difficulty with at least some of prior art stents is that they do not readily conform to the vessel shape. In addition, the relatively long length of such prior art stents has made it difficult to treat curved vessels, and has also effectively prevented successful implantation of multiple such stents. Anticoagulants have historically been required at least for the first three months after placement. These and other complications have resulted in a low level of acceptance for such stents within the medical community, and to date stents have not been accepted as a practical method for treating chronic restenosis.
[0012] Thus there has been a long felt need for a stent which is effective to maintain a vessel open, without resulting in significant thrombosis, which may be easily delivered to the affected area, easily expanded to the desired size, easily conformed to the affected vessel, and easily used in multiples to treat curved vessels and varying lengths of lesions.
SUMMARY OF THE INVENTION
[0013] The present invention substantially reduces the complications and overcomes the limitations of the prior art devices. The endovascular support device of the present invention comprises a device having very low mass which is capable of being delivered to the affected area by means of a slightly modified conventional balloon catheter similar to that used in a standard balloon angioplasty procedure.
[0014] The support device of the present invention may then be expanded by normal expansion of the balloon catheter used to deliver the stent to the affected area, and its size can be adjusted within a relatively broad range in accordance with the diagnosis of the treating physician.
[0015] Because of the range of diameters through which the support device of the present invention may be expanded, it may be custom expanded to the specific lesion diameter, and is readily conformable to the vessel shape. In addition, a plurality of support devices of the present invention may be readily implanted in a number commensurate with the length of the lesion under treatment. As a result, curved or “S” shaped vessels may be treated.
[0016] The stent, or endovascular support device, of the present invention may preferably be comprised of implantable quality high grade stainless steel, machined specially for intravascular applications. The support device may comprise, in effect, a metal circle or ellipsoid formed to create a plurality of axial bends, thereby permitting compression of the stent onto a delivery catheter, and subsequent expansion once in place at the affected area.
[0017] It is one object of the present invention to provide a stent which substantially overcomes the limitations of the prior art.
[0018] It is a further object of the present invention to provide a stent capable of being implanted simply and reliably.
[0019] Another object of the present invention is to provide a stent which does not result in significant thrombosis at the point of implant.
[0020] Yet another object of the present invention is to provide a stent which can be selectively sized in accordance with the anatomic configuration dictated by the lesion itself.
[0021] A still further object of the present invention is to provide a method for supplying an endovascular support device which permits a plurality of such devices to be implanted commensurate with the length of the lesion under treatment.
[0022] These and other objects of the present invention can be better appreciated from the following detailed description of the invention, taken in conjunction with the attached drawings.
FIGURES
[0023] [0023]FIG. 1 shows a perspective view of an endovascular support device constructed according to the present invention, in its expanded form.
[0024] [0024]FIG. 2 shows a support device constructed according to the present invention and compressed onto a balloon catheter.
[0025] [0025]FIG. 3 shows a support device compressed onto a balloon catheter as shown in FIG. 2, and positioned within a sectioned portion of an affected area of a artery or other vessel.
[0026] [0026]FIG. 4 shows a support device according to the present invention in its expanded form within a sectioned portion of a vessel including a lesion.
[0027] [0027]FIG. 5 shows a support device of the present invention in its expanded form within a sectioned portion of a lesion after removal of the balloon catheter.
[0028] [0028]FIGS. 6 a - b show alternative configurations of a support device according to the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0029] Referring first to FIG. 1, an endovascular support device 10 , referred to hereinafter more conveniently as a stent, constructed in accordance with the present invention can be seen in perspective view. The stent 10 of FIG. 1 is shown in its expanded form, prior to compression over a suitable delivery system as discussed in detail hereinafter.
[0030] In a preferred embodiment, the stent 10 comprises a single piece of material, bent to form a plurality of upper axial turns 12 and lower axial turns 14 . In the embodiment shown in FIG. 1, four upper turns 12 are connected to the four lower turns 14 by substantially straight segments 16 . The axial turns 12 and 14 can be seen to permit the stent 10 to be compressed or expanded over a wide range while still maintaining significant mechanical force, such as required to prevent a vessel from restenosing. While a preferred embodiment comprises a single piece of material, in some instances a suitably welded wire may be acceptable.
[0031] It will be appreciated that the number of turns 12 and 14 can vary over a reasonably wide range, and may in fact vary between two and ten such turns or peaks. However, it is currently believed that the optimum number of turns or peaks will range between three and five for most applications, and particularly for cardiovascular applications.
[0032] The stent 10 is preferably constructed of implantable materials having good mechanical strength. An embodiment which has proven successful in preliminary testing is machined from 316LSS implantable quality stainless steel bar stock. The bar stock is machined to form substantially a toroid, which is then acid etched in phosphoric and sulfuric acid at approximately 180• to 185• to break the edges. The etched toroid is then plated with copper to avoid galling and to provide lubricity.
[0033] The copper plated toroid is then bent to the shape of the stent 10 shown in FIG. 1, after which the copper plating is stripped from the stent. The stent is then returned to the acid bath to reduce the wire size to the desired diameter, which is in the range of 0.002″ to 0.025″. It is presently believed that the optimum wire size for the final product is in the range of 0.008″ to 0.009″. It will be appreciated that the strength of the stent—that is, its ability to prevent restenosis—is inversely proportional to the number of peaks or turns in the stent, so that stents having a greater number of turns will typically be formed of larger wire diameters. Finally, although not required in all cases, the outside of the stent may be selectively plated with platinum to provide improved visibility during fluoroscopy. The cross-sectional shape of the finished stent may be circular, ellipsoidal, rectangular, hexagonal, square, or other polygon, although at present it is believed that circular or ellipsoidal may be preferable.
[0034] The minimum length of the stent, or the distance between the upper turns 12 and lower turns 14 , is determined in large measure by the size of the vessel into which the stent will be implanted. The stent 10 will preferably be of sufficient length as to maintain its axial orientation within the vessel without shifting under the hydraulics of blood flow (or other fluid flow in different types of vessels), while also being long enough to extend across at least a significant portion of the affected area. At the same time, the stent should be short enough as to not introduce unnecessarily large amounts of material as might cause undue thrombosis. Typical cardiovascular vessels into which the stent 10 might be implanted range from 1.5 millimeters to five millimeters in diameter, and corresponding stents may range from one millimeter to two centimeters in length. However, in most instances the stent will range in length between 3.5 millimeters and 6 millimeters. Preliminary testing of stents having a length between 3.5 millimeters and 4.5 millimeters has been performed with good success outside the United States, and testing on animals is also ongoing.
[0035] Once the wire size of the stent 10 has been reduced to the desired size, the stent 10 may be crimped onto a balloon 100 , as shown in FIG. 2, for delivery to the affected region 102 of a vessel 104 such as a coronary artery. For the sake of simplicity, the multiple layers of the vessel wall 104 are shown as a single layer, although it will be understood by those skilled in the art that the lesion typically is a plaque deposit within the intima of the vessel 104 .
[0036] One suitable balloon for delivery of the stent 10 is manufactured by Advanced Cardiovascular Systems, Inc., of Santa Clara, Calif. (“ACS”), and is eight millimeters in length with Microglide• on the shaft only. The stent-carrying balloon 100 is then advanced to the affected area and across the lesion 102 in a conventional manner, such as by use of a guide wire and a guide catheter (not shown). A suitable guide wire is the 0.014″ Hi Torque Floppy manufactured by ACS, and a suitable guiding catheter is the ET.076 lumen guide catheter, also manufactured by ACS.
[0037] Once the balloon 100 is in place across the lesion 102 , as shown in FIG. 3, the balloon 100 may be inflated, again substantially in a conventional manner. In selecting a balloon, it is helpful to ensure that the balloon will provide radially uniform inflation so that the stent 10 will expand equally along each of the peaks. The inflation of the balloon 100 , shown in FIG. 4, causes the expansion of the stent 10 from its crimped configuration back to a shape substantially like that shown in FIG. 1. The amount of inflation, and commensurate amount of expansion of the stent 10 , may be varied as dictated by the lesion itself, making the stent of the present invention particularly flexible in the treatment of chronic restenosis.
[0038] Because of the inflation of the balloon, the lesion 102 in the vessel 104 is expanded, and causes the arterial wall of the vessel 104 to bulge radially, as simplistically depicted in FIG. 4. At the same time, the plaque deposited within the intima of the vessel is displaced and thinned, and the stent 10 is embedded in the plaque or other fibrotic material adhering to the intima of the vessel 104 .
[0039] Following inflation of the balloon 100 and expansion of the stent 10 within the vessel 104 , the balloon is deflated and removed. The exterior wall of the vessel 104 returns to its original shape through elastic recoil. The stent 10 , however, remains in its expanded form within the vessel, and prevents further restenosis of the vessel. The stent maintains an open passageway through the vessel, as shown in FIG. 4, so long as the tendency toward restenosis is not greater than the mechanical strength of the stent 10 . Because of the low mass of the support device 10 of the present invention, thrombosis is less likely to occur. Ideally, the displacement of the plaque deposits and the implantation of the stent 10 will result in a smooth inside diameter of the vessel 104 , although this ideal cannot be achieved in all cases.
[0040] One of the advantages of the stent 10 is that multiple stents may be used in the treatment of a single lesion. Thus, for example, in the event the affected area shown in FIGS. 3 and 4 was longer than the stent 10 , additional stents 10 could be positioned elsewhere along the lesion to prevent restenosis. In preliminary testing, up to four stents have been used successfully along a single lesion. Due to the conformability of the stent 10 , not only can varying lesion lengths be treated,but curved vessels and “S” shaped vessels may also be treated by the present invention. In instances where it is known in advance that multiple stents will be the preferred method of treatment, a plurality of such stents may be positioned along a single balloon catheter for simultaneous delivery to the affected area.
[0041] As discussed above, the number of peaks or turns 12 and 14 in the stent 10 may vary between two and ten. To this end, shown in FIGS. 6 a and 6 b are two alternative configurations of the stent 10 . The alternative embodiment shown in 6 a can be seen to have three upper and three lower peaks or turns, while the embodiment shown in FIG. 6 b can be seen to have ten upper and ten lower peaks.
[0042] While the primary application for the stent 10 is presently believed to be treatment of cardiovascular disease such as atherosclerosis or other forms of coronary narrowing, the stent 10 of the present invention may also be used for treatment of narrowed vessels in the kidney, leg, carotid, or elsewhere in the body. In such other vessels,the size of the stent may need to be adjusted to compensate for the differing sizes of the vessel to be treated, bearing in mind the sizing guidelines provided above.
[0043] Having fully described a preferred embodiment of the invention, those skilled in the art will immediately appreciate, given the teachings herein, that numerous alternatives and equivalents exist which do not depart from the present invention. It is therefore to be understood that the present invention is not to be limited by the foregoing description, but only by the appended claims. | An endovascular support device for treatment of chronic restenosis or other vascular narrowing is disclosed together with a method of manufacture and a method for delivering a plurality of such devices to an affected area of a vessel. In a preferred embodiment, the endovascular support device comprises a unitary wire-like structure configured to form a plurality of upper and lower peaks which may be compressed for delivery to an affected area of a coronary or peripheral vessel in a human, and then expanded to maintain a passageway through the vessel. | 0 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an image forming apparatus in which an image of a document is optically scanned and the image is formed on a recording medium.
2. Discussion of Background
A conventional image forming apparatus or copying apparatus using an optical scanner accommodates only one document on the document table at a time, and copies the document only one frame a time by means of a single scanning operation. Therefore, in copying plural documents, the optical scanner must scan the documents on the document table plural times corresponding to the number of documents. Such repetitious scanning of documents is time-consuming and troublesome work.
SUMMARY OF THE INVENTION
Accordingly, an object of the present invention is to provide an image forming apparatus in which two documents on the document table can be scanned during one scanning operation by an optical scanner, and a precise setting of the documents on the document table can be easily performed.
To achieve the above object, there is a provided an image forming apparatus according to the invention including a document table for holding a document placed thereon, optical scanning means movably provided along the document table to optically scan the document placed on the document table, first and second indicating means provided at respective ends of the document table to indicate the allowable copy ranges, designating means for designating a scanning area provided by placing the document on the document table in accordance with the first and/or second indicating means, and means for controlling the movement of the optical scanning means to scan the scanning area designated by the designating means.
BRIEF DESCRIPTION OF THE DRAWINGS
A more complete appreciation of the invention and many of the attendant advantages thereof will be readily obtained as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings, wherein:
FIG. 1 is a plan view showing one embodiment of an image forming apparatus according to the present invention;
FIGS. 2-4 are respective views for explaining operation of the embodiment shown in FIG. 1:
FIG. 5 is a perspective view showing the outer appearance of the embodiment shown in FIG. 1;
FIG. 6 is a schematic cross-sectional side view showing a section of the embodiment of the invention shown in FIG. 1;
FIG. 7 is a plan view showing an operation panel of the embodiment of FIG. 1;
FIG. 8 is a perspective view showing driving portions of the embodiment of the invention of FIG. 1;
FIG. 9 is a perspective view of a scanning mechanism for moving an optical scanner in the embodiment of FIG. 1;
FIG. 10 is a perspective view of a driving mechanism for moving indicators in the embodiment of FIG. 1; and
FIG. 11 is a block diagram showing the overall control system for the embodiment of FIG. 1.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to the drawings, wherein like reference numerals designate identical or corresponding parts throughout the several views, FIGS. 5 and 6 are schematic views of the image forming apparatus, for example an electrostatic copying apparatus, of the invention. A document table 2 made of transparent glass is fixed on an upper portion of a main body 1 for supporting a document. An optical scanner 3 is provided and reciprocatively moves in the direction of arrow A along a lower surface of document table 2. Scanner 3 includes an exposure lamp 4 to illuminate a document placed on table 2 and mirrors 5, 6 and 7 to reflect the light reflected from the document. When optical scanner 3 moves from the left side to right side in FIG. 6, optical scanner 3 optically scans the document placed on table 2. Mirrors 6 and 7 are moved at half the speed of exposure lamp 4 and mirror 5, whereby an optical path length from the document to a photosensitive drum 10, described later, is kept constant. The reflected light from the document is reflected by mirrors 5, 6 and 7 then passed through a copy magnification changing lens block 8. Further, the reflecting light is the reflected by a mirror 9, and led to the surface of photosensitive drum 10. At this time, photosensitive drum 10 is exposed to a slit of light.
Operation of the drum 10 is next described. First, drum 10 is charged by a charger 11 while drum 10 is rotated in the direction of arrow C. Then, drum 10 is illuminated with light reflected from the document to create an electrostatic latent image of the document on the surface thereof. The electrostatic latent image is then visualized by application thereto of toner from a developing unit 12. Then, either an upper cassette 13 or a lower cassette 14 is selected and copy sheets P contained therein are taken out sheet-by-sheet by means of a feed roller, either 15 or 16. Each sheet P is directed to a pair of aligning rollers 19 through a sheet guide 17 or 18, and then sheet P is fed to a transfer station. Cassettes 13 and 14 are removably inserted into the right lower portion of main body 1. One of cassettes 13 and 14 is selected by operation of an operation panel to be described later. Cassette size sensors 60 1 and 60 2 are provided in the insertion holes for cassettes 13 and 14. Cassette size sensors 60 1 and 60 2 each contain a plurality of microswitches which are turned on and off in response to the size of the inserted cassette.
Copy sheet P fed to the transfer station contacts with photosensitive drum 10. While contacting the drum 10, a charge transfer unit 20 applies charge to copy sheet P and the toner image is transferred from drum 10 onto copy sheet P. Copy sheet P with the transferred toner image is then separated from photosensitive drum 10 by a separating unit 21, and is transferred to a pair of fixing rollers 23 by a transfer belt 22. A pair of fixing rollers 23 apply heat and pressure to copy sheet P, thereby fixing the toner image. After fixing, copy sheet P is discharged to a tray 25 attached to the outside of main body 1 by a pair of discharge rollers 24. Photosensitive drum 10, after it is subjected to the toner image transfer process, reaches a charge remover 26. Charge remover 26 removes charges on photosensitive drum 10, then the residual toner on the surface of drum 10 is removed by a cleaner 27. Further, an after image (residual charge) is erased by a discharge lamp 28. At this point, drum 10 is returned to its initial state. A cooling fan 29 is provided near discharge roller pair 24 to prevent an excessive temperature rise in main body 1.
FIG. 7 shows an operation panel 30 provided on the upper surface of main body 1. Panel 30, as shown, includes a copy button 30 1 for starting the copying operation, ten keys 30 2 for setting a desired number of copies, a display 30 3 for displaying states of the copying operation or jammed copy sheets, select keys 30 4 for selecting copy sheets of a desired size and a size display 30 5 for displaying a selected copy sheet size arranged on the panel. On the left side of the panel, copy magnification select keys 30 6 are arranged for selecting copy magnifications of enlargement or reduction. Between display 30 3 and size display 30 5 , scan direction designating keys 30 7 and 30 8 are arranged for designating the scanning direction of optical scanner 3 (i.e., moving direction of a first carriage 41 1 to be described later) and LEDs (Light Emitting Diode) 30a and 30b are provided on the upper side of designating keys 30 7 and 30 8 to display the designation made by designating keys 30 7 or 30 8 . In the case that main body 1 has applied thereto electric power and is in the normal mode, designating key 30 7 is selected automatically and LED 30a is lit up.
FIG. 8 shows an allocation of drive sources which are made of pulse motors. The drawing of FIG. 8 is depicted as if viewed from the rear side of the copying apparatus, while the FIG. 5 drawing shows the front side of the copying apparatus. A magnification changing motor 31 is provided for changing the location of copy magnification changing lens block 8. A motor 32 changes the distance (optical path) between mirror 5 and mirror pair 6 and 7 when the copy magnification is changed. A scanning motor 33 moves exposure lamp 4 and mirror 5 and mirror pair 6 and 7 for scanning the document. A shutter motor 34 moves the shutter (not shown) to adjust the charging width of the charge on photosensitive drum 10 which is formed by the charger 11 when the copy magnification is changed. A developing motor 35 drives the developing roller of developing unit 12. A drum motor 36 drives photosensitive drum 10. A fixing motor 37 drives transfer belt 22, fixing roller pair 23 and discharge roller pair 24. A paper feed motor 38 drives feed rollers 15 and 16. A paper feed motor 39 drives aligning roller pair 19. A fan motor 40 drives cooling fan 29.
FIG. 9 shows a scanning mechanism for moving the optical scanner formed of exposure lamp 4 and mirrors 5, 6 and 7 along document table 2. Mirror 5 and exposure lamp 4 are supported by a first carriage 41 1 , and mirrors 6 and 7 are supported by a second carriage 41 2 . These carriages 41 1 and 41 2 can move in the direction of the arrow A along guide rails 42 1 and 42 2 . Scanning motor 33 has a 4-phase pulse motor which drives a pulley 43. An endless belt 45 is wound around this pulley 43 and an idle pulley 44. First carriage 41 1 supporting mirror 5 is fixed at one end to the midportion of endless belt 45. A couple of rotatable pulleys 47 and 47 are mounted to a guide 46 of second carriage 41 2 . A wire 48 is wound around pulleys 47 and 47. One end of wire 48 is fixed to a fixing piece 49, while the other end is fixed to fixing piece 49 via a coiled spring 50. One end of first carriage 41 1 is fixed to the mid-portion of wire 48. With the rotation of pulse motor 33, belt 45 rotates causing first carriage 41 1 to move. In turn, second carriage 41 2 also moves. As this time, pulleys 47 and 47 serve as a fall block. Therefore, second carriage 41 2 moves at half of the speed of first carriage 41 1 while traveling in the same direction as first carriage 41 1 . The moving direction of first and second carriage 41 1 and 41 2 can be changed by reversing the rotating direction of pulse moter 33.
When the enlargement or reduction copy is established, the allowable copy ranges are indicated on document table 2 corresponding to designated size of the copy sheets. Namely, if Px and Py mean size of copy sheets selected by select keys 30 4 and K means copy magnifications selected by copy magnification select keys 30 6 , copy allowable ranges X and Y can be expressed as follows.
X=Px/K
Y=Py/K
X is indicated by indicators 51 and 52 provided under the transparent glass of document table 2 and Y is indicated by a scale 53 provided on the upper surface of first carriage 41 1 as shown in FIG. 5.
As shown in FIG. 10, indicators 51 and 52 are fixed to a wire 57 wound around pulleys 54 and 55 via a coiled spring 56. Pulley 55 is rotated by a motor 58. When motor 58 drives pulley 55, the distance between indicator 51 and indicator 52 is varied in accordance with the copy magnification. Scale 53 (shown in FIGS. 5 and 9) provided on first carriage 41 1 is moved to a desired position (a home postion) in accordance with the copy sheet size and copy magnification by driving motor 33.
FIG. 11 shows the overall control system of the present invention. This control system includes a main processor 71, and first and second sub-processors 72 and 73. Main processor 71 detects signals from operation panel 30 and cassette size sensors 60 1 and 60 2 , and controls a high voltage transformer 76 for supplying high voltage to the various charging units, discharge lamp 28, a solenoid (BLD) 27a for actuating a cleaning blade of cleaner 27, a heater 23a of fixing roller pair 23, exposure lamp 4 and motors 31-40 and 58. Of the motors 31-40 and 58, motors 35, 37, 40 and a motor 77 for supplying toner to developing unit 12 are controlled by main processor 71 through a motor driver 78. Motors 31-34 are controlled by first subprocessor 72 through a pulse motor driver 79. Motors 36, 38, 39 and 58 are controlled by second subprocessor 73 through a pulse motor driver 80. Exposure lamp 4 is controlled by main processor 71 through a lamp regulator 81. A heater 23a is controlled by main processor 71 through a heater controller 82. Main processor 71 sends motor drive and stop commands to first and second sub-processors 72 and 73. These sub-processors 72 and 73 send status signals representing the drive and stop of motors to main processor 71. First sub-processor 72 is supplied with position data from a motor phase sensor 83 for detecting the initial position of each of motors 31-34.
The essential parts of the present invention will next be described. As shown in FIG. 1, scales 90 and 91 indicate locations of placing the documents at respective ends of document table 2. Each of scales 90 and 91 is marked with "A4" (210×297 mm) and "B5" (182×257 mm) indicating the upper and lower limits of the copy allowable ranges. The length L between scale 90 and scale 91 is set to a size slightly longer than the maximum size of documents (e.g. A3 size: 297×420 mm or LEDGER size: 11×17 inches). L1 is a width represents a half of the maximum size of the documents, namely L1 represents a width of A4 size: 210×297 mm or LETTER size: 81/2×11 inches. A relation between L and L1 is as follows:
L=L1+L1 +δ (δ≧0)
In the case of actually making a copy, first carriage 41 1 is located at a middle portion between scale 90 and scale 91. Namely, a length L0≃L/2 represents a home position of first carriage 41 1 . Documents G1 and G2 are placed along scales 90 and 91, respectively of the table as shown in FIG. 1. As discussed hereinafter, documents G1 and G2 will be called the left document G1 and the right document G2, respectively.
The copying operation in the case of left document G1 placed on table 2 will be described with the aid of FIG. 2. In this case, scan direction designating keys 30 7 is depressed, whereby LED 30a is lit. In this state, when copy button 30 1 is depressed, first carriage 41 1 moves from a point H1 to a point H2 which is very close to scale 90, as shown by the arrow X. Upon turning point H2, the exposure lamp 4 provided on first carriage 41 1 is energized and thereby produces exposing light. Then first carriage 41 1 moves from the point H2 to the point H1, whereby left document G1 is optically scanned. In finished the optical scanning, exposure lamp 4 is de-energized and first carriage 41 1 stops at the home position in the middle portion of document table 2.
FIG. 3 shows the state when a right document G2 is placed along scale 91 of table 2. In this case, scan direction designating key 30 8 is depressed, whereby LED 30b is lit. In this state, when copy button 30 is depressed, exposure lamp 4 provided on first carriage 41 1 is energized. Then first carriage 41 1 moves from a point H3 to a point H4 which is very close to scale 91, as shown by the arrow Y, whereby right document G2 is optically scanned. When first carriage 41 1 reaches point H4, optical scanning is finished. At this time, exposure lamp 4 is de-energized, then first carriage 41 1 is returned to the home position in the middle portion of document table 2.
FIG. 4 shows a state where both the left and right documents G1 and G2 are placed along scales 90 and 91, respectively, of table 2. In this case, both of the scan direction designating keys 30 7 and 30 8 are depressed, whereby LEDs 30a and 30b are lit. In this state, when copy button 30 1 is depressed, first carriage 41 1 moves from the point H1 towards scale 90, as shown by the arrow Z. When first carriage 41 1 reaches the point H2 which is very close to scale 90, exposure lamp 4 is energized. Then, first carriage 41 1 moves from the point H2 to H1, whereby the left document G1 is optically scanned. The optical scanning of left document G1 is then finished, and then first carriage 41 1 moves from the point H3 to H4 which is very close to scale 91 for optical scanning of the right document G2. At point H4, optical scanning of documents G1 and G2 is finished. After that, exposure lamp 4 is de-energized, and first carriage 41 1 is returned to the home position H1.
While first carriage 41 1 moves from the point H1 to H3 after the optical scanning and copying of the left document G1, a copy sheet is taken out from cassettes 13 or 14 and aligned by aligning roller 19. The copy sheet is transported to photosensitive drum 10. A toner image corresponding to right document G2 is transfered from drum 10 to the copy sheet upon the optical scanning by moving first carriage 41 1 from the point H3 to H4.
If the gap size δ between the point H1 and H3 is small, the moving of first carriage 41 1 is decelerated or stopped in between H1 and H3 so that the movement of first carriage 41 1 from H3 to H4 coincides with the timing of copy sheet feeding.
As described above, first carriage 41 1 is able to scan the document due to first carriage 41 1 moving from middle portion of document table 2 in both the left and right directions. Therefore, two documents placed on document table can be copied by only one optical scanning operation. As a result, the copy speed can be improved.
As scales 90 and 91 are provided at respective ends of document table 2, a precise setting of both documents on document table 2 can be easily performed.
Further, as first carriage 41 1 is standing by at the middle portion of document table 2, first carriage 41 1 is able to scan the document quickly even if only one document is placed on the left or right portion of document table 2.
Obviously, numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein. | An image forming apparatus including a document table for holding a document placed thereon, an optical scanner movably provided along the document table to optically scan the document placed on the table, first and second indicators or scales provided at respective ends of the document table to indicate the allowable copy ranges, a designating device for designating a scanning area provided by placing the document on the document table in accordance with at least one of the first and second indicators, and a controller for controlling the movement of the optical scanner to scan the scanning area designated by the designating device. Two full-sized documents on the document table can be scanned during one scanning operation by the optical scanner, and a precise setting of the documents on the document table can be easily performed. | 6 |
FIELD OF THE TECHNOLOGY
The present invention relates to a control device comprising: a reference frame; a stick; a pivot mounting the stick to the reference frame, the pivot defining a pivot axis; and an actuator for rotating the stick about the pivot axis.
BACKGROUND
A first known control device of this kind is described in US 2006/0254377. The stick is driven about two perpendicular pivot axes (A, B) by respective rotary actuators. A balance weight is provided on the A-axis in order to provide vertical mass balance about the B-axis. In other words, the balance weight ensures that there is no net induced moment about the B-axis when the device is subjected to a vertical acceleration perpendicular to the A and B axes.
A first problem with this arrangement is that the balance weight adds to the total weight of the device. A second problem is that the balance weight adds to the total volume of the device. A third problem is that the device is not horizontally mass balanced. Therefore, if the device is subjected to a horizontal acceleration, then there will be a net induced moment about the A or B axis. This mass imbalance must be compensated by one or both of the actuators, which adds complexity to the system.
A second known control device of this kind is described in U.S. Pat. No. 6,708,580. This device is also not horizontally mass balanced.
SUMMARY
In a first aspect, a control device comprises: a reference frame; a stick; a pivot mounting the stick to the reference frame and defining a pivot axis; and an actuator for rotating the stick about the pivot axis, wherein the centres of mass of the actuator and the stick are offset from the pivot axis such that if the control device is subjected to an acceleration orthogonal to the pivot axis, then the mass of the actuator and the mass of the stick generate moments about the pivot axis which act in opposite directions.
By offsetting the centres of mass of the actuator and the stick from the pivot axis, the mass of the stick can be at least partially balanced by the mass of the actuator without requiring an additional balance weight.
Typically a line passing through the pivot axis and the centre of mass of the stick also passes through the actuator. Preferably this line passes substantially through the centre of mass of the actuator. This enables the device to be mass balanced with respect to both vertical and horizontal acceleration of the device (in the case where the pivot axis is horizontal). In the more general case, if the line passes substantially through the centre of mass of the actuator, then the device is mass balanced with respect to two axes which are perpendicular to the pivot axis. However the centre of mass of the actuator may be slightly offset from this line and still provide an element of mass balance.
The actuator may be a linear actuator (such as a hydraulic piston or linear electric actuator) but more preferably the actuator is a rotary actuator having a stator coupled to the slick and a rotor coupled to the reference frame by a drive link and configured to rotate relative to the stator about a drive axis which is not co-linear with the pivot axis.
In a further aspect, a control device comprises: a reference frame; a stick; a pivot mounting the stick to the reference frame and defining a pivot axis; and a rotary actuator having a stator coupled to the stick and a rotor coupled to the reference frame by a drive link and configured to rotate relative to the stator about a drive axis which is not co-linear with the pivot axis.
In contrast with the devices described in US 2006/0254377 and U.S. Pat. No. 6,708,580 the drive axis of the rotary actuator is not co-linear with the pivot axis, enabling a more mass balanced arrangement. Also, a rotary actuator is typically more compact and lighter than a linear actuator, and is also typically easier to backdrive.
Preferably the drive link is pivotally coupled to the rotor by a first drive pivot and to the reference frame by a second drive pivot.
In certain examples the drive axis is not parallel with the pivot axis. For instance it may lie at a perpendicular or acute angle with the pivot axis. In other embodiments of the invention the drive axis is substantially parallel with the pivot axis.
Preferably the device is substantially mass balanced about the pivot axis.
BRIEF DESCRIPTION OF THE DRAWINGS
Examples will now be described with reference to the accompanying drawings, in which:
FIG. 1 is a front upper view of a first one-axis device in a nominal position;
FIG. 2 is a rear ¾ view of the first one-axis device in the nominal position;
FIG. 3 is a rear ¾ view of the first one-axis device in a deflected position;
FIG. 4 shows a second one-axis device in a nominal position;
FIG. 5 shows the second one-axis device in a deflected position;
FIG. 6 is a side view of a first two-axis device in a nominal position;
FIG. 7 is an upper ¾ view of the first two-axis device in the nominal position;
FIG. 8 is a front ¼ view of the first two-axis device in a rolled position;
FIG. 9 is a side ¼ view of the first two-axis device in the rolled position;
FIG. 10 is a side view of the first two-axis device in a pitched position;
FIG. 11 is an upper side view of the first two-axis device in the pitched position;
FIG. 12 is a side view of a second two-axis device in a nominal position;
FIG. 13 is a side view of the second two-axis device in a rolled position;
FIG. 14 is a side view of the second two-axis device in a pitched position;
FIG. 15 is a rear ¼ view of a third two-axis device in a nominal position;
FIG. 16 is a front ¼ view of the third two-axis device in the nominal position;
FIG. 17 is a front ¼ view of a fourth two-axis device in a nominal position; and
FIG. 18 shows a third one-axis control device.
DETAILED DESCRIPTION
The control device shown in FIGS. 1-3 comprises a mounting plate 6 a and a pair of pivot supports 6 b fixed to the mounting plate 6 a . The mounting plate 6 a is fixed in turn to the structure of a vehicle or flight simulator.
A stick is attached to a pivot block 11 . The stick comprises a shaft 3 and a handle 4 . A pivot shaft 7 extends from opposite sides of the pivot block 11 , and is journalled in the pair of pivot supports 6 b so that the stick is free to rotate about the pivot axis X defined by the pivot shaft 7 .
A rotary actuator has an output shaft 2 which is fixed to the pivot block 11 and extends from an opposite side of the pivot axis X. The actuator has a casing 1 coupled to the mounting plate 6 a by a drive link 5 . The drive link 5 is pivotally coupled to the casing 1 by a first drive pivot and to the mounting plate 6 a by a second drive pivot.
In the arrangement of FIG. 1 , the output shaft 2 of the actuator remains fixed in relation to the stick (and thus acts as a stator) and the casing 1 of the actuator is configured to rotate about the drive axis of the actuator relative to the stator (and thus acts as a rotor). If the casing 1 rotates anticlockwise, then the drive link 5 drives the actuator down and the stick up as shown in FIG. 3 . If the casing 1 rotates clockwise, then the drive link 5 drives the actuator up and the stick down.
A torque sensor 20 is provided to sense the torque applied to the output shaft 2 . The torque sensor may be implemented for example by a set of strain gauges or piezo-electric elements. The torque sensor measures the force applied to the stick by a pilot.
When operating in an active mode, the actuator applies a force to the stick, for instance to provide force feedback to the pilot. When in passive mode the actuator has no power applied to it and the pilot is able to move the stick by driving the actuator backwards without a significant resistance. Alternatively a device to disconnect the actuator drive may be fitted to decouple the actuator.
Instead of employing a torque sensor 20 for measuring the torque applied to the output shaft 2 of the actuator, a force sensor 21 may be fixed to the drive link 5 . In both cases the force/torque sensor will sense the moment about the pivot axis X.
By positioning the torque/force sensors to directly sense the output of the actuator, the sensors are insensitive to g induced moments and therefore the active control of the stick is also unaffected by g loads.
The centres of mass of the actuator and the stick are offset on opposite sides of the pivot axis X. As a result the device is vertically mass balanced about the pivot axis X—the vertical direction being perpendicular to the pivot axis X and to the axis Y labelled shown in FIG. 3 .
Therefore if the stick is subjected to a vertical acceleration of ng then the moment about the pivot axis X in the vertical direction is given by:
M=−l 1 m 1 ng+l 2 m 2 ng equation (1)
where:
l 1 is the distance between the pivot axis X and the centre of mass of the stick; m 1 is the mass of the stick (including the shaft 3 and the handle 4 ); l 2 is the distance between the pivot axis X and the combined centre of mass of the actuator and force sensor; and m 2 is the combined mass of the actuator and force sensor.
For mass balance we want M=0 or:
l 1 m 1 ng=l 2 m 2 ng equation (2)
which reduces to:
l 1 m 1 =l 2 m 2 equation (3)
Thus by choosing values which satisfy equation (3), the device is vertically mass balanced about the pivot axis X.
Also, a line (labelled A in FIGS. 1-3 ) passing through the pivot axis X and the centre of mass of the stick also passes substantially through the centre of mass of the actuator. Therefore the device is horizontally mass balanced about the pivot axis X.
FIGS. 4 and 5 show a second one-axis control device. The device is similar to the device of FIGS. 1-3 , and equivalent features are given the same reference numeral. In the arrangement of FIGS. 1-3 the drive axis of the actuator is substantially co-linear with the line A and perpendicular to the pivot axis X. By contrast, in the arrangement of FIG. 4 the drive axis D is perpendicular to the line A and parallel with the pivot axis X.
The casing 1 of the actuator is fixed to the pivot block 11 by an arm 12 , and the output shaft 2 is coupled to the mounting plate 6 a by the drive link 5 , and a crank shaft 13 extending at right angles to the drive axis. The drive link 5 is pivotally coupled to the crank shaft 13 by a first drive pivot and to the mounting plate 6 a by a second drive pivot.
In the arrangement of FIG. 4 , the casing 1 remains fixed in relation to the stick (and thus acts as a stator) and the output shaft 2 rotates (and thus acts as a rotor). If the output shaft 2 rotates anticlockwise, then the drive link 5 drives the stick up and the actuator down as shown in FIG. 5 . If the output shaft 2 rotates clockwise, then the drive link 5 drives the stick down and the actuator up.
In common with the device of FIG. 1 , a torque sensor (not shown) is provided to sense the torque applied to the output shaft 2 .
FIGS. 6-11 show a first two-axis control device. The device is similar to the device of FIGS. 1-3 , and equivalent features are given the same reference numeral.
The mounting plate 6 a is fixed to a casing 8 of a second (Y-axis) actuator. Instead of being fixed to the mounting plate 6 a , the pivot supports 6 b are fixed to a mounting bracket 9 , which is fixed in turn to an output shaft 10 of the Y-axis actuator. Thus in the two-axis device the pivot supports 6 b and mounting bracket 9 provide a first (X-axis) reference frame and the mounting plate 6 a provides a second (Y-axis) reference frame. The drive link 5 is pivotally coupled to the casing 1 by a first drive pivot and to the mounting bracket 9 by a second drive pivot.
FIGS. 12-14 show a second two-axis control device. The device is similar to the device of FIGS. 6-11 , and equivalent features are given the same reference numeral.
In contrast to the arrangement of FIGS. 6-11 (and in common with the arrangement of FIG. 4 ) the drive axis of the X-axis actuator is at right angles to the line A. The casing 1 of the actuator is fixed to the pivot block 11 , and the output shaft 2 of the X-axis actuator is coupled to the mounting bracket 9 by the drive link 5 .
The two-axis devices shown in FIGS. 6-15 are provided with an X-axis torque sensor (not shown) to sense the torque applied to the X-axis output shaft 2 and a Y-axis torque sensor (not shown) to sense the torque applied to the Y-axis output shaft 10 .
FIGS. 15 and 16 show a third two-axis control device. The device is similar to the device of FIGS. 12-14 , and equivalent features are given the same reference numeral. In contrast to the arrangement of FIGS. 12-14 , the output shaft of the X-axis actuator is coupled to an L-shaped bracket 10 which is rigidly connected to the pivot block 11 . The casing 1 of the X-axis actuator is coupled to the mounting bracket 9 by the drive link 5 . Thus in this case the output shaft of the actuator acts as a stator, and the casing acts as a rotor. This arrangement has the potential to save some space when roll deflections occur. A similar variant of the device of FIGS. 4 and 5 may also be used.
FIG. 17 show a fourth two-axis control device. The device is similar to the device of FIGS. 6-11 , and equivalent features are given the same reference numeral. In contrast to the arrangement of FIGS. 6-11 , the casing 1 of the X-axis actuator is rigidly connected to the pivot block 11 , and the output shaft is coupled to the mounting bracket 9 by the drive link 5 . Thus in contrast to the arrangement of FIGS. 6-11 , the output shaft of the actuator acts as a rotor and the casing 1 acts as a stator.
FIG. 18 show a third one-axis control device. The device is similar to the device of FIGS. 1-3 , and equivalent features are given the same reference numeral. In contrast to the device of FIGS. 1-3 , the actuator is angled downwardly with respect to the line A passing through the pivot axis X and the centre of mass of the stick. Although the device is not mass balanced against horizontal acceleration orthogonal to the pivot axis X, since the centre of mass of the actuator lies in a vertical plane containing the line A the device is mass balanced against vertical acceleration.
The two-axis devices of FIGS. 6-17 are vertically and horizontally mass balanced about both the X and Y-axes.
The devices shown in the figures may be used on a vehicle such as a helicopter. For instance the one-axis devices shown in FIGS. 1-5 and 18 may be used as the collective lever of a helicopter. Alternatively the devices may be used in a simulator.
Although the above has been described above with reference to one or more preferred embodiments, it will be appreciated that various changes or modifications may be made without departing from the scope of the invention as defined in the appended claims. | A control device comprising: a reference frame; a stick; a pivot mounting the stick to the reference frame and defining a pivot axis; and an actuator for rotating the stick about the pivot axis. Mass balance is achieved by offsetting the centers of mass of the actuator and the stick from the pivot axis. Typically a line joining the centers of mass of the actuator and the stick substantially passes through the pivot axis. The actuator is a rotary actuator having a stator coupled to the stick and a rotor coupled to the reference frame. | 6 |
FIELD OF INVENTION
[0001] This invention relates to bedding and bed sheets and in particular but not exclusively to a bed sheet with a removable and replaceable panel.
BACKGROUND OF THE INVENTION
[0002] Bedding and bed linen is known prior art. The changing of sheets is a routine and often time consuming task especially where there are several beds to be made. Where the bed has a heavy mattress under which bed sheets have to be tucked, the effort of lifting such mattresses can also require great physical effort.
[0003] The process of placing a standard sheet on any mattress is a skilled task since the corners of the sheet have to be securely tucked under the four corners of the mattress. Access to the under side of the mattress is often restricted by the construction and design of the bed itself such as where there are bed ends, panels and rails. These structures are often coupled with the sheer weight of many prior art mattresses such as those of the latex type construction making the task ever more difficult.
[0004] The typical and prior art method of changing a standard bed sheet set is to either lift or entirely remove the mattress from the bed and then to remove the sheets by pulling the sheet out from beneath the mattress. The process is then basically reversed to re-make the bed.
[0005] Prior art in relation to standard bed sheets has mainly concentrated on simplifying the often cumbersome process of changing the sheets without a need to remove the mattress. Such prior art sheets commonly disclose the use of elastic around the peripheral edge of the sheet commonly referred to as a fitted sheet adapted to keep the bed sheet in place on the mattress. There is also prior art relating to standard sheets which disclose the use of a mattress protector and/or the use a waterproofing sheet underlying the fitted sheet. Such prior art includes U.S. Pat. No. 7,047,580 (Finn) which discloses a multi-layer mattress protector which utilises a least two moisture proof layers with the top moisture proof layer being releasably attached to and removable from the bottom moisture proof layer. The top moisture proof layer can also be removed from the mattress protector while someone is in the bed.
[0006] Common disadvantages or limitations of the prior art include the problem where the depth of the elasticised sides of fitted sheets often do not extend far enough beneath the mattress to ensure that the sheet remains firmly in place. Prior art disclosing the use of mattress protectors beneath fitted sheets have the disadvantage that there is an extra cost as well as an increase in labour and time to remove the separate mattress protector beneath the sheets when they have to be washed. The same problems also apply to the use of waterproof sheets beneath fitted sheets which also require frequent washing.
[0007] In the case of bedding used by infant occupants, there is also a problem wherein the arms and legs of the infant can become entangled especially where there is a gap between the top and bottom of the sheet. The problem with the use of mattress protectors and waterproof sheets underlying bed sheets is also more acute where used with young children or the infirm where the constant supply of mattress protectors and moisture proof sheeting is an important limitation especially in commercial and institutional application.
[0008] In the case of infant use, safety is a priority and there have been numerous cases of injury and even death from suffocation and/or strangulation especially where sheets have become loose and the infant has become entangled in them. In the case of infant application, the process of placing a standard sheet on a cot or crib mattress is often made difficult because the corners of the sheet have to be tucked very securely under the four corners of the mattress. Access to the corners of a cot or crib mattress is often restricted by bars, panels, slats or rails which are inherent in the design of most prior art cots and cribs. Mattress access can be further restricted by the presence of bumpers which are often used to prevent the child from injuring itself. Current mattress designs, whether of inner spring or foam construction often have squared off corners which are designed to limit the ability of an infant to access areas between the mattress and the insides of the cot or crib. Such designs further impede the ease or speed with which a prior art cot or crib sheet can be changed.
[0009] A typical method of changing a cot or crib sheet set is to remove the bumpers, if present, lift or entirely remove the mattress from the cot or crib and then remove the standard sheet by pulling the sheet from beneath the mattress. The process is reversed to remake the bedding of the cot or crib.
[0010] Naturally, prior art inventions relating to cot or crib sheets have concentrated on simplifying the cumbersome process of changing the sheets without the need to remove the mattress or bumpers from the cot or crib.
OBJECT OF THE INVENTION
[0011] It is therefore an object of the present invention to provide an improved bed sheet system which seeks to overcome or ameliorate the disadvantages or limitations of the prior art or to at least provide the public with a useful choice.
STATEMENT OF INVENTION
[0012] Accordingly in one aspect therefore the invention resides in a bed sheet, comprising in combination,
[0000] a top panel for covering a mattress top,
a surrounding side panel adapted to surround the side edges of the mattress,
the top panel removably attachable to the side panel to form a bed sheet for the mattress wherein in use,
the top panel can be detached and removed from the side panel when the bed sheet is covering the mattress whereby the side panels are left in position on the side edges of the mattress.
[0013] Preferably the top panel is removably attached to the side panel by fastening means in the form of a continuous zipper fastener. In the alternative the top panel can be removably attached to the side panel by means of hook and loop fasteners such as Velcro™.
[0014] The top panel can also be removably attached to the side panel by means of press studs or other equivalent readily detachable fasteners.
[0015] Preferably a flap of material can be used to hide or protect the fastening means from inadvertent release.
[0016] Preferably the top panel incorporates a waterproof layer.
[0017] More preferably the top panel is lined with a waterproof layer that is also hypoallergenic and has anti-fungal, anti-asthmatic and dust-mite inhibition properties.
[0018] In a preferred example of the invention, for typically infant application, the invention resides in a bed sheet, comprising in combination.
[0000] a mattress case adapted to fully enclose a mattress,
the case comprising top and bottom panels joined together to form the mattress case, the top panel of which is removable when the mattress case is covering the mattress whereby the bottom panel is left in position on the mattress.
[0019] Preferably in one version the top and bottom panels of the mattress case are joined together by a surrounding side panel to accommodate the thickness of the mattress.
BRIEF DESCRIPTION OF DRAWINGS
[0020] In order for the invention to be better understood and put into practical effect, reference will now be made to the accompanying drawings wherein
[0021] FIG. 1 shows a preferred embodiment of the invention according to Example 1, and
[0022] FIG. 2 shows a preferred embodiment invention according to Example 2.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Example 1
[0023] Referring now to the accompanying drawings an initially to FIG. 1 , there is shown a preferred bed sheet system 10 according to Example 1. The sheet system includes a side panel 12 and a removable top panel 14 which are securely attached together by the use of a detachable fastener 16 , in this case, preferably by a continuous zipper fastener 16 . The sheet has no bottom panel shown by broken line 12 a representing the edges of the side panel 12 underneath the mattress 18 . This system provides for the ease of changing the sheets by removing or attaching the top panel to the surrounding side panels while still covering the mattress 18 . The system in combination creates a safe sleeping environment for young children and the physically and mentally handicapped for whom the accidental removal of the top panel could cause a safety issue. The attachment means in the form of the continuous zipper fastener 16 is positioned in such a manner that it cannot be easily accessed by the infirm, child or adult occupant. Preferably while the fastener is a zipper fastener, other attaching and detaching means can also be utilised such as hook and eye fasteners, for example Velcro™, clasps, press studs, buttons and plurality of prior art snap fasteners. In this embodiment where the removable attachable means is a zipper, the slide of the zipper is preferably located on the base or side panel of the sheet system. The zipper can be made of any appropriate material but is preferably a continuous moulded plastic separating zipper. In addition, the zipper can be attached in such a way that the pull of the zipper can be hidden under the base of the zipper when the zipper is fully closed. The slide of the zipper preferably remains with the base or side of panel of the sheet system. The zipper is attached in such a way that the zipper pull can be completely hidden from view and is not accessible to the infirm, child and adult occupant when covered by a flap of material 14 a . The zipper 16 preferably surrounds the entire perimeter of the top surface of the mattress and extends where the base of the zipper or where the zipper is inserted is located. The teeth of the zipper preferable extend under the zipper insert and the zipper pull can be pushed under the insert. The side panel and removable top panel can be made of any material suitable for sheeting and bedding. A waterproof, hypo-allergenic, dust mite resistant, anti-asthmatic and mould resistant lining can be incorporated into the top panel to provide added protection to the mattress. In preferred embodiments the sheet system is made of polyester/-cotton fabrics.
[0024] It is expected that the removable top panel and corresponding half of the zipper attachment means will be laundered much more frequently than the base or side panel. The preferred embodiment with the plastic moulded separating zipper has been shown to withstand a significant number of washing and tumble dryings without affecting the integrity and continuous function of the zipper and top panel.
[0025] The side panel or base of the sheet system is substantially identical to the length of the mattress plus twice the depth of the mattress. Preferably a number of elasticised strips 20 , 22 are placed on either side panel and end panel 23 or on each 26 , 28 , 30 end where on all four vertical corners or seams allow for improved adjustability of fit for a multitude of sizes of mattresses as well as to maintain the integrity of the removable top panel. Preferably the removable top panel of the preferred sheet system is substantially almost identical in dimension to the top surface of the mattress. The half of the moulded plastic zipper that does not contain the slide is attached to the removable top panel 14 in such a manner that a fabric flap 14 a can be used to provide a cover for the zip when the top panel is attached to the side panel. A waterproof, hypo-allergenic, dust mite resistant, anti-asthmatic, mould resistant lining is incorporated into the removable top panel to prevent damage to the mattress in the event of an accident. This lining also aides in maintaining the integrity of the top panel through numerous washings and dryings.
Example 2
[0026] Referring now to FIG. 2 , there is shown a preferred embodiment of the invention according to Example 2. Example 2 shows a pediatric or infant application of the invention. As with Example 1, the paediatric or infant application uses a safety sheet system 40 which includes a bottom panel 42 and removable top panel 44 which are securely attached by means of a continuous zipper fastener 46 . The design of the preferred embodiment eliminates the possibility of an infant removing the sheet and wrapping or entangling itself in the fabric of the sheet. The top panel is completely removable and attachable to the bottom panel by use of the continuous zipper means. This system provides for the ease of changing of the sheets by using the zipper to either remove or attach a top panel to the bottom panel. This system also creates a safer sleeping environment for the infant as the preferred zipper fastener is positioned in such a manner that the infant or child cannot access it. While the preferred attachment means is a continuous zipper fastener, other attachment means such as hook and eye fasteners for example Velcro™, clasp, press studs, buttons and a plurality of snap fasteners can also be used. In a most preferred embodiment, the use of the zip provides a simple means of attaching the top panel 44 to the bottom panel 42 wherein the slide of the zipper can be located on the bottom panel of the sheet system. The zipper may be made out of any appropriate material but the preferred version is of a moulded plastic construction. In addition the zipper can be attached in such a way that the pull of the zipper can be hidden under the base of the zipper when the zipper is completely closed. The pull or slide of the zipper is also preferably located in an inaccessible portion of the sheet system. The removable top panel is designed in such a manner that the simple attaching means can be covered by a flap of material 44 a that extends beyond the attaching site. The zipper in this embodiment is attached in such a way that the zipper pull or slide can be completely hidden from view and inaccessible from an infant occupant. The zipper surrounds the entire perimeter of the surface of the mattress 46 and extends to where the base of the zipper or a zipper insert is located. The teeth of the zipper extend under the zipper insert and the zipper pull can pushed under the insert out of view. The bottom panel and the removable top panel of the sheet system can be made of any material suitable for sheeting or bedding. A waterproof, hypo-allergenic, dust mite resistant, anti-asthmatic, mould resistant lining has been incorporated into the under-surface of the top panel to provide protection to the mattress. In preferred embodiments, the sheet system is preferably made from polyester/-cotton fabrics.
[0027] It is expected that the removable top panel and the corresponding half of the zipper attachment means will be laundered much more frequently than the rest of the mattress case. The preferred embodiment with the moulded plastic zipper fastener has been shown to withstand a significant number of washings and tumble dryings yet still maintain its integrity and function as initially designed.
[0028] The bottom portion or bottom panel 42 of the mattress case is almost identical in length to the length of the cot or crib mattress plus twice the thickness of the mattress 46 to allow for the base of the sheet system to completely cover the bottom and four sides of the cot or crib mattress.
[0029] In the alternative, a side panel 48 equal in width to the thickness of the mattress may be used between the top and bottom panels.
[0030] A number of strips 52 , 54 , 56 , 58 or wide elastic have been strategically placed across the bottom panel and the sides 60 , 62 , 64 to allow for improved adjustability of fit to mattresses of different makes and sizes as well as to maintain the positional integrity of the removable top panel. The section of the moulded plastic zipper fastener that incorporates the zipper slide is attached to the bottom side of the sheet system with the slide at an inaccessible end of the bottom panel.
[0031] The removable top panel of the sheet system is also almost identical in dimensions to the top surface of the mattress. The half of the moulded plastic zipper fastener that does not contain the slide is attached to the removable top panel in such a manner that a fabric flap can be used to cover zipper when it is attached to the bottom of the mattress case. A waterproof, hypo-allergenic, dust mite resistant, anti-asthmatic, mould resistant lining has also been incorporated into the removable top panel to prevent damage to the mattress in the event of an accident. The lining also aides in maintaining the integrity of top panel through numerous washing and dryings.
ADVANTAGES OF THE INVENTION
[0032] The examples of the preferred embodiments hereinbefore described have several advantages over the prior art. In the case of the infant or paediatric application, safe sleeping recommendations with a simple bed sheet system are recommended and endorsed by various organisations concerned with sudden infant death syndrome and other child safety bodies. The sheet systems allow for the saving in time and physical effort required to change a prior art standard or cot or crib sheet set wherein only the top panel has to be removed as opposed to changing the complete sheet.
[0033] In terms of cost savings, where only a removable top panel is required to be laundered there is both a financial as well as a resource saving of both water, electricity and laundry detergent. Furthermore as the top panels can include a mattress protection lining, there is no need to purchase a separate mattress protector. The removal of a top panel caters to tired or sleeping infants when having to change the sheets due to an accident. Importantly the ability to change simply the top panel of a sheet or mattress case without having to lift a mattress or bend over a cot or crib, bars, panels, slates or rails limits the potential for lower back or abdominal strain of the user.
[0034] The present sheet system is also able to be utilised in any situation both on a private, commercial or institutional basis where numerous sheets have to be changed.
VARIATIONS
[0035] It will of course be realised that while the foregoing has been given by way of illustrative example of this invention, all such and other modifications and variations thereto as would be apparent to persons skilled in the art are deemed to fall within the broad scope and ambit of this invention as is herein set forth.
[0036] Throughout the description and claims this specification the word “comprise” and variations of that word such as “comprises” and “comprising”, are not intended to exclude other additives, components, integers or steps. | A bed sheet, comprising in combination, a top panel for covering a mattress top, a surrounding side panel adapted to surround the side edges of the mattress, the top panel removably attachable to the side panel to form a bed sheet for the mattress wherein in use, the top panel can be detached and removed from the side panel when the bed sheet is covering the mattress whereby the side panels are left in position on the side edges of the mattress. | 0 |
BACKGROUND OF THE INVENTION
This invention relates to geophysical exploration for petroleum and minerals. More particularly, this invention is directed to geophysical prospecting by means of the seismic technique.
Seismic prospecting involves generating seismic waves at the surface of the earth by means of a seismic source. The seismic waves travel downward into the earth and are reflected and/or refracted due to differences in acoustic impedance at the interfaces of various subsurface geological formations. Detectors, called seismometers, or geophones, located along the surface of the earth and/or in a borehole produce analog electrical seismic-trace signals in response to detected seismic wave reflections and/or refractions. The analog electrical seismic-trace signals from the seismometers, or geophones, can then be recorded. Alternatively, the analog electrical seismic-trace signals from the seismometers, or geophones, can be sampled and digitized prior to being recorded. The seismic-trace data recorded in iether manner is subsequently processed and analyzed for determining the nature and structure of the subsurface formations. Specifically, this invention is directed to testing the operability of the recorder of a cableless seismic digital recording system used for acquiring and processing seismic-trace data.
The cableless seismic digital recording system is a field system developed for seismic prospecting for digitally recording seismic-trace signals produced by seismometers, or geophones, without the need for multiconductor cables or alternate means such as multi-channel radio telemetry for transmitting seismic-trace data to a central recording point. In particular, the cableless seismic digital recording system includes small, portable recorders placed near the seismometer, or geophone, locations and arranged for producing individual recordings in response to control signals transmitted from a control point over a communications link, preferably a radio communications link. Cableless seismic digital recording systems are disclosed in Broding et al. U.S. Pat. No. 3,806,864 and Weinstein et al. U.S. Pat. No. 3,946,357 hereby incorporated by reference into this specification to form a part thereof.
Broding et al. U.S. Pat. No. 3,806,864, for example, discloses a cableless seismic digital recording system wherein out of a large array of recorders remotely deployed in a prospect area only those recorders needed for producing a given set of recording are selectively activated over a radio communications link and caused to record seismic-trace data. The remaining recorders remain essentially quiescent until there is a desire to produce a set of recordings for the prospect areas where they are situated. As disclosed in Broding et al. U.S. Pat. No. 3,806,864, the seismic-trace data is preferably recorded on a magnetic tape cartridge.
Since the recorders of the cableless seismic digital recording system disclosed in Broding et al. U.S. Pat. No. 3,806,864 are remotely deployed and activated by a radio communications link, from a practical standpoint operation of the recorders cannot be monitored during seismic prospecting. Consequently, Broding U.S. Pat. No. 3,952,283 discloses that when the seismometers, or geophones, and associated recorders are deployed, the individual recorders are activated (for example, by a radio transmitter or the like), and each activated recorder generates an aural and/or visual signal if the required connections have been made to the recorder and the recorder circuits are functional. Therefore, an indication is given that the seisometer, or geophone, has been connected to the recorder, the recorder has received a coded radio signal and the coded radio signal included the address for the particular recorder, a magnetic tape cartridge is in place in the recorder but the end of tape has not been reached, the recorder battery is adequately charged, and the recorder reset has been checked. Consequently, an inoperative recorder can be detected by inspection without having to verify an actual recording.
Now, many techniques for generating and recording seismic waves are currently in use. Exploding-gas and compressed-air guns placed on the surface of the earth and dynamite are examples of high energy seismic sources which generate a sharp pulse (impulse) of seismic energy. Vibrators, which generate a "chirp" signal of seismic energy, and hammers are examples of low energy surface seismic sources. In the case of vibrators, the recorded seismic wave reflections and/or refractions are cross-correlated with a replica (called the "pilot signal") of the original "chirp" signal in order to produce recordings similar to those which would have been produced with a high energy impulsive seismic source. This process is known as "vibroseis."
Considered in more detail, vibroseis seismic prospecting, commercialized by Continental Oil Company, typically employs a large, vehicle-mounted vibrator as a seismic source. The vehicle is deployed to a prospect area, and the vibrator is positioned in contact with the surface of the earth. Thereafter, the vibrator is activated for imparting vibrations to the earth, thereby causing seismic waves to propagate through the subsurface formations. The seismic wave reflections and/or refractions are detected by seisometers, or geophones, deployed in the prospect area.
Advantageously, the use of a vibrator can be more economical than the use of dynamite. Furthermore, as compared to the use of a high energy impulsive seismic source, such as dynamite, the frequency of the seismic waves generated by a vibrator can be selected by controlling the frequency of the pilot signal to the power source, such as a hydraulic motor, which drives the vibrator. More particularly, the frequency of the pilot signal to the vibrator power source can be varied, that is, "swept," for obtaining seismic-trace data at different frequencies. Consider, for example, Doty et al. U.S. Pat. No. 2,688,124 which discloses how a low energy seismic wave, such as generated by a vibrator, can be used effectively for seismic prospecting if the frequency of the vibrator "chirp" signal which generates the seismic wave is swept according to a known pilot signal and the detected seismic wave reflections and/or refractions are cross-correlated with the pilot signal in order to produce seismic-trace recordings similar to those which would have been produced with a high energy impulsive seismic source. Typically, the pilot signal is a swept frequency sine wave which causes the vibrator power source to drive the vibrator for coupling a swept sine wave "chirp" signal into the earth. A typical swept frequency operation can employ, for example, a 10- to 20-second long sine wave "chirp" signal with a frequency sweep of 14 to 56 Hz. The swept frequency operation yields seismic-trace data which enables the different earth responses to be analyzed, thereby providing a basis on which to define the structure, such as the depth and thickness, of the subsurface formations.
Unfortunately, recorded seismic-trace data always includes some background (ambient) noise in addition to the detected seismic waves reflected and/or refracted from the subsurface formations (referred to as "seismic signal"). Ambient noise is not repeatable with or dependent on the seismic source. The ambient noise appears in many forms, such as atmospheric electromagnetic disturbances, wind, motor vehicle traffic in the vicinity of the prospect area, recorder electrical noise, etc.
When a high energy impulsive seismic source is used, such as dynamite, the level of the detected seismic signal is usually greater than the ambient noise. Use of the cableless seismic digital recording system disclosed in Broding et al. U.S. Pat. No. 3,806,864 is most advantageous in instances when seismic-trace data is generated by a high energy impulsive seismic source. This is because the data storage capacity of commercially available magnetic tape cartridges is adequate for recording the seismic-trace data.
However, when a low energy surface seismic source is used, such as a vibrator used in vibroseis seismic prospecting, the ambient noise can be at a level greater than the seismic signal. For that reason, seismic-trace records are often produced involving the repeated initiation of the low energy surface seismic source at about the same origination point, thereby producing a sequence of seismic-trace data based on seismic wave reflections and/or refractions that have traveled over essentially the same path and therefore have approximately the same travel times. Because the data storage capacity of commercially available magnetic tape cartridges such as used in the cableless seismic digital recording system disclosed in Broding et al. U.S. Pat. No. 3,806,864 is limited, the capacity is not always adequate for recording every repetition individually as well as accommodating the increase in record length required when a low energy surface seismic source is used.
In order to obviate the limitation of the data storage capacity of commercially available magnetic tape cartridges such as used in the cableless seismic digital recording system disclosed in Broding et al. U.S. Pat. No. 3,806,864, seismic-trace data generated by low energy surface seismic sources can be vertically stacked (summed or composited) prior to recording in order to economize tape usage. Weinstein et al. U.S. Pat. No. 3,946,357 and Broding U.S. Pat. No. 4,017,833, hereby also incorporated by reference into this specification to form a part thereof, disclose hard-wired digital circuitry in the recorder of a cableless seismic digital recording system for vertically stacking seismic-trace data acquired by the recorder. Weinstein et al. U.S. Pat. No. 3,946,357 discloses a recorder including an adder circuit which sums newly acquired seismic-trace data received from a shift register with previously accumulated seismic-trace data temporarily stored in random access memory between consecutive initiations of the seismic source, and the accumulated sum is later recorded on a magnetic tape cartridge. Broding U.S. Pat. No. 4,017,833 discloses a recorder including a plurality of recirculating dynamic shift registers connected in cascade for storing the accumulated sum between consecutive initiations of the seismic source in order to economize power consumption. A co-pending patent application of Read et al. Ser. No. 454,405 filed Dec. 29, 1982, filed on the same date as this application and assigned to a common assignee and hereby incorporated by reference into this specification to form a part thereof, discloses microcomputer means in the recorder of a cableless seismic digital recording system for weighting as well as vertically stacking consecutive traces for improving the signal-to-noise ratio of seismic-trace data collected during seismic prospecting with low energy surface seismic sources.
The seismic-trace data processing circuits (the hard-wired digital circuitry disclosed in Weinstein et al. U.S. Pat. No. 3,946,357 and Broding U.S. Pat. No. 4,017,833 and the microcomputer means disclosed in the aforementioned Read et al. application) are highly desirable for processing seismic-trace data during seismic prospecting with low energy surface seismic sources. However, incorporation of such seismic-trace data processing circuits in cableless seismic digital recording system recorders has resulted in increased complexity of the recorder circuits. The need exists for not only checking the functionality of those recorder circuits checked as disclosed in Broding U.S. Pat. No. 3,952,283 but also testing the operability of more complex seismic-trace data processing circuits of a recorder of a cableless seismic digital recording system used during seismic prospecting with low energy surface seismic sources where the seismic-trace data must at least be summed prior to recording. This invention is directed to facilitate incorporation of test capabilities in a cableless seismic digital recording system recorder for checking the operability of the recorder seismic-trace signal acquisition as well as seismic-trace data processing circuits used during seismic prospecting with any type of seismic source, including high energy impulsive seismic sources and low energy surface seismic sources.
SUMMARY OF THE INVENTION
In accordance with the invention, means is provided in a cableless seismic digital recording system recorder used during seismic prospecting with any type of seismic source, including high energy impulsive seismic sources, such as dynamite, and low energy surface seismic sources, such as a vibrator, for testing the operability and for facilitating the maintenance of the recorder. The recorder preferably includes a microprocessor circuit having a read only memory which stores sets of programmed instructions. In accordance with a preferred embodiment of the invention, logic control signals needed for testing the operability of the recorder are generated by diagnostic routines contained within the programmed instructions. Tests are performed in response to actuable means, such as switches, of a control panel included in the recorder. The results of the tests are preferably displayed on the control panel, for example, as codes on a display means, such as an incandescent display.
The recorder preferably includes means for illuminating the recorder's displays; means for displaying the recorder's serial number; means for collecting data and/or displaying excursions of the recorder's gain-ranging amplifier, preferably without recording data on the recorder's magnetic cartridge tape; means for initiating a test of the recorder's arithmetic processing unit and random access memory and displaying a coded test result; and means for performing a cyclic redundancy check of the recorder's read only memory and displaying a coded test result. However, in accordance with various embodiments of the invention, only selected features for testing the operability and facilitating the maintenance of the recorder can be incorporated if only such features are desired.
In accordance with one embodiment of the invention, actuable means is provided in the recorder of a cableless seismic digital recording system, the actuable means being connected to display means and the recorder's gain-ranging amplifier for displaying excursions of the amplifier. Furthermore, a terminating resistor can be connected across the recorder's seismometer input connector for the amplifier, the actuable means being connected to the display means and the amplifier for indicating the operability of the amplifier. In either event, the excursions of the amplifier can be displayed without recording on the recorder's magnetic cartridge tape.
In another embodiment of the invention, actuable means is provided in the recorder, the actuable means being connected to the recorder's arithmetic processing unit and random access memory for testing the operability of the arithmetic processing unit and random access memory. The actuable means produces a test result code which is displayed by display means.
In yet another embodiment of the invention, actuable means is provided in the recorder, the actuable means being connected to the recorder's read only memory for performing a cyclic redundancy check of the read only memory. The actuable means produces a test result code which is displayed by display means.
There are further embodiments of the invention. In one embodiment of the invention, for example, actuable means is provided connected to display means for testing the display means by illuminating the display means so that a visual inspection of the display means can be conducted.
Finally, in accordance with the invention a method is provided for testing the weighting and vertical stacking operation of the recorder. The preferred method includes connecting the recorder to a test signal source; acquiring and weighting first and second test signals; vertically stacking the weighted test signals; and reproducing the weighted and vertically stacked test signals, the process preferably being repeated for each weighting mode. Preferably, the weighted and vertically stacked test signals are normalized before being reproduced.
Therefore, in accordance with various embodiments of the invention, display means included in the recorder can be tested for assuring that the display means is functional. The serial number of the recorder can be displayed for the purpose of identifying the recorder. Also, knowledge of the serial number permits the operability of the recorder to be charted over time. The gain-ranging amplifier included in the recorder can be tested by displaying the excursions of the gain-ranging amplifier without recording on the magnetic cartridge tape included in the recorder, thereby conserving tape usage. The arithmetic processing circuit and random access memory of the seismic-trace data processing means included in the recorder can be tested with a coded result being displayed. A cyclic redundancy check can be performed on the read only memory included in the recorder with a coded result being displayed. Finally, the weighting and vertical stacking operation of the recorder can be tested.
The tests in accordance with the invention check reliability of the recorder. The test also facilitate maintenance of a recorder which does not function properly.
BRIEF DESCRIPTION OF THE DRAWINGS
The above and other features of this invention and a better understanding of the principles and details of the invention will be evident to those skilled in the art in view of the following description of the preferred embodiments given in conjunction with the accompanying drawings, in which:
FIG. 1A is a diagrammatic cross-section of the earth which shows a field surveying operation using a cableless seismic digital recording system in accordance with the invention;
FIG. 1B illustrates deployment of the cableless seismic digital recording system shown in FIG. 1A;
FIG. 2 is a block diagram of electronic circuitry for a cableless seismic digital recording system recorder in accordance with the invention;
FIG. 3 illustrates the test features of the invention included in the cableless seismic digital recording system recorder shown in FIG. 2;
FIG. 4, comprising FIGS. 4A and 4B, shows the control panel of the cableless seismic digital recording system recorder shown in FIG. 2;
FIG. 5 shows a test setup in accordance with the invention; and
FIG. 6 illustrates the desired test signals obtained through the use of the test setup shown in FIG. 5.
By way of background, in a cableless seismic digital recording system, each of a plurality of small, portable recorders is placed near and connected to a seismometer, for example, in a prospect area for recording one trace of a multiple seismic-trace record. Each recorder is preset to be responsive to and activated by coded signals transmitted over a communications link, preferably a radio communications link, from a control point to all of the recorders. Initially, in producing a seismic-trace record, the coded signals transmitted to all recorders contain coded signals corresponding to the preset indicia of only those recorders desired to be activated. Also, record-header block identification data and recording-parameter data are transmitted from the control point for operation of the activated recorders and to be recorded digitally on the magnetic tape cartridges of the activated recorders together with additional identifying and operating information peculiar to and entered in each recorder. Immediately following is transmitted a zero-time mark. The identifying and operating information and zero-time mark are recorded with the timed sequence of digitized seismic-trace data associated with the corresponding seismometer. At the end of the recording, the activated recorders automatically de-activate, reset themselves, and assume radio standby status in readiness for the next activation and digital recording sequence. Those recorders of the larger array which do not receive the particular coded signals necessary for them to be activated remain in an intermediate standby status without any movement of the recording tape. When the location of the recorder and corresponding seismometer is to be changed, the recorded tape can be removed, and a fresh supply of blank recording tape inserted. The recorded tapes can then be transported to a central location for playback and storage of the seismic-trace data in any desired form and format of digital-computer storage and work tape.
By way of further background, with reference now to the drawings. FIG. 1A shows in diagrammatic fashion an earth cross-section with recorders 421-441 positioned for recording seismic-trace data. Spaced at intervals along a profile survey line extending along the earth's surface 19, the recorders 421-441 each include a radio receiver circuit, having an antenna, and a small magnetic tape device, preferably of the cartridge type. Each of the recorders 421-441 is connected to at least one seismometer and preferably to a group of interconnected seismometers 20 producing a single seismic-trace signal in the manner customary in seismic prospecting as shown in FIG. 1B.
At or near the positions occupied by the recorders 428 and 429 in FIG. 1A are respectively shown diagrammatically a first seismic source 21 and a second seismic source 22. At any convenient control point, there is a control means 23, including control circuits and a radio transmitter, which controls and coordinates the operation of the recorders 421-441. A preferred control means is more fully disclosed in a co-pending patent application of Bogey et al. Ser. No. 454,402 Dec. 29, 1982 filed on the same date as this application and assigned to a common assignee and hereby incorporated by reference into this specification to form a part thereof.
The various seismometers or seismometer groups 20 are initially deployed along the profile survey line, and each of the seismometers or seismometer groups is then electrically connected to the amplifier input terminal of the associated one of the recorders 421-441 as shown more clearly in FIG. 1B. For the purposes of illustration, the reference numbers 421-441 can be considered to function also as identification numbers for the locations of the seismometers or seismometer groups 20. As each seismometer or seismometer group 20 and associated one of the recorders 421-441 are placed at a location, that location number, or address, is entered into the recorder to become both the coded signal which will subsequently activate the recorder, as well as the recorder position identification to be supplied by the recorder and recorded as part of the record-header block identification data.
Seismic-trace data acquisition by each of the recorders is initiated by the coded radio signals transmitted over the one-way radio communications link with a single transmitter at the control point, or base station. An almost unlimited number of recorders can be remotely deployed simultaneously at any location in the prospect area within the radio transmission range of the control point.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 2 shows in block diagram form the circuitry of each of the recorders 421-441 in FIG. 1 for recording seismic-trace data. The circuitry is more fully disclosed in the aforementioned co-pending Read et al. application. The circuitry shown in FIG. 2 is capable of recording seismic-trace data generated by any type of seismic source, including high energy impulsive seismic sources and low energy surface seismic sources.
The structure and operation of the recorders 421-441 in FIG. 1 as used in seismic prospecting are disclosed in the aforementioned co-pending application of Read et al. This invention provides means in each of the recorders 421-441 for testing the operability and for facilitating the maintenance of the recorder. However, a general description of the structure and operation of the recorders 421-441 will now be given for the purpose of facilitating an understanding of the test features incorporated in each of the recorders in accordance with the invention.
Generally, each of the recorders 421-441 includes electronic and electromechanical circuitry as shown in FIG. 2, namely, a power supply circuit 26, a data acquisition circuit 27, a radio receiver circuit 28, a control panel circuit 30, and a magnetic tape cartridge recorder, which includes a drive circuit 32 and an encoder circuit 34, the latter being for encoding seismic-trace data to be recorded on magnetic cartridge tape 36. Each of the recorders 421-441 in FIG. 1 also includes a microcomputer means 38 as shown in FIG. 2. The microcomputer means 38 includes an input/output circuit 39 which is the interface between the microcomputer means and the other electronic and electromechanical circuitry. The microcomputer means 38 also includes a microprocessor circuit 40 having an associated scratch pad random access memory 45. The programmed instructions for the microprocessor circuit 40 are contained in a read only memory (ROM) 42. The seismic-trace data weighting and vertical stacking method which forms the subject matter of a co-pending patent application of Warmack Ser. No. 454,401, filed Dec. 29, 1982 or the subject matter of a co-pending patent application of Smith et al. Ser. No. 454,403, filed on the same date as this application and assigned to a common assignee and hereby incorporated by reference into this specification to form a part thereof, is preferably included in the sets of programmed instructions stored in the ROM 42. The microcomputer means 38 also includes an arithmetic processing unit (APU) 44, which performs weighting and vertical stacking under control of the microprocessor circuit 40 during seismic prospecting with a low energy surface seismic source, and a random access memory (RAM) 46 for storing seismic-trace data acquired during seismic prospecting with a high energy impulsive seismic source as well as weighted and vertically stacked seismic-trace data during seismic prospecting with a low energy surface seismic source between initiations of the low energy surface seismic source. Seismic-trace data stored in the RAM 46 is reproducibly recorded on the magnetic cartridge tape 36.
Coded radio signals transmitted by the control means 23 in FIG. 1 initiate an operation or sequence of operations by each of the activated recorders 421-441 from a set of predetermined operations embodied in the programmed instructions stored in the ROM 42 in FIG. 2. For example, on the one hand, when one of the activated recorders 421-441 in FIG. 1 receives coded radio signals indicative of the initiation of a high energy impulsive seismic source, the seismic-trace signal is sampled, digitized, and stored in the RAM 46 in FIG. 2. The seismic-trace data can then be normalized and recorded on the magnetic cartridge tape 36. On the other hand, when one of the activated recorders 421-441 in FIG. 1 receives coded radio signals indicative of the initial initiation of a low energy surface seismic source, the seismic-trace signal is sampled, digitized, weighted, and stored in the RAM 46 in FIG. 2. For a subsequent initiation of the low energy surface seismic source, the stored seismic-trace data from previous initiations can be vertically stacked, that is, summed, with the weighted seismic-trace data representative of the subsequent initiation. The procedure can be successively repeated until the weighted seismic-trace data representative of a selected number of initiations of the low energy surface seismic source has been vertically stacked. The accumulated seismic-trace data can then be normalized and recorded on the magnetic cartridge tape 36.
FIG. 3 illustrates the modes of operation and test features included in the sets of programmed instructions 50 stored in the ROM 42 in FIG. 2 of each of the recorders 421-441 in FIG. 1. Logic control signals needed for the circuits of each of the recorders 421-441 (power up/down, sampling, tape transport on/off, etc.) are generated by specialized control routines 52 as shown in FIG. 3. Receiver routines 54 interpret the coded radio signals transmitted by the control means 23 and cause each of the recorders 421-441 in FIG. 1 which are activated to be placed in various of the following operational modes.
With reference again to FIG. 3, in accordance with shooter's box routines 56, each of the activated recorders 421-441 in FIG. 1 can be used for initiating the seismic source. When the seismic source location transmitted by the control means 23 corresponds to the preprogrammed address of one or more of the activated recorders 421-441, a shooter's circuit 49 as shown in FIG. 2 in each recorder will energize at a designated source initiation time. The shooter's circuit 49 can be used to detonate a dynamite charge or initiate a sweep generator, for example. The initiation time is determined by a variable advance which can be entered on the control panel 30 as will be described in more detail in connection with FIG. 4. Multiple shooter's boxes can be selected simultaneously for initiating multiple shot seismic sources. The control means 23 in FIG. 1 can initiate a simultaneous selection of multiple shooter's boxes by transmitting a "shooter's call" of 9900 to 9999 in the instance where each of the recorders 421-441 selected as a shooter's box has an address within these limits. Consequently, as many as 100 unique shooter's boxes can be simultaneously selected.
Seismic-trace signals representative of the seismic source can be recorded by the same recorder which initiates the seismic source. Uphole signals indicative of the initial seismic wave from a high energy impulsive seismic source are detected and recorded, and the "uphole" time, that is, the time delay between initiation and detection of the direct seismic wave, can be calculated. The uphole time is also recorded in the header of the following record and can be displayed. The first or last initiation of a sequence of low energy surface seismic source initiations can be selectively recorded. Pilot signals from multiple vibrator initiations can be recorded for similarity analysis.
With reference again to FIG. 3, dynamite data processing routines 58 are used with high energy impulsive seismic sources. In accordance with the dynamite data processing routines 58, each of the activated recorders 421-441 in FIG. 1 merely records seismic-trace data. The seismic-trace data is not weighted or vertically stacked in the dynamite data processing mode. After recording is complete, each of the activated recorders 421-441 is de-activated. Gain-ranging amplification excursions can be displayed as will be described later.
With reference again to FIG. 3, stacking data processing routines 60 are used with low energy surface seismic sources. In accordance with the stacking data processing routines 60, several weighting and recording modes are available.
The weighting modes available in each of the activated recorders 421-441 in FIG. 1 are selectable by coded radio signal. They preferably include: IPW(0), unweighted floating-point sum; IPW(1), inverse average absolute value weighting; IPW(2), inverse average square value weighting; and IPW(4), inverse average fourth-power weighting.
In response to the initial initiation of a low energy surface seismic source the seismic-trace signal is sampled, digitized, weighted, and stored in the RAM 46 in FIG. 2. For subsequent initiations of the low energy surface seismic source, the stored seismic-trace data from the previous initiation is vertically stacked, that is, summed, with the weighted seismic-trace data representative of the subsequent initiations. The procedure is successively repeated until the weighted seismic-trace data representative of a selected number of initiations of the low energy surface seismic source has been vertically stacked.
Preferably, weighting values for each seismic-trace signal are obtained by linearly interpolating between the weighting values computed over predetermined portions of the traces, or windows. Computation and application of the weighting values along with vertical stacking, or summation, is preferably accomplished in a 4-byte format. Each set of seismic-trace data for a sequence of initiations is weighted and summed in the RAM 46. After the last set of weighted seismic-trace data in a sequence is vertically stacked, the cumulative sum stored in the RAM 46 is preferably normalized and then recorded on the magnetic cartridge tape 36. After normalization, the seismic-trace data is preferably converted back to a 2-byte format prior to being recorded.
In the stacking data processing mode, the recording is either "immediate," that is, at the end of the current sequence of operations, or "delayed," that is, at the beginning of the next sequence of operations (when a coded radio signal is transmitted to acquire the first set of seismic-trace data in the subsequent sequence). Following the "immediate" recording, each of the activated recorders 421-441 in FIG. 1 is de-activated; if a "delayed" recording is made, each recorder remains activated between initiations. Gain-ranging amplification excursions can be displayed after each seismic-trace signal acquisition cycle as will be described later.
In the stacking data processing mode, the activated recorders 421-441 remain activated between initiations so as to retain the accumulated seismic-trace data in RAM 46 in FIG. 2. If, however, the time between any two initiations in a sequence reaches ten minutes, for example, a timer in each of the activated recorders 421-441 in FIG. 1 causes each recorder to be de-activated.
Considered in more detail, when the recorders 421-441 are activated in the stacking data processing mode, the ten-minute timer is started to prevent a possible recorder lock-up with power on, unnecessarily consuming battery power. Therefore, the total time between initiations cannot reach ten minutes, or the activated recorders 421-441 are automatically de-activated, and, consequently, any vertically stacked seismic-trace data previously acquired is lost. Should conditions dictate that the time allowance be exceeded, a TEST CALL transmitted by the control means 23 to any of the recorders 421-441 will reset the timer of each of the recorders. Furthermore, if such a TEST CALL is transmitted, an aural alarm in the recorder which is TEST CALLed sounds before the recorder is de-activated.
As shown in FIG. 3, control panel routines 62 are included in the sets of programmed instructions stored in the ROM 42 in FIG. 2. The control panel routines 62 in FIG. 3 are executed in response to the actuation of switches included in the control panel 30 in FIG. 2.
In accordance with the invention, diagnostic routines 64 in FIG. 3 are also included in the sets of programmed instructions stored in the ROM 42 in FIG. 2. The diagnostic routines 64 in FIG. 3 are executed in connection with the control panel routines 62 upon actuation of certain switches included in the control panel 30 in FIG. 2. Logic signals needed for testing the operability of each of the recorders 421-441 in FIG. 1 are generated by the diagnostic routines 64 in FIG. 3.
FIG. 4 shows the control panel 30 of each of the recorders 421-441 in FIG. 1. The switches included in the control panel 30 in FIG. 4 under control of the control panel routines 62 in FIG. 3 and are preferably pushbutton switches which can be used for performing "alternate" functions in a manner similar to the pushbuttons included in hand-held calculators. There are six display select switches generally indicated by the numeral 72 in FIG. 4.
The primary functions of the six display select switches 72 are shown in FIG. 4A. An END OF RECORDING (EOR) pushbutton 74 shown in FIG. 4, in addition to performing the end-of-recording function, serves as an alternate key, much like that found on a hand-held calculator. The alternate functions of the display select switches 72, illustrated in FIG. 4B, including test features in accordance with the invention, are performed whenever the EOR pushbutton 74 is depressed simultaneously with the display select switches 72.
The primary and alternate functions which relate to the operation of the recorders 421-441 in FIG. 1 are disclosed in the aforementioned Read et al. application. The alternate functions which relate to the test features of the invention preferably include: SERIAL NO., which causes the serial number of each of the recorders 421-441 to be displayed by a display 76 as shown in FIG. 4, preferably a four-digit incandescent display; GAIN TEST, which collects seismic-trace data and causes the gain-ranging amplifier excursions to be displayed by the display 76 without recording data on tape, indicating the status of the data acquisition circuit 27 in FIG. 2; DISPLAY TEST, which lights all segments of the display 76 in FIG. 4; and APU/MEMORY TEST, which initiates a test of the arithmetic processing unit 44 and RAM 46 in FIG. 2 and causes a coded test result to be displayed by the display 76 in FIG. 4. (A cyclic redundancy check (CRC) is also performed on the ROM 42 in FIG. 2. A CRC comprises the addressing of selected storage locations in the ROM 42, reading out of data in those storage locations, processing the data by means of some algorithm for generating a number, and comparing the number with a reference, for example, a number in a look-up address.)
The test data provided by the alternate functions indicated above is valuable during operation and maintenance of the recorders 421-441 in FIG. 1. Such functions are not known in commercially available cableless seismic digital recording system recorders.
The following describes the procedures for field setup and testing of each of the recorders 421-441. It is assumed that the recorders 421-441 have been deployed as illustrated in FIG. 1.
Confidence in the operability of the recorders 421-441 can be established by routine testing. The testing can be categorized into control panel tests, basic functional tests, and, finally, weighting and vertical stacking tests.
Included in the tests are a visual test of the display 76 in FIG. 4, a dynamic test of the random access memory circuits 45 and 46 and arithmetic processing unit 44 circuit, a CRC of the ROM 42, and a gain test for verifying the operation of the gain-ranging amplifier included in the data acquisition circuit 27 in FIG. 2. Also, the serial number of each of the recorders 421-441 in FIG. 1 can be displayed. The various tests are as follows.
The DISPLAY TEST is initiated by depressing simultaneously the EOR pushbutton 74 and a CONSTANT B display select switch 78 in FIG. 4 which causes "8888" to be displayed by the display 76. A visual inspection can then be made for the purpose of checking for burned-out display segments. When the CONSTANT B display select switch 78 is released, the recorder is de-activated.
Simultaneously depressing the EOR pushbutton 74 and a STATION NO. display select switch 80 causes the serial number of the recorder to be displayed by the display 76. Consequently, the serial number of the recorder can be identified, and the operability of the recorder can be charted over time.
The EOR pushbutton 74 and a Y COORDINATE display select switch 82 when depressed simultaneously cause the high and low gain data collected during the last seismic-trace recording, or after running a gain test diagnostic routine, to be displayed by the display 76. In the latter instance, a 500-ohm terminating resistor is connected across the seismometer connector of the recorder. Thereafter, simultaneously depressing the EOR pushbutton 74 and a CONSTANT A display select switch 84 executes the gain test. The display 76 goes blank, and an aural alarm sounds. The aural alarm is sounded for approximately eight seconds while seismic-trace data from the seismometer connector is read in through the data acquisition circuit 27 in FIG. 2, and the highest and lowest gain values encountered are stored. Upon completion of the test, the aural alarm is stopped, and the display 76 in FIG. 4 illuminates and displays the highest and lowest gain values encountered as seismic-trace data was read in from the seismometer connector (the gains should be from 12 to 15). Since gain in the recorder is preferably represented in 6 dB steps, a display of "1506," for example, indicates that the highest gain used during the eight-second test was 15, or 90 dB, while the lowest gain was 6, or 36 dB. Used primarily as an indication of the gain-ranging amplifier status, the gain test can be used in the field for determining the proper setting for the preamplifier gain. Gain data remains displayed for approximately three seconds or can be recalled by simultaneously depressing the EOR pushbutton 74 and the Y COORDINATE display select switch 82.
Simultaneously depressing the EOR pushbutton 74 and a RECORD LENGTH display select switch 86 executes a dynamic test of the random access memory circuits 45 and 46, the arithmetic processing unit circuit 44, and a CRC of the ROM 42 in FIG. 2. The display 76 in FIG. 4 indicates which test is being performed by illuminating a 1, 2, or 3, respectively, after which a status code is displayed which shows the results of the test. The status code preferably remains displayed for about three seconds. A definition of the preferred status codes is given in Table I below.
TABLE I______________________________________Memory/APU/CRC Test Status CodesCode Status______________________________________0000 Memory Good, APU Good, CRC Good0095 Memory Good, APU Bad, CRC Not Tested0055 Memory Good, APU Good, CRC Bad2800 Scratch Pad Memory Bad, APU Good, CRC Good2895 Scratch Pad Memory Bad, APU Bad, CRC Not Tested2855 Scratch Pad Memory Bad, APU Good, CRC BadXX00 Stacking Memory Bad, APU GoodXX95 Stacking Memory Bad, APU BadXX55 Stacking Memory Bad, APU Good, CRC Bad______________________________________
"XX" reads "32" for a 32K RAM 46 and "64" for a 64K RAM 46 in FIG. 2.
Should the display 76 in FIG. 4 illuminate an invalid status code, the random access memory circuits 45 and 46 in FIG. 2 can be checked and the test rerun for confirming the arithmetic processing unit 44 and ROM 42 status. The scratch pad random access memory 45 will fail any time a single memory location is found bad; however, the test of the RAM 46 allows up to five bad locations and will display the number of bad locations encountered instead of displaying a 32" or "64" in the status word. A CRC failure ("55") indicates that the ROM 42 has failed.
Finally, a test can be conducted of the weighting and vertical stacking operation. However, before the stacking data processing mode tests are described, operation of the recorders 421-441 in FIG. 1 in the stacking data processing mode will be described to provide familiarization with expected results.
Each of the recorders 421-441 determines the particular stacking data processing mode by interrogating the SPARE transmitted by the control means 23 among the coded radio signals. The preferred codes for the SPARE are shown in Table II.
TABLE II______________________________________SPARE Codes______________________________________Digit 10 Dynamite (non-stacking) Mode1 Stacking ModeDigit 20 Normal processing1 Call for normalization after stacking, and record on tape at next call (Stacking Mode).8 Master reset9 Call for normalization after stacking, and record on tape immediately thereafter (Stacking Mode). The recorder powers down immediately after recording on tape. Digit 3*0 IPW(0)1 IPW(1)2 IPW(2)4 IPW(4)______________________________________ *Default values are IPW(2) for 3, 5, 6, and 7; IPW(0) for 8; and IPW(1) for 9.
In accordance with the test of the stacking data processing mode, the test setup shown in FIG. 5 is preferably assembled. A digital-to-analog converter 90 and a strip chart recorder 92 are for monitor purposes. An oscillator 94 is an audio-frequency oscillator. The oscillator 94 is preferably a low-distortion (0.1% maximum) audio sine wave circuit having, for example, 15 Hz and 30 Hz outputs capable of 0 dB (calibrated) 100 mV RMS with -30 to -36 dB attenuation from the 0 dB output level.
The stacking data processing mode test can be conducted as follows: (a) the recorder is set for 200 mV input range, five-second record length, all filters out; (b) the control means 23 sends two transmissions separated by 14 seconds in the IPW(0) mode; (c) the seismometer input following the first transmission is 30 Hz at -30 to -36 dB, and the seismometer input following the second transmission is 15 Hz at 0 dB from the oscillator 94 (A third or final "normalization" transmission is also preferably sent, which causes the weighted and vertically stacked data to be normalized.); (d) the above steps (b) and (c) are repeated with the control means alternatively set for the IPW(1), IPW(2), and IPW(4) modes.
A second or two of graph paper is obtained from the strip chart recorder 92 for each of the four records. With the four weighting and vertical stacking modes, various results which are related to the 15 Hz and 30 Hz signals are obtained as explained below in connection with FIG. 6.
The IPW(0) trace should look like FIG. 6A. In the IPW(0) mode, the two traces (15 Hz and 30 Hz) are added directly with no adjustment to the amplitudes. Since the 30 Hz signal is so much smaller than the 15 Hz, only the 15 Hz will be seen. The IPW(1) trace should look something like FIG. 6B and should definitely not appear as in FIG. 6A or 6C. In the IPW(1) mode, the small amplitude 30 Hz signal is digitally amplified to be the same amplitude as the 15 Hz, then they are added. The relative phases of the 15 Hz and 30 Hz signals will vary from trace to trace (In the IPW(1) mode, the appearance of the trace will vary somewhat from test to test). The IPW(2) and IPW(4) traces should look like FIG. 6C. In the IPW(2) and IPW(4) modes, the large amplitude 15 Hz signal is greatly attenuated relative to the amplitude of the 30 Hz signal. Therefore, the trace shows the strong dominance of the 30 Hz signal.
The tests in accordance with the invention check the reliability of the cableless seismic digital recording system recorder. The tests also facilitate maintenance of a recorder which does not function properly.
While the invention has been described with a certain degree of particularity, it is manifest that many changes can be made in the details of construction and the arrangement of components without departing from the spirit and scope of this disclosure. It is understood that the invention is not limited to the exemplified embodiments set forth herein but is to be limited only by the scope of the appended claims, including the full range of equivalency to which each element thereof is entitled. | Test features are incorporated in an improved cableless seismic digital recording system recorder. The improved recorder facilitates application of earlier cableless seismic digital recording systems to situations in which seismic-trace data is generated by low energy surface seismic sources, such as vibrators and hammers. A seismometer, or geophone, is connected to a remotely deployed radio-controlled portable recorder which contains circuitry for sampling, digitizing, processing, storing, and recording seismic-trace data. Coded radio signals instruct the recorder to commence an operation or sequence of operations from a predetermined set of programmed instructions stored in program read only memory included in the recorder. Such operations include data acquisition; optional weighting and vertical stacking (summing); normalization; recording; and seismic source initiation. Test features include control panel display of operational status and verification of gain-ranging amplifier operation. | 6 |
FIELD OF THE INVENTION
[0001] The present invention relates to a fuel cell device, and particularly to a fuel cell device providing self generation and with the function of mobile charging.
BACKGROUND OF THE INVENTION
[0002] The fuel cell could provide various features, such as extremely long operation time, without charging, low pollution, and low noise, and has been treated as a new generation of energy technology when the energy saving and environmental protection issues have been emphasized worldwide. Currently, a lot of high technology companies have worked hard to develop a micro fuel cell device to replace the existing batteries as the power source for portable electronic products. Unfortunately, the fuel cell device provided by each manufacturer could only be applied for a specific power consumption apparatus, but not suitable for other brands, or other types of power consumption apparatus for use. Secondly, the conventional fuel cell device could not provide the functions as a charger, and it still needs to combine with the independent power from the power consumption apparatus itself, and rely on the associated facilities, such as water management and heat management, provided by the power consumption apparatus itself, so as to keep the power supply from breaking down. Thus, the conventional fuel cell devices not only have the above-mentioned defects, but also have a large development space to work on.
[0003] The inventor of the present invention has been in view of the conventional defects, and worked for the improvement to disclose a fuel cell device with charger function, which could not only have self-generation and supply the electricity to various electronic products for operation, but also could function as a charger for various electronic products.
SUMMARY OF THE INVENTION
[0004] The main object of the present invention is to provide a fuel cell device, which could not only supply the power to various electronic products for usage and provide with the charger function, but also could charge different electronic products anytime and anywhere to realize the mobile charging idea.
[0005] To this end, the present invention provide a fuel cell device with charger function, which comprises: a base; a fuel cell stack, which is fixed at the base; at least one cathode fuel inlet, which is configured at the end of the upper surface of the fuel cell stack; a system fan, which is configured on the first side of the fuel cell stack; a wind cover, in which one end of the wind cover is tightly coupled with the first side of the fuel cell stack, and the other end of the wind cover is tightly coupled with the system fan; a display, which is configured on the second side of the fuel cell stack; a circuit board, which is vertically fixed with the base, and configured on the third side of the fuel cell stack; a condenser structure, which is configured on the fourth side and on the upper surface of the fuel cell stack, and the inlet of the condenser structure is coupled with the system fan; a condensing fan, which is tightly fixed on one side of the condenser structure; a mixing tank, which is tightly coupled with the side of the condenser structure on the same side of the condensing fan, and the mixing tank is connected to the anode fuel inlet of the fuel cell stack and the condenser structure with pipes, respectively; and, a pump, which is tightly configured on one side of the mixing tank.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] The present invention would be detailed described in the following to make the skilled in the art further understand the objects, features and advantages of the present invention with the embodiments and the attached figures, wherein:
[0007] FIG. 1 is a three-dimensional appearance view of the fuel cell device according to the present invention;
[0008] FIG. 2A is a front view and a partial perspective view of the internal assembly structure of the fuel cell device according to the present invention;
[0009] FIG. 2B is a rear view of the internal assembly structure of the fuel cell device according to the present invention;
[0010] FIG. 2C is a three-dimensional exploded diagram of the fuel cell device in FIG. 2A ; and
[0011] FIG. 3 is a layout diagram for the internal pipes of the fuel cell device according to the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0012] FIG. 1 is a three-dimensional appearance view of the fuel cell device according to the present invention. The fuel cell device 1 according to the present invention could be used as a charger. As shown in FIG. 1 , from the appearance, the fuel cell device 1 at least comprises a display 100 and a connection interface 102 ; in which, the connection interface 102 is at least used as an output for the power generated by the fuel cell stack in the fuel cell device 1 , and is used to connect with an electronic device, such as notebook computer, mobile phone, personal digital assistant (PDA), or any kind of portable electronic machine, and the means for the connection interface 102 could employ various electrical connection to realize, such as the conventional universal serial bus (USB) or cable. Also, the connection interface 102 could comprise a connection terminal for outputting different levels of voltage, such as 5V, 9V, 12V or 17V to the electronic device for usage. Furthermore, the display 100 according to the present invention could display various electric messages in the operation for the fuel cell device 1 , for example, the messages for insufficient power, saturation, or failure removal. And, the display 100 in the present invention is suitable to employ a compact liquid crystal display (LCD).
[0013] FIG. 2A is a front view and a partial perspective view of the internal assembly structure of the fuel cell device according to the present invention. FIG. 2B is a rear view of the internal assembly structure of the fuel cell device according to the present invention. FIG. 2C is a three-dimensional exploded diagram for the fuel cell device in FIG. 2A . As shown in FIG. 2A and FIG. 2B , the fuel cell device 1 according to the present invention comprises: a display 100 , a base 104 , a fuel cell stack 106 , a system fan 108 , a wind cover 110 , a circuit board 112 , a condenser structure 114 , a condensing fan 116 , a mixing tank 118 , and a pump 120 .
[0014] The internal configuration for these components in the fuel cell device 1 would be described in details. First, the fuel cell stack 106 is fixed with the base 104 , and the cathode fuel inlets 1060 as the air inlets are configured at the end of the upper surface of the fuel cell stack 106 . As shown in FIG. 2A , the fuel cell stack 106 is presented as a rectangular cylinder in appearance. The system fan 108 is configured on the first side of the fuel cell stack 106 , and provided with the function to introduce the air from the cathode fuel inlets 1060 to the reaction area inside the fuel cell stack 106 . One end of the wind cover 110 is similarly tightly coupled with the first side of the fuel cell stack 106 , and the other end of the wind cover 110 is tightly coupled with the system fan 108 . With the configuration of the wind cover 110 , it could effectively improve the performance for introducing air into the fuel cell stack 106 by the system fan 108 . The display 100 is configured on the second side of the fuel cell stack 106 . The circuit board 112 is vertically fixed with the bas 104 , and configured on the third side of the fuel cell stack 106 . The fuel cell device 1 according to the present invention further comprises at least on circuit component, wherein these circuit components are configured on the circuit board 112 , and the circuit components are electrically connected with the fuel cell stack 106 . These circuit components could be used to establish a power management circuit, so that the power generated by the fuel cell stack 106 could be matched with the power required by the electronic device.
[0015] Next, the condenser structure 114 , the condensing fan 116 , the mixing tank 118 and the pump 120 would be described. As shown in FIG. 2A , the condenser structure 114 is configured on the upper surface of the fuel cell stack 106 , and configured on the fourth side of the fuel cell stack 106 , and the inlet of the condenser structure 114 is coupled with the system fan 108 . As for the direct methanol fuel cell (DMFC), the condenser structure 114 is used to condense the steam from the system fan 108 into a liquid water. Of course, the recycled condensing water could be used by the fuel cell again. The condensing fan 116 is tightly fixed with one side of the condenser structure 114 , with the function to enhance the condensing effect of the condenser structure 114 . The mixing tank 118 is tightly coupled with the side of the condenser structure 114 on the same side of the condensing fan 116 , and the mixing tank 118 is connected with the anode fuel inlet of the fuel cell stack 106 and the condenser structure 114 with pipes, respectively. As for the direct methanol fuel cell, the mixing tank 118 is used to store the methanol aqueous solution. The pump 120 is tightly configured on one side of the mixing tank 118 , and usually employs a kind of dosing pump as the embodied component.
[0016] FIG. 3 is a layout diagram of the internal pipes of the fuel cell device 1 according to the present invention. As shown in FIG. 3 , the pump 120 is connected between the mixing tank 118 and an external fuel tank 30 with pipes for pulling the fuel in the fuel tank 30 into the first inlet 1180 of the mixing tank 118 ; wherein, the fuel tank 30 is usually used to store high density fuel. As for the direct methanol fuel cell, the fuel tank 30 is used to store the pure methanol. Moreover, the fuel cell device 1 further comprises: a first pump 32 and a second pump 34 ; wherein, the first pump 32 is connected between the mixing tank 118 and the fuel cell stack 106 with pipes for pulling the fuel in the mixing tank 118 into the anode fuel inlet 1062 of the fuel cell stack 106 ; and, the second pump 34 is connected between the mixing tank 118 and the condenser structure 114 with pipes for pulling the condensing water generated from the condenser structure 114 into the second inlet 1182 of the mixing tank 118 . As for the condensing water generated by the condenser structure 114 , it is mainly condensed by cooling and heat dissipation from the steam 36 generated by the fuel cell stack 106 . Furthermore, the anode fuel outlet 1064 of the fuel cell stack 106 in the fuel cell device 1 according to the present invention is also connected with the third inlet 1184 of the mixing tank 118 with pipes, so that the fuel without complete reaction in the fuel cell stack 106 could be recycled back to the mixing tank 118 .
[0017] The fuel cell device 1 with charger function according to the present invention could have self-generation, and provide with water management and heat management mechanism by itself, which is particularly suitable for application during a trip and for the area without public electricity system, and becomes the advantage of the present invention.
[0018] The present invention have been described in details with the preferred embodiments as above, and these disclosed embodiments are not used to limit the scope of the present invention. The skilled in the art could have some changes and modification without departing from the spirit and scope of the present invention, and these changes and modification are still belonged to the attached claims of the present invention. | The present invention discloses a fuel cell device with charger function, which comprises a base, a fuel cell stack, a system fan, a wind cover, a display, a circuit board, a condenser structure, a condensing fan, a mixing tank and a pump. The fuel cell device could not only supply the power to various electronic products for usage and provide with the charger function, but also could charge different electronic products anytime and anywhere to realize the mobile charging idea. | 8 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a Continuation of International Application No. PCT/FR2006/002230, filed Oct. 4, 2006, which was published in the French language on Apr. 19, 2007, under International Publication No. WO 2007/042639 A2 and the disclosure of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] The present invention concerns protecting a human body part, in particular the foot.
[0003] The foot has a shock absorbing layer called the footpad able to support up to eight times the weight of the body. The footpad also allows the mechanical “load” imposed by the weight of the body to be distributed. Various patients suffer from inflammation, callosities or pain, linked to inevitable wear of the natural footpad with age. Some people also suffer from foot abnormalities (callosities, corns, soft corns, hallux valgus) or cutaneous injuries (irritations, fissures, plantar warts, etc.). In addition, for some people, such as diabetics suffering from neuropathies or arteriopathies, it is absolutely vital to protect certain parts of the foot to avoid lesions from appearing.
[0004] Some polymer gels like polydimethylsiloxane oil (PDMS) silicone gels, such as those described in French Patent FR 2 712 487 or commercialized by Millet Innovation under the trademark Epithélium 26®, have viscoelastic features similar to human tissues. These materials are therefore particularly adapted to be used as protection modules to protect a human body part and in particular the foot. When they are used in the form of a cushion, these materials turn out to be efficient to relieve pains and protect all the painful areas of the foot.
[0005] Polymer gels are usually soft and stick more or less to the skin. Their implementation in the field of chiropody generally requires shaping the polymer gel by applying it onto the foot part to be protected. Then, so that it keeps its shape, the gel is fixed using a layer of glue on a piece of cloth, the polymer gel in conjunction with the piece of cloth constituting a protection module.
[0006] The implementation of such protection modules therefore entails to assembling several elements using glue, in the presence of the person for whom the protection module is intended.
[0007] The use of glue raises numerous difficulties. It entails, in particular, allowing a certain drying time in specific temperature conditions. In addition, contrary to silicone gels, glues are usually not neutral on a physiological level. The same is true for solvents which evaporate during the glue drying phase.
[0008] In addition, some protection modules in the form of cushions made of silicone gel are associated with a holding element to hold the cushion on the foot. The holding element has a curved semi-cylindrical shape to enter the interdigital space near the big toe and be held therein. To avoid any risk of lesion formation, the holding element is made of the same material as the cushion or a material having similar viscoelastic properties.
[0009] It is difficult to manufacture such a protection module. Indeed, it is not conceivable to make the protection module by molding in one part, because the shape of the holding element causes problems of draft. In addition, a silicone gel having the desired physical properties is not adapted to injection molding. The protection module must therefore be made in two different components, which must then be assembled, for example using glue or similar adhesive.
BRIEF SUMMARY OF THE INVENTION
[0010] An aim of the present invention is to simplify assembling and/or keeping the shape of one or more components made of polymer gel. The present invention more particularly aims to suppress the use of glue.
[0011] These aims are achieved by taking advantage of a surprising effect, which occurs upon contacting some polymer gels with a sheet made of a microporous material.
[0012] More particularly, according to a first aspect, the invention provides a method for assembling a first material made of polymer gel with a second material. According to the invention, the second material is made of a microporous material. The method comprises contacting the first material with the second material without adding glue or other adhesive, the polymer gel linking both materials by penetrating micropores of the second material and creating a developed contact surface greater than the apparent contact surface between the two materials.
[0013] According to one embodiment, the second material comprises an agent able to fix to the polymer gel.
[0014] According to one embodiment, the agent able to fix to the polymer gel comprises silica particles.
[0015] According to one embodiment, the second material comprises a polyolefin.
[0016] According to one embodiment, the second material comprises polyethylene.
[0017] According to one embodiment, the polymer gel is a silicone gel.
[0018] According to one embodiment, the polymer gel comprises a polydimethylsiloxane obtained by mixing silicone oils.
[0019] According to one embodiment, the polymer gel is obtained from a partially polymerized mix of silicone oils.
[0020] According to one embodiment, the method comprises conforming the first material by applying the first material onto the body part to be protected, before contacting it with the second material.
[0021] According to one embodiment, the first material has the form of a cushion and the second material has the form of a sheet.
[0022] According to one embodiment, the second material is used to assemble between them two components formed of the first material, the polymer gel of the two components being attracted into the second material.
[0023] According to one embodiment, the method comprises conforming at least one of the components made of polymer gel, before contacting with the second material.
[0024] According to a second aspect, the invention also relates to an assembly of a first material made of polymer gel to a second material. According to the invention, the second material is made of a microporous material, the assembly being obtained by contacting the first material with the second material without adding glue or other adhesive, the polymer gel linking both materials by penetrating micropores of the second material and creating a developed contact surface greater than the apparent contact surface between the two materials.
[0025] According to one embodiment, the second material comprises an agent able to fix to the polymer gel.
[0026] According to one embodiment, the agent able to fix to the polymer gel comprises silica particles.
[0027] According to one embodiment, the second material comprises a polyolefin.
[0028] According to one embodiment, the second material comprises polyethylene.
[0029] According to one embodiment, the polymer gel is a silicone gel.
[0030] According to one embodiment, the polymer gel comprises a polydimethylsiloxane obtained by mixing silicone oils.
[0031] According to one embodiment, the polymer gel is obtained from a partially polymerized mix of silicone oils.
[0032] According to one embodiment, the second material is used to assemble between them two components formed in the first material, the polymer gel of the two components being attracted into the second material.
[0033] According to a third aspect, the invention also relates to a module for protecting a human body part, comprising an assembly as described above, the first material forming a cushion, and the second material having the form of a sheet.
[0034] According to one embodiment, the cushion is conformed by being applied onto the body part to be protected before being fixed to the microporous sheet to be maintained in shape.
[0035] According to one embodiment, the cushion has an opening, in order to form with the sheet a cavity susceptible of containing an active substance.
[0036] According to one embodiment, the module comprises a holding element formed in the first material, fixed without glue to another face of the microporous sheet, by penetration of the polymer gel into micropores of the sheet after contacting the holding element with the sheet.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0037] The foregoing summary, as well as the following detailed description of the invention, will be better understood when read in conjunction with the appended drawings. For the purpose of illustrating the invention, there are shown in the drawings embodiments which are presently preferred. It should be understood, however, that the invention is not limited to the precise arrangements and instrumentalities shown. In the drawings:
[0038] FIG. 1 is a perspective view of a component made of polymer gel intended for the treatment of fissures on the heel, according to an embodiment of the invention;
[0039] FIG. 2 is a perspective view showing the implementation of the component shown in FIG. 1 , according to an embodiment of the invention;
[0040] FIG. 3 is a perspective view of the component shown in FIGS. 1 and 2 , assembled onto a support according to an embodiment of the method of the invention;
[0041] FIG. 4 is an exploded transverse sectional view of a protection module comprising different components made of polymer gel, assembled according to an embodiment of the method of the invention;
[0042] FIG. 5 is a perspective view of the assembled protection module shown in FIG. 4 ; and
[0043] FIG. 6 is a perspective view of a bandage made according to an embodiment of the method of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0044] FIG. 1 shows a component 11 in the form of a small bar of substantially triangular cross-section, a face of which is concave in order to adapt to the external edge of a foot heel. The component 11 is made of a polymer gel, such as a silicone gel obtained by partial polymerization of a mix of silicone oils. This material advantageously has viscoelastic features similar to human tissues. The component 11 is, for example, made of a material comprising partially polymerized polydimethylsiloxane oils (PDMS), commercialized by Millet Innovation under the trademarks EPITHELIUM 26, EPITHELIUM 27 or EPITHELIUM 28.
[0045] The component 11 is preferably made in the form of a profile, whose section and dimensions are adapted to the part of the foot for which it is intended. In the example of FIG. 1 , it is intended for being applied onto the rear edge of the heel part in contact with the floor, in standing position. The aim of the component 11 is particularly to protect this part of the foot in the event of deep heel fissures, or in case of particular weakness of the part, for example due to a post-surgical or, more usually, a post-traumatic situation.
[0046] In FIG. 2 the component 11 is curved to adapt to the outline of the heel part. Maintaining the shape of the component is performed according to the invention by a sheet 12 made of a microporous material on which the component 11 is applied. The sheet 12 , for example, comprises a microporous material made of polyolefin, such as polyethylene or a mix of polyolefins, doped by silica powder, and optionally, carbon black. The size of the open cells of the microporous material is, for example, between 0.1 and 1 μm.
[0047] In FIG. 3 the component 11 , curved in the manner shown in FIG. 2 , is contacted with the sheet 12 , the whole forming a protection module 1 according to the invention. Upon contact, the component 11 and the sheet 12 instantaneously stick to each other. This surprising effect can be explained by the microporous feature of the sheet 12 and by the fact that a part of the silicone oils constituting the component 11 are not completely polymerized and are therefore in the liquid state. Due to its porosity, the sheet 12 has microcavities or micropores on the surface, forming a developed total surface much greater than the apparent surface of the sheet. Upon contacting the sheet 12 , the non-polymerized silicone oils of the component 11 are attracted by capillarity into the microcavities of the sheet surface. The result is that the developed contact surface between the component 11 and the sheet 12 is much greater than the apparent surface of the component contacting with the sheet. The mechanical link thus obtained between the component 11 and the sheet 12 turns out to be resistant, in particular, to shear and to a lesser extent to tear off, given the attraction of the terminations of silicon oils toward the silica particles which are the filler of the material 12 . Assembling the component 11 and the sheet 12 , therefore, does not require adding glue or other adhesive.
[0048] Advantageously, the sheet 12 comprises an agent able to fix to the polymer gel. The agent comprises, for example, silica particles. The proportion in volume of silica particles is, for example, between 35 and 80%. The diameter of the silica particles is, for example, between 0.01 and 20 μm. Such a sheet is, for example, commercial available under the trademark AEROSHOES®.
[0049] The free oils (not polymerized) turn out to have the property of being very attracted to silica. They are, therefore, immediately attracted into the sheet when contacting the sheet with the component 11 . Bridges are then created within the microporous material between the terminations of PDMS molecules and silica. The bridges form very resistant mechanical links. The resistance of the fixation of the component on the sheet is consolidated by these bridges, which are very numerous, due to the great developed contact surface between the polymer gel and the sheet.
[0050] Assembling the protection module 1 may also be done easily by a chiropodist in the presence of the person for whom the protection module is intended. After fixing the component onto the sheet 12 , the edges of the sheet which stick out from the component may be cut.
[0051] FIG. 4 shows a cushion 21 to be fixed onto a holding element 22 to make a protection module 2 . The holding element has a curved, semi-cylindrical shape adapted to be located in the interdigital space near the big toe. The cushion and the holding element are made of a polymer gel.
[0052] According to the invention, a sheet 23 made of a microporous material is used to fix the holding element 22 on the cushion 21 . As previously described with reference to FIGS. 2 and 3 , simply contacting the sheet 23 with the polymer gel of the cushion and the holding element makes it possible to obtain a very strong mechanical link, without it being necessary to use glue or other adhesive. This method allows the protection module 2 shown in FIG. 5 , comprising the holding element 22 fixed on a face of the cushion 21 by the sheet 23 , to be obtained.
[0053] The chiropodist may, therefore, adapt the protection module to the person for whom it is intended, independently choosing a cushion and a holding element, adapted to the person's morphology. The two components are then assembled by applying a piece of microporous sheet onto the cushion substantially at the location of the holding element, and then assembling the holding element once the cushion has been placed onto the foot. In this manner, the position of the holding element on the cushion is adapted to the morphology of the person's foot. The components made of polymer gel may also be shaped on the foot before assembling.
[0054] The cushion and the holding element may be made of a material comprising partially polymerized polydimethylsiloxane oils. The microporous sheet may be made of polyolefin advantageously filled with silica.
[0055] FIG. 6 shows another application of the method according to the invention. The Figure shows a bandage 3 comprising a planar component 31 made of polymer gel and having a central opening 33 . The component 31 is fixed to a microporous sheet 32 , according to the method of the invention. The central opening 33 of the component 31 is thus closed on one side by the sheet 32 , so as to form a cavity intended to receive a material (liquid, paste or gel) containing an active principle. Holding the bandage on the skin is, for example, performed by the intrinsic adhesive power of the polymer gel. Some silicone gels have such an adhesive power.
[0056] The materials described above may be used to make the component 31 of polymer gel and the microporous sheet 32 .
[0057] In the applications previously described, liquids containing an active principle, such as antibacterials, antimycotic agents, deodorants, anti-inflammatory drugs, and the like, may be incorporated into the components made of polymer gel. It turns out that the presence of such liquids does not impact the solidity of the mechanical link with the microporous sheet.
[0058] It will appear clearly to those skilled in the art that the method according to the present invention is susceptible of various other embodiments and applications. Thus, the invention is not limited to the use of a polyolefin sheet filled with silica. It is, however, important that the polymer gel be capable of attraction by capillarity within the microporous material constituting the sheet. This last feature does not necessarily require that the polymer gel be a silicone gel, or that the polymer gel be obtained from a mix of partially polymerized polydimethylsiloxane oils.
[0059] It is not necessary either that the sheet comprise an agent, such as silica, able to fix to the polymer gel, since the mechanical link between the microporous sheet and a component made of polymer gel is obtained by the fact that the polymer gel penetrates into the sheet microporosities in order to obtain a developed contact surface much greater than the apparent contact surface between the sheet and the polymer gel, as explained above. In fact, the aim of providing such an agent in the microporous sheet is only to consolidate the solidity of the link.
[0060] The invention is not only applicable to the manufacture of foot protectors. It also applies to the manufacture of protectors of other body parts, all of these applications implementing the surprising property of these two materials spontaneously assembling upon contact.
[0061] It will be appreciated by those skilled in the art that changes could be made to the embodiments described above without departing from the broad inventive concept thereof. It is understood, therefore, that this invention is not limited to the particular embodiments disclosed, but it is intended to cover modifications within the spirit and scope of the present invention as defined by the appended claims. | A method is provided for fixing a silicone gel component, including a step of contacting the gel component with a sheet made of microporous material, such that the silicone gel is attracted upon contact with the sheet, thereby forming an assembly in which the component is fixed to the sheet without glue or adhesive. The method is applicable to the production of modules for protecting a human body part, in particular the foot. | 1 |
RELATED APPLICATIONS
[0001] This application claims priority to Chinese Application Serial Number 201310561010.8, filed Nov. 12, 2013, which is herein incorporated by reference.
BACKGROUND
[0002] 1. Field of Invention
[0003] The invention relates to a level shift circuit and a DC-DC buck converter controller for using the same, and more particularly relates to a level shift circuit with a power-saving function and a DC-DC buck converter controller for using the same.
[0004] 2. Description of Related Art
[0005] In the conventional DC-DC buck converting circuit, a level shift circuit is required to adjust the signal level for correctly turn on and off the high-side transistor of an N-type MOSFET. However, the conventional current type level shift circuit has a large power consumption and leakage paths, and so is not suitable for light-load. On the other hand, the conventional pulse type level shift circuit has no problems of leakage paths and large power consumption, but the pulse type level shift circuit keeps levels of output signals thereof through a parasitic capacitance of a transistor. When a reference level of the level shift circuit flutters, it is easy to cause a logic state of the output signal of the level shift circuit to be changed. Thus, the anti-interference ability of the pulse type level shift circuit is very poor.
[0006] FIG. 1 is a schematic diagram of a conventional current type level shift circuit. A first logic low level VS 1 and a first logic high level VP 1 are two logic levels of a first logic family. A second logic low level VS 2 and a second logic high level VP 2 are two logic levels of a second logic family. The function of the level shift circuit is used to transforming a high logic level and a low logic level of one logic family, i.e., the first logic high level VP 1 and the first logic low level VS 1 , into the other logic family, i.e. the second logic high level VP 2 and the second logic low level VS 2 .
[0007] When a first input signal S is at the first logic high level VP 1 and a second input signal R is at the first logic low level VS 1 , a transistor MN 4 is turned on and a transistor MN 5 is turned off. At this moment, a current of a current source Ib flows through the current mirror composed of transistors MN 1 and MN 2 to make a current mirrored flow through the transistors MP 1 , MN 4 and MN 2 . A transistor MP 2 also simultaneously mirrors the current of the transistor MP 1 to make a level of a first output signal Q raise to the second logic high level VP 2 . Moreover, because the transistor MN 5 is cut off and leads to no current, the transistors MP 4 and MP 3 are also cut off. Because the level of the first output signal Q is at the second logic high level VP 2 and a transistor MN 7 is turned on, a potential of a second output signal QN is reduced to the second logic low level VS 2 . Similarly, when the first input signal S is at the first logic low level VS 1 and the second input signal R is at the first logic high level VP 1 , the level of the first output signal Q is at the second logic low level VS 2 and the level of the second output signal ON is at the second logic high level VP 2 . According to the level shift mentioned above, the first input signal S and the second input signal R of the first logic high level VP 1 and the first logic low level are transformed into the first output signal Q and the second output signal QN of the second logic high level VP 2 and the second logic low level VS 2 .
[0008] For ensuring a transforming speed of the level shift, when the first input signal S is at a high level and the second signal R is at a low level, the current flowing from the second logic high level VP 2 via the transistors MP 1 , MN 4 and MN 2 to the first logic low level VS 1 is designed to be larger. Similarly, when the first input signal S is at a low level and the second input signal R is at a high level, the current flowing from the second logic high level VP 2 via the transistors MP 4 , MN 5 and MN 3 to the first logic low level VS 1 is also designed to be larger. This circuit design can ensure the transforming speed of the level shift in the current type level shift circuit. However, such circuit design has the higher power consumption. Especially, the DC-DC buck converting circuit operates under a light-load, such as the diode emulation mode. In this mode, the larger current continuously flowing through the current type level shift circuit is not conducive to power-saving. The second logic high level VP 2 may be provided by an extra boost circuit, not provided by an independent voltage source. The larger current continuously flowing leads to the second logic high level VP 2 falling down and so a voltage difference between the second high level VP 2 and the second logic low level VS 2 is decreased.
[0009] FIG. 2 is schematic diagram of a conventional improved current type level shift circuit. Compared with that shown in FIG. 1 , the improved current type level shift circuit extra increases transistors MN 8 and MN 9 . The main function of the transistors MN 8 and MN 9 is voltage suppression, and gate electrodes thereof are coupled to the first logic high level VP 1 for ensuring source electrodes of the transistors MN 8 and MN 9 , i.e., potentials of drain electrodes of the transistors MN 4 and MN 5 are clamped under the first logic high level VP 1 . Under this circuit design, both the transistors MN 4 and MN 5 can be low-voltage transistors, and it is conducive to raise the switching speed of the transistors MN 4 and MN 5 . However, large power consumption problem still exists.
[0010] FIG. 3 is a schematic diagram of a conventional pulse type level shift circuit. Pulse signals VPS and VPR are pulse signals respectively triggered on rising-edges of the first input signal S and the second signal R, and have narrow pulse widths. The pulse signals VPS and VPR are respectively coupled to gate electrodes of transistors MN 2 and MN 3 . FIG. 4 shows waveform diagrams of the pulse type level shift circuit shown in FIG. 3 . When both the first input signal S and the pulse signal VPS are at the first logic high level VP 1 and the second input signal R is at the first logic low level VS 1 , a large current flows from the second logic high level VP 2 via the transistors MP 1 , MN 4 and MN 2 to the first logic low level VS 1 . The transistor MP 2 mirrors a current of the transistor MP 1 to make the first output signal Q raise to the second logic high level VP 2 , while the second output signal QN is at the second logic low level VS 2 . When the first input signal S is still at the first logic high level VP 1 and the pulse signal VPS is changed to be at the first logic low level VS 1 , the current of the transistor MP 1 is zero. At this moment, the whole level shift circuit does not consume any current. Similarly, when both the second input signal R and the pulse signal VPR are at the first logic high level VP 1 and the first input signal S at is the first logic low level VS 1 , the large current flows from the second logic high level VP 2 via the transistors MP 4 , MN 5 and MN 3 to the first logic low level VS 1 . The transistor MP 3 mirrors the current of the transistor MP 4 to make the second output signal QN raise to the second logic high level VP 2 , while the first output signal Q is at the second logic low level VS 2 . Soon after, when the second input signal R is still at the first logic high level VP 1 and the pulse signal VPR is changed to be at the first logic low level VS 1 . At this moment, the whole level shift circuit does not consume any current.
[0011] Advantages of the pulse type level shift circuit are speeding up the translating speed of the level shift due to the large current flowing through the pulse type level shift circuit, and lowering power consumption due to no current consumption after level shift has completed. However, the pulse type level shift circuit still has defects. When both the pulse signals VPR and VPS are at the logic low level, the levels of the first output signal Q and the second output signal QN are kept by the parasitic capacitances of the transistors, which causes the pulse type level shift circuit has poor anti-noise ability.
[0012] FIG. 5 is a schematic diagram of a level shift circuit disclosed in U.S. Pat. No. 7,839,197 of RICHTEK Technology Corporation. The level shift circuit shown in FIG. 5 is designed with the advantages of the pulse type level shift circuit and the current type level shift circuit. FIG. 6 shows waveform diagrams of the pulse type level shift circuit shown in FIG. 5 . When the first input signal S and the pulse signal VPS are at the first logic high level VP 1 and the second input signal R is at the first logic low level VS 1 , a current flows from the second logic high level VP 2 via the transistors M 1 , M 5 and M 11 and a basic current source 642 to the first logic low level VS 1 . At this moment, a transistor M 8 mirrors a current of the transistor M 1 to make the first output signal Q be at the second logic high level VP 2 and the second output signal QN be at the second logic low level VS 2 . When the first input signal S is still at the first logic high level VP 1 and the pulse signal VPS is changed to be at the first logic low level VS 1 , the transistor M 111 is cut off and the basic current source 642 still maintains a small basic current flowing through the transistors M 5 and M 1 , and the small current is used to maintain the first output signal Q to continuously be at the second logic high level VP 2 . Similarly, when the second input signal R and the pulse signal VPR are at the first logic high level VP 1 and the first input signal S is at the first logic low level VS 1 , the current flows from the second logic high level VP 2 via the transistors M 4 , M 6 and M 12 and a basic current source 644 to the first logic low level VS 1 . At this moment, a transistor M 7 mirrors a current of the transistor M 4 to make the second output signal QN be at the second logic high level VP 2 and the first output signal Q become the second logic low level VS 2 . When the second input signal R is still at the first logic high level VP 1 and the pulse signal VPR is changed to be at the first logic low level VS 1 , the transistor M 12 is cut off and the basic current source 644 still maintains a small basic current flowing through the transistors M 6 and M 4 , and the small current is used to maintain the second output signal QN to be continuously at the second logic high level VP 2 . The transistors M 2 and M 3 are two mirror acceleration transistors.
[0013] Advantages of the level shift circuit shown in FIG. 5 involves the advantage of the high speed level shift of the pulse type level shift circuit and the good anti-noise ability of the current type level shift circuit. FIG. 7 shows waveform diagrams of the second logic high level VP 2 and the second logic low level VS 2 of the level shift circuit shown in FIG. 5 . In the continuous current mode, the converting circuit continuously operates to make the boost circuit retain the potential of the second logic high level VP 2 . However, in the diode emulation mode, the basic current sources 642 and 644 of the level shift circuit still provide the small current and continuously consumes the energy stored in the boost circuit, and it causes the voltage difference between the second logic high level VP 2 and the second logic low level VS 2 slowly dropping down and further is possible to cause the problem of the logic error level of the first output signal Q and the second output signal QN.
SUMMARY
[0014] In view of the problems of the level shift circuit of the prior art, the level shift circuit of the present invention can avoid the level shift circuit consuming additional currents for achieving the advantages of reducing the power consumption, and further avoid the logic error level of the output signal when the converting circuit is operating under the light-load.
[0015] To accomplish the aforementioned and other objects, the present invention provides a level shift circuit, comprising a signal input circuit, a signal output circuit and a state detecting circuit. The signal input circuit is coupled between a first level and a second level, configured to receive a first input signal and a second input signal. Levels of the first input signal and the second input signal are switched between the first level and a third level. The signal input circuit generates a first current when the first input signal is at the third level, and generates a second current when the second input signal is at the third level. The signal output circuit is coupled between the second level and a fourth level, configured to output a first output signal and a second output signal. Levels of the first output signal and the second output signal are switched between the second level and the fourth level. The first output signal is switched to the second level when the signal input circuit generates the first current. The second output signal is switched to the second level when the signal input circuit generates the second current. The state detecting circuit detects an operating state of a converting circuit, and accordingly determines whether generating a stop signal for stopping the signal input circuit generating the first current and the second current.
[0016] The present invention also provides a DC-DC buck converter controller, adapted to control a first power switch and a second power switch of a converting circuit connected in series. The first power switch is coupled to an input voltage and a connection node, and the second power switch is coupled to the connection node and a common potential. The DC-DC buck converter controller comprises a feedback control circuit, a level shift circuit and a driver. The feedback control circuit generates a pulse width modulating signal according to a detecting signal indicative of a state of the converting circuit. A level of the pulse width modulating signal is switched between the common potential and a driving potential. The level shift circuit generates a level shift signal according to the pulse width modulating signal. The level shift circuit comprises a signal input circuit, a signal output circuit and a state detecting circuit. The signal input circuit is coupled between the common potential and a reference potential. The signal input circuit generates a first current when the pulse width modulating signal is at the driving potential, and generates a second current when the pulse width modulating signal is at the common potential. The signal output circuit is coupled between the reference potential and the connection node, configured to output the level shift signal. A level of the level shift signal is switched between the reference potential and a potential of the connection node. The level shift signal is switched to the reference potential when the signal input circuit generates the first current, and the level shift signal is switched to the potential of the connection node when the signal input circuit generates the second current. The state detecting circuit detects an operating state of the converting circuit and accordingly determines whether generating a stop signal for stopping the signal input circuit generating the first current and the second current. The driver is coupled to the level shift circuit and the feedback control circuit, and generates a high-side control signal and a low-side control signal according to the pulse width modulating signal and the level shift signal for respectively turning on and off the first power switch and the second power switch.
[0017] Besides, the level shift circuit of the present invention also can additionally add a time delay for avoiding the noise interference and further raising anti-noise ability.
[0018] It is to be understood that both the foregoing general description and the following detailed description are exemplary, and are intended to provide further explanation of the invention as claimed. In order to make the features and the advantages of the invention comprehensible, exemplary embodiments accompanied with figures are described in detail below.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] The present invention will now be specified with reference to its preferred embodiment illustrated in the drawings, in which:
[0020] FIG. 1 is a schematic diagram of a conventional current type level shift circuit.
[0021] FIG. 2 is a schematic diagram of a conventional modified current type level shift circuit.
[0022] FIG. 3 is a schematic diagram of a conventional pulse type level shift circuit.
[0023] FIG. 4 shows waveform diagrams of the pulse type level shift circuit shown in FIG. 3 .
[0024] FIG. 5 is a schematic diagram of a level shift circuit disclosed in U.S. Pat. No. 7,839,197 of RICHTEK Technology Corporation.
[0025] FIG. 6 shows waveform diagrams of the pulse type level shift circuit shown in FIG. 5 .
[0026] FIG. 7 shows waveform diagrams of the second logic high level VP 2 and the second logic low level VS 2 of the level shift circuit shown in FIG. 5 .
[0027] FIG. 8 is a schematic diagram of a level shift circuit according to a first preferred embodiment of the present invention.
[0028] FIG. 9 shows waveform diagrams of the level shift circuit shown in FIG. 8 .
[0029] FIG. 10 is schematic diagram of a DC-DC buck converter controller applying a level shift circuit of a preferred embodiment of the present invention.
[0030] FIG. 11 shows waveform diagrams of the level shift circuit shown in FIG. 10 .
[0031] FIG. 12 shows waveform diagrams of the reference potential VBS and the connection node potential VPH in the level shift circuit shown in FIG. 10 .
[0032] FIG. 13 is a schematic diagram of a level shift circuit according to a second preferred embodiment of the present invention.
[0033] FIG. 14 is a schematic diagram of a level shift circuit according to a third preferred embodiment of the present invention.
[0034] FIG. 15 shows waveform diagrams of the level shift circuit shown in FIG. 14 .
[0035] FIG. 16 is a schematic diagram of a current detecting circuit according to a preferred embodiment of the present invention.
[0036] FIG. 17 is a schematic diagram of an inductance current detecting circuit according to a preferred embodiment of the present invention.
[0037] FIG. 18 is a schematic diagram of a delay judging circuit according to a preferred embodiment of the present invention.
[0038] FIG. 19 shows waveform diagrams of the delay judging circuit shown in FIG. 18 .
DETAILED DESCRIPTION
[0039] In the following detailed description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the disclosed embodiments, it will be apparent, however, that one or more embodiments may be practiced without these specific details. In other instances, well-known structures and devices are schematically shown in order to simplify the drawings.
[0040] FIG. 8 is a schematic diagram of a level shift circuit according to a first preferred embodiment of the present invention. The level shift circuit comprises a signal input circuit 102 , a signal output circuit 104 and a state detecting circuit 110 . The signal input circuit 102 is coupled between a first level VSS 1 and a second level VPP 2 , configured to receive a first input signal S and a second input signal R. Also referring to FIG. 9 , FIG. 9 shows waveform diagrams of the level shift circuit shown in FIG. 8 . Levels of the first input signal S and the second input signal R are switched between the first level VSS 1 and a third level VPP 1 . In the present embodiment, the signal input circuit 102 comprises transistors MN 1 ˜MN 5 , MP 1 and MP 4 , a current switch MNO and a current source Ib. The current source Ib is coupled to the third level VPP 1 or the second level VPP 2 , and provides a current In flowing through the transistor MN 1 when the current switch MNO is turned on. The transistors MN 2 and MN 3 mirror the current In of the transistor MN 1 for respectively providing a first current I 1 and a second current I 2 . The signal input circuit 102 generates the first current I 1 flowing through the transistors MP 1 , MN 4 and MN 2 when the first input signal S is at the third level VPP 1 , and generates the second current I 2 flowing through the transistors MP 4 , MN 5 and MN 3 when the second input signal R is at the third level VPP 1 . The signal output circuit 104 is coupled between the second level VPP 2 and a fourth level VSS 2 , configured to output a first output signal Q and a second output signal QN. Levels of the first output signal Q and the second output signal QN are switched between the second level VPP 2 and the fourth level VSS 2 .
[0041] The signal output circuit 104 comprises transistors MP 2 ˜MP 3 and MN 6 ˜MN 7 . When the signal input circuit 102 generates the first current I 1 , the transistor MP 2 of the signal output circuit 104 mirrors the first current I 1 to make the first output signal Q be switched to the second level VPP 2 . At this moment, the second output signal QN is switched to the fourth level VSS 2 . Similarly, the signal input circuit 102 generates the second current I 2 , the transistor MP 3 of the signal output circuit 104 mirrors the second current I 2 to make the second output signal QN be switched to the second level VPP 2 . At this moment, the first output signal Q is switched to the fourth level VSS 2 .
[0042] The state detecting circuit 110 detects an operating state of a converting circuit (not shown), such as detecting the voltage and/or the current, for judging the operating state, and determines whether generating a stop signal Ssd for stopping the signal input circuit 102 to generate the first current I 1 and the second current I 2 according to the operating state of the converting circuit. In the present embodiment, detecting the current of the converting circuit is taken as an example to illustrate.
[0043] The state detecting circuit 110 comprises a delay judging circuit 112 and a current detecting circuit 118 . The current detecting circuit 118 is coupled to the converting circuit for detecting a current of the converting circuit and generates a light-load notice signal Ss when detecting the current of the converting circuit is smaller than a light-load judging value. The state detecting circuit 110 determines whether generating the stop signal Ssd according to the light-load notice signal Ss. The delay judging circuit 112 is coupled to the current detecting circuit 118 , and generates the stop signal Ssd when the current detecting circuit 118 generates the light-load notice signal Ss lasting a preset delay time period. The delay judging circuit 112 comprises an AND gate 114 and a delay circuit 116 . The delay circuit 116 outputs a delay signal Sd when continuously receiving the light-load notice signal Ss for the preset delay time period. The AND gate 114 is coupled to the delay circuit 116 and the current detecting circuit 118 , and generates the stop signal Ssd when receiving both the light-load notice signal Ss and the delay signal Sd.
[0044] If the stop signal Ssd is not generated, the current switch MNO is turned on. Under this condition, the current In provided by the current source Ib flows through the transistor MN 1 , and the transistors MN 2 and MN 3 mirror the current In and respectively generate the first current I 1 and the second current I 2 . However, if the converting circuit operates in a light-load state, the stop signal Ssd is generated to cut off the current switch MNO. Under this condition, the current of the transistor MN 1 is zero, and so both the transistors MN 2 and MN 3 of the signal input circuit 102 have no current. That is, the signal input circuit 102 stops generating the first current I 1 and the second current I 2 . Thus, when the converting circuit operates under the light-load state, for example: the discontinuous current mode, the diode emulation mode, and so on, the level shift of the present invention reduce the power consumption to achieve the power-saving advantage.
[0045] FIG. 10 is schematic diagram of a DC-DC buck converter controller applying a level shift circuit of a preferred embodiment of the present invention. The converting circuit comprises a first power switch T 1 and a second power switch T 2 connected in series, an inductance L and a capacitance COUT. The first power switch T 1 is coupled to an input voltage VIN and a connection node PHASE, and the second power switch T 2 is coupled to the connection node PHASE and a common potential GND. The inductance L is coupled to the connection node PHASE and the output capacitance COUT, and the output capacitance COUT provides an output voltage VOUT. The DC-DC buck converter controller generates a high-side control signal UG and a low-side control signal LG for respectively turning on and off the first power switch T 1 and the second power switch T 2 . The DC-DC buck converter controller comprises a feedback control circuit, a level shift circuit and a driver 160 . The feedback control circuit comprises an error amplifier 130 and a PWM (pulse width modulated) logic circuit 140 . The error amplifier 130 receives a reference signal VREF and a detecting signal indicative of a state of the converting circuit, and generates an error amplification signal Sea according to the state of the converting circuit. In the present embodiment, the detecting signal represents the output voltage VOUT, and in actual application, it also can be a detecting signal indicative of an output current of the converting circuit. The PWM logic circuit 140 is coupled to the error amplifier 130 and generates a PWM (pulse width modulating) signal Sp according to the error amplification signal Sea. The PWM logic circuit 140 is coupled to a driving potential VDD and the common potential GND, and so a level of the PWM signal Sp is switched between the common potential GND and the driving potential VDD. The level shift circuit is coupled to a connection node potential VPH of the connection node PHASE, the driving potential VDD, the common potential GND and a reference potential VBS, and generates a level shift signal Sq (i.e., the first output signal Q or the second output signal QN of the embodiment in FIG. 8 ) according to the PWM signal Sp. The reference potential VBS, providing a potential higher than the input voltage VIN, is used for ensuring that the DC-DC buck converter controller correctly control the first power switch T 1 to be turned on and off. The reference potential VBS may be provided by a voltage source independent of the input voltage VIN, or additionally adding a bootstrap circuit 150 as the present embodiment. The bootstrap circuit 150 is coupled to the connection node PHASE and the input voltage VIN, and provides the reference potential VBS through the switching process of the first power switch T 1 .
[0046] The level shift circuit of the present invention may be the level shift circuit shown in FIG. 8 or a level shift circuit shown in other embodiments. In the present embodiment, take the level shift circuit shown in FIG. 8 to illustrate. For conveniently understand the operation of the DC-DC buck converter controller with respect to that shown in FIG. 8 , relationships of the logic levels between the two embodiments are illustrated in the following: the first level VSS 1 , the second level VPP 2 , the third level VPP 1 and the fourth level VSS 2 respectively corresponding to the common potential GND, the reference potential VBS, the driving potential VDD and the connection node potential VPH.
[0047] The level shift circuit comprises a level shift circuit 100 and a state detecting circuit 110 . The level shift circuit 100 , coupled to the common potential GND, the reference potential VBS, the driving potential VDD and the connection node potential VPH, comprises a signal input circuit 102 , a signal output circuit 104 and an inverter 106 . The inverter 106 is configured to receive the PWM signal Sp, and provides an inverted PWM signal Sp′. The PWM signal Sp and the inverted PWM signal Sp′ respectively serve as the first input signal S and the second input signal R for inputting into the signal input circuit 102 . The signal input circuit 102 generates a first current I 1 when the PWM signal Sp is at the driving potential VDD, and generates a second current I 2 when the PWM signal Sp is at the common potential GND. The signal output circuit 104 is configured to generate the level shift signal Sq, and the level shift signal Sq is switched to the reference potential VBS when the signal input circuit 102 generates the first current I 1 , and the level shift signal Sq is switched to the connection potential VPH when the signal input circuit 102 generates the second current I 2 .
[0048] The state detecting circuit 110 detects an operating state of the converting circuit and accordingly determines whether generating a stop signal Ssd for stopping the signal input circuit 102 to generate the first current I 1 and the second current I 2 . In the present embodiment, the state detecting circuit 110 is coupled to the connection node PHASE for detecting the current of the inductance L. The state detecting circuit 110 comprises a delay judging circuit 112 and a current detecting circuit 118 . The current detecting circuit 118 detects the current of the inductance L and generates a light-load notice signal Ss when detecting that a current of the inductance L is lower than a current reverse threshold value. The delay judging circuit 112 is coupled to the current detecting circuit 118 and generates the stop signal Ssd when the current detecting circuit 118 continuously generates the light-load notice signal Ss for a preset delay time period Td.
[0049] The driver 160 is coupled to the level shift circuit and the feedback control circuit and generates the high-side control signal UG and the low-side control signal LG according to the PWM signal Sp and the level shift signal Sq for respectively turning on and off the first power switch T 1 and the second power switch T 2 . The driver 160 comprises an upper driver 162 and a lower driver 164 . The upper driver 162 is coupled to the bootstrap circuit 150 and the connection node PHASE for receiving the reference potential VBS and the connection node potential VPH. The upper driver 162 is also coupled to the level shift circuit, and generates the high-side control signal UG according to the level shift signal Sq. The lower driver 164 is coupled to the feedback control circuit, and generates the low-side control LG according to the PWM signal Sp.
[0050] FIG. 11 shows waveform diagrams of the level shift circuit shown in FIG. 10 . Also referring to FIG. 10 , the current detecting circuit 118 generates the light-load notice signal Ss when judging an inductance current flowing reversely. The delay judging circuit 112 generates the stop signal Ssd when the light-load notice signal Ss lasts the preset delay time period Td. Referring to FIG. 8 , the stop signal Ssd cuts off the current switch MNO to make the current of the transistor MN 1 be zero, thereby stopping the first current I 1 and the second current I 2 . Besides, it is worth to notice that the lower driver 164 cuts off the second power switch T 2 for avoiding the inductance current flowing reversely against the coming reverse inductance current. At this moment, because both the first power switch T 1 and the second power switch T 2 are cut off, the connection node potential VPH of the connection node PHASE is oscillating. The bootstrap circuit 150 is coupled to the connection node PHASE, and so the oscillation of the connection node potential VPH affects the reference potential VBS. That leads to the noise interference. In the prior art, the current In is immediately cuts off to cause the erroneous level shift signal Sq of the level shift circuit 100 . In contrast, in the present invention, the current In within the preset delay time period Td from when both the first power switch T 1 and the second power switch T 2 are cut off still exists to solve the noise-interference problems. Moreover, after oscillation of the connection node potential VPH (i.e., passing the preset delay time period Td), the current In is stopped for power-saving.
[0051] FIG. 12 shows waveform diagrams of the reference potential VBS and the connection node potential VPH in the level shift circuit shown in FIG. 10 . When the current detecting circuit 118 detects the inductance current flowing reversely, i.e., the converting circuit enters into the light-load state, for example: DEM or DCM. After the preset delay time period, the state detecting circuit 110 generates the stop signal Ssd for cutting off the current In to make the level shift circuit 100 stop generating the first current I 1 and the second current I 2 . At this moment, no more current of the level shift circuit 100 flows from the reference potential VBS to the connection node potential VPH, and that ensures the level difference of the reference potential VBS and the connection node potential VPH being maintained.
[0052] FIG. 13 is a schematic diagram of a level shift circuit according to a second preferred embodiment of the present invention. Compared with the embodiment shown in FIG. 8 , the main differences are that a signal input circuit 202 adds transistors MN 8 and MN 9 , and a signal output circuit 204 adds transistors MP 5 and MP 6 . Gate electrodes of the transistors MN 8 and MN 9 are coupled to the third level VPP 1 to ensure source electrodes of the transistors MN 8 and MN 9 , i.e., the drain electrodes of the transistors MN 4 and MN 5 , being clamped below the third level VPP 1 . Thus, the transistors MN 4 and MN 5 can use the low-voltage transistor to reduce the cost of the level shift circuit. The transistors MP 5 and MP 6 functions as an accelerating circuit. A gate electrode of the transistor MP 5 is coupled to a gate electrode of the transistor MP 1 , and a drain electrode thereof is coupled to a gate electrode of the transistor MP 4 . When the first current I 1 is generated, the transistors MP 1 and MP 5 are simultaneously turned on. At this moment, the transistor MP 5 can quickly raise the gate electrode of the transistor MP 4 and completely cut off the transistor MP 4 for quickly cutting off the second current I 2 . Similarly, a gate electrode of the transistor MP 6 is coupled to the gate electrode of the transistor MP 4 , and a drain electrode thereof is coupled to the gate electrode of the transistor MP 1 . When the second current I 2 is generated, the transistors MP 4 and MP 6 are simultaneously turned on. At this moment, the transistor MP 6 can quickly raise the gate electrode of the transistor MP 1 and completely cut off the transistor MP 1 for quickly cutting off the first current I 1 .
[0053] FIG. 14 is a schematic diagram of a level shift circuit according to a third preferred embodiment of the present invention. The embodiments shown in FIG. 8 and FIG. 13 transfer the first input signal S and the second input signal R with the lower logic levels of the first level VSS 1 and the third level VPP 1 into the first output signal Q and the second output signal QN with the higher logic levels of the fourth level VSS 2 and the second level VPP 2 . The level shift circuit shown in FIG. 14 transfer the first input signal S and the second input signal R with the higher logic levels of the fourth level VSS 2 and the second level VPP 2 into the first output signal Q and the second output signal QN with the lower level of the first level VSS 1 and the third level VPP 1 .
[0054] FIG. 15 shows waveform diagrams of the level shift circuit shown in FIG. 14 . Also referring to FIG. 14 , a signal input circuit 302 is coupled between the first level VSS 1 and the second level VPP 2 and receives the first input signal S and the second input signal R. The levels of the first input signal S and the second input signal R are switched between the fourth level VSS 2 and the second level VPP 2 . The signal input circuit 302 comprises the transistors MP 1 ˜MP 5 , MN 1 and MN 6 , the current switch MNO and the current source Ib. The current source Ib is coupled to the first level VSS 1 , and provides a current Ip flowing through the transistor MP 1 when the current switch MNO is turned on. A signal output circuit 304 is coupled between the third level VPP 1 and the first level VSS 1 and outputs the first output signal Q and the second output signal QN. The levels of the first output signal Q and the second output signal QN are switched between the third level VPP 1 and the first level VSS 1 . The level shift circuit of the present embodiment is similar to the level shift circuits shown in FIG. 8 and FIG. 13 , and the detailed description of the circuit operation can refer to the corresponding description in FIG. 8 and FIG. 13 , and it will not repeated in here.
[0055] FIG. 16 is a schematic diagram of a current detecting circuit according to a preferred embodiment of the present invention. In order to clearly understand the operation of the current detecting circuit, the current detecting circuit is applied to the circuit of FIG. 8 for illustrating. The current detecting circuit comprises a comparator Com and a RS flip-flop. The low-side control signal LG is used to enable and disable the comparator Com. The comparator Com is enabled when the low-side control signal LG is at a high level, i.e., the second power switch T 2 is turned on, and is disabled when the low-side control signal LG is at a low level. A non-inverting input end of the comparator Com receives a current detecting signal Ise, and an inverting end thereof receives a light-load judging value Vrc. In the present embodiment, the light-load judging value Vrc is the ground potential, i.e., the common potential GND. When the second power switch T 2 is turned on, the comparator Com is enabled for detecting whether the current of the second power switch T 2 flows reversely. When the current detecting signal Ise is higher than the light-load judging value Vrc, the comparator Corn generates a high level signal for triggering the RS flip-flop generating the light-load notice signal Ss. In actual application, the connection node potential VPH may serve as the current detecting signal Ise. When the connection node potential VPH is larger than zero, it represents that the inductance current flows reversely, i.e. from the inductance into the second power switch T 2 and so the converting circuit operates in the light-load state. At this moment, the current detecting circuit generates the light-load notice signal Ss.
[0056] FIG. 17 is a schematic diagram of an inductance current detecting circuit according to a preferred embodiment of the present invention. The inductance current detecting circuit comprises a transconductance amplifier GM, a sample and hold circuit S/H, a detecting capacitance C and resistances Re and Rcsn. The inductance L is connected the series of the detecting capacitance C and the resistance Re in parallel. The inductance L has an inherent DC resistance DCR, and so a voltage across Vc of the capacitance C is proportional to an inductance current IL of the inductance L. A non-inverting input end of the transconductance amplifier GM is coupled to a connection node of the resistance Re and the detecting capacitance C, and an inverting input end thereof is coupled to the other end of the capacitance C through the resistance Rcsn. The transconductance amplifier GM generates an output current Icsn at an output end according to voltage levels at the non-inverting input end and the inverting input end. The non-inverting input end of the transconductance amplifier GM is coupled to the output end. Thus, the output current Icsn flows through the resistance Rcsn and form a voltage across of the resistance Rcsn to compensate the voltage across Vc of the capacitance C for making the voltage difference of the inverting input end and the non-inverting input end of the transconductance amplifier GM be zero. When the inductance current IL flows reversely, i.e., the inductance current IL flows back from the output voltage VOUT to the connection node PHASE, and the output current Icsn is smaller than or equal to zero. The sample and hold circuit S/H detects the voltage across Vc of the capacitance C at every cycle and accordingly generates the current detecting signal Ise. When the inductance current IL flows reversely, the current detecting signal Ise is larger than zero and so the inductance current detecting circuit generates the light-load notice signal Ss.
[0057] FIG. 18 is a schematic diagram of a delay judging circuit according to a preferred embodiment of the present invention. The delay judging circuit comprises a switch Md, a current source Id, a capacitance Cd, a comparator Dd and an AND gate Ad. One end of the switch Md is coupled to the driving potential VDD, and the other end thereof is coupled to the current source Id. One end of the capacitance Cd is coupled to a connection node of the switch Md and the current source Id, and the other end thereof is coupled to the ground. A non-inverting input end of the comparator Dd receives a delay reference voltage Vr, and an inverting input end thereof is coupled to the capacitance Cd.
[0058] FIG. 19 shows waveform diagrams of the delay judging circuit shown in FIG. 18 . When the light-load notice signal Ss is at a low level, the switch Md is turned on for making a voltage of the capacitance Cd be raised to the driving potential VDD, which is higher than the delay reference voltage Vr. At this moment, the AND gate Ad stops outputting the stop signal Ssd (i.e., the stop signal Ssd is at a low level). When the light-load notice signal Ss is changed to a high level, the switch Md is cut off. At this moment, the current source Id starts discharging the capacitance Cd, and so the voltage of the capacitance Cd starts dropping from the driving potential VDD. After the preset delay time period Td, the voltage of the capacitance Cd is lower than the delay reference voltage Vr, the comparator Dd output a high level signal. At this moment, both two signals received by the two input ends of the AND gate Ad are at high levels and the AND gate Ad outputs the stop signal Ssd. When the light-load notice signal Ss is changed from the high level to the low level, the switch Md is turned on for immediately charging the voltage across of the capacitance Cd to be the driving potential VDD. At this moment, the AND gate Ad stops outputting the stop signal Ssd.
[0059] While the preferred embodiments of the present invention have been set forth for the purpose of disclosure, modifications of the disclosed embodiments of the present invention as well as other embodiments thereof may occur to those skilled in the art. Accordingly, the appended claims are intended to cover all embodiments which do not depart from the spirit and scope of the present invention. | A level shift circuit and a DC-DC buck converter controller for using the same are disclosed. The level shift circuit is capable of detecting a state of a converting circuit, and avoids a current leakage when determining that the converting circuit is operating under a light-load. Therefore, the level shift circuit and the DC-DC converting controller provided by the present invention can reduce power consumption under the light-load and have power-saving advantage. | 8 |
This application is related to, but in no way dependent upon the following applications: U.S. patent application Ser. No. 07/458,129 and Ser. No. 07/685,352; filing date, Apr. 15, 1991, now U.S. Pat. No. 5,086,251, issue date, Feb. 2, 1992, commonly owned herewith.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to means for repeatably attaining the desired configuration of a cathode ray tube (CRT) front panel, or faceplate, of the tensioned mask type. Such CRTs may have the shadow mask mounting means affixed directly to the CRT panel. The CRT panel also carries the image forming screen of the CRT, which is, generally, a matrix of phosphor elements.
There have been proposed a variety of ways and means for making CRTs having interchangeable screens and shadow masks in order to simplify the manufacture thereof. However, any interchangeable system requires that the standard screen matrix be reproducibly positioned on each faceplate so as to register with any standard shadow mask. It will be remembered that the shadow mask apertures and the phosphor elements must register, i.e. be in operational alignment, for a suitable image to be formed on the screen. It follows that the substrates onto which the screen matrices are deposited, i.e. the screening surface of the CRT panels, must have a consistent configuration.
2. Discussion of the Related Art
As previously noted, tensioned mask CRTs may have the mask mounting means affixed to the faceplate. While this construction affords a multiplicity of advantages, certain problems concerning panel glass strain are attendant therewith. An improved system for affixing the mask mounting means is disclosed in the above-cited related U.S. patent application, Ser. No. 07/458,129, now U.S. Pat. No. 5,086,251, issue date, Feb. 2, 1992. Therein, the coefficients of thermal expansion (or contraction, if preferred, hereinafter CTE) of the mask mounting means, sometimes referred to as rails, and the panel glass are deliberately mismatched, with the mask mounting CTE being lower than the glass CTE to provide the panel assembly, i.e., the panel with its attached mask mounting means; with resistance to damage from thermal processing.
However, as is evident from FIG. 5 of that disclosure, included herein as FIG. 1, the panel assembly is distorted from its there desired flat shape by the disclosed system, resulting in a panel assembly distorted convexly toward the screening surface, as seen in FIG. 4.
Such distortion is not desirable where the registration and proper operation of an interchangeable mask and screen would be predicated upon the geometries of a planar panel assembly whose screening surface is flat to within, e.g., plus or minus one-quarter of a mil (0.00025 inches). It will be appreciated by the artisan that a cylindrical panel assembly utilizing a tensioned mask would have much the same requirements for repeatability of the desired geometry.
Therein lies a desiderata for such panel assemblies which are resistant to thermal shock and, as well, provide a repeatable configuration for the application of the phosphor screen.
OBJECTS OF THE INVENTION
It is an object of the invention to provide CRT panels having repeatable screening surface configuration so as to improve the manufacture and performance of tensioned mask cathode ray tubes.
Other attendant advantages will be more readily appreciated as the invention becomes better understood by reference to the following detailed description and compared in connection with the accompanying drawings, in which like reference numerals designate like parts throughout the figures. It will be appreciated that the drawings may be exaggerated for explanatory purposes
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is graph of panel distortion when utilizing mask mounting means whose CTE is mismatched with that of the panel glass.
FIG. 2 is plan view of a preferred tensioned mask CRT panel showing of mask mounting means attached hereto and having twelve panel measuring points labeled thereon
FIG. 3 is a sectional view of a CRT panel with mask support means and distortion counteracting rails attached to opposite sides of the panel.
FIG. 4 is a perspective view of an undesirable distorted panel.
FIG. 5 is a graph showing the distortional effects of mask support rails, counteracting rails, and ground counteracting rails.
FIG. 6 is a cross sectional view of a CRT cylindrical faceplate and funnel with a counteracting rail attached thereto.
FIG. 7 is a block diagram of a method according to the present invention.
FIG. 8 illustrates a method of using a devitrifying frit as the strain-inducing structure.
FIG. 9 illustrates an alternative strain-inducing structure embodiment for use with the present invention wherein the strain-inducing structure and the mask support means are combined in a unitary body.
FIG. 10 illustrates an alternative strain-inducing structure embodiment, for use with the present invention, utilizing a high magnesia content structure located on the same side of the panel as the mask support means.
FIG. 11 illustrates mask support means having a strain inducing structure as an integral shoulder thereof.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
As seen in FIG. 3, a section of a flat faceplate, or CRT front panel 11 is composed of glass. The panel 11 has an inner surface 13 which has deposited thereon a screen 15 comprised of a matrix of phosphor elements 17. Affixed to the inner surface 13 is mask support means 19 preferably comprising a ceramic rail 21 with a metal strip or cap 23. Four such mask support means 19 would ordinarily be applied to the panel 11 in a rectangular array, as seen in FIG. 2. The ceramic rail 21 is cemented at its base 25 to the panel 11 by means of a known devitrifying frit 27 which turns solid at high temperatures, as described in the above-cited, co-owned application Ser. No. 07/458,129. Affixed to the metal cap 23 by welding or the like, in an operational color CRT is a tensioned foil shadow mask 29. A distortion counteracting, or strain inducing, means 30 shown as a ceramic rail 32 is attached, according to one embodiment of the present invention, on the outer surface 33 of the panel 11, in order to balance or over-balance the deformation forces applied to the panel by mask support means 19, as further explained below.
The preferred mask support means 19, as described in S/N: 07/458,129, has a coefficient of thermal expansion (CTE) lower than that of the panel glass. This is intentionally done to produce favorable residual stresses at the rail ends 31 to improve thermal cycling throughput during manufacture. As a related effect, the inner surface 13 of the panel 11 deforms, or distorts, convexly as graphed in FIG. 1. This will be denominated an inward or positive deflection.
As seen in FIG. 4, and with reference to the labeled positions of FIG. 2, a rendering of the graph of FIG. 1 shows that the panel 11 has domed with the greatest inward deflection being in the middle of the long rails 34, at B and H, with the next greatest inward deflections being in the middle of the short rails 36, at E and K. Outward or negative deflection occurs at the corners of the panel 11, i.e., at A, L; C,D; F,G; and I,J.
As seen in FIG. 3, an uncapped ceramic rail 32 having a shape and size substantially similar to the ceramic mask support rail 21 is affixed by frit 27 on the outside panel surface 33 at a point opposite the support rail 21. However, in order to over-balance the panel deformation induced by the mask support rails 19, the counter-rail 32 is composed of a ceramic having a lower percentage of magnesia. Such a ceramic will have a lower CTE than the mask rail 21 and, therefore, induce more strain, and hence more deformation, into the panel 11. The current preferred composition of the mask support ceramic rails formula designation No. 297A is 28% magnesia, 62% talc, 6% barium carbonate and 4% ball clay. The counter-rail 32 will be considered hereinafter as having only a 26% magnesia content although various lower magnesia contents may be suitably used. Counter-rails having twenty-two percent magnesia have been found to spall the panel. As the percentage of magnesia decreases, the talc percentage is increased.
Referring now to the graph of FIG. 5, deflection along the rails with only mask support means 19 applied to the inner surface 13 of the panel 11 is represented buy the first bars 35. It can be seen from the first bars 35 that the highest inward deviation is about 1.3 mils and the highest outward deviation is about 0.7 mils for a total of about 2.0 mils. The third bars 37 represent deflection along the rails with both the mask support means 19 applied to the panel inner surface 13 and the distortion counteracting means 30, at 26% magnesia content, applied to the panel outside surface 33, as per FIG. 3, resulting in a panel distorted in a direction opposite that of line 35. It can be seen on line 37 that the highest inward deviation is about 0.8 mils and the highest outward deviation is about 0.9 mils for a total of about 1.7 mils. The fourth bars 38 shows the effects of removing mass from the counter rail 32 by grinding the rails from a 0.260 inch height to a 0.080 inch height. Therein, the highest outward deviation is about 0.9 mils, for a total of about 1.3 mils. This illustrates the effect of removing too much material from the counter-rails.
As can be seen the panel has, after the grinding of the counterrail to 0.080 inches resumed the inward deflection of the panel due to strain from the mask support rails, but to a lesser degree, owing to the counterbalancing strain of the remaining counter rail mass. The amount of reduction in panel deflection from the over-warped state to the "normal", or planar, state by removal of a given mass from the counter rail is predictable though not necessarily linear, and will depend upon the composition of the counter rail, its placement, and its mismatch with the strain induced by the mask support rail. Total panel deflection in the 0.4 mil range has been attained experimentally, starting with glass in the 1.3 mil range of deflection.
Referring again to the graph of FIG. 5, the second bars 63 represents deflection along the rails with both the mask support means 19 applied to the panel inner surface 13 and the distortion counteracting means 30 of formula 297A, ie. 28% magnesia, applied to the panel outside surface 33, as per FIG. 3, without additional grinding. It can be seen from the second bars 63 that the highest inward deviation is about 0.2 mils and the highest outward deviation is about 0.3 mils, for a total of about 0.5 mils. Thus, by applying the distortion counteracting means 30 to the panel 11, the rail-strains distorting the panel are more balanced and a much flatter panel is obtained. Accordingly, the panel inner surface 13 is more nearly the shape intended for the application of a standard screen thereto. It will be noted that this flatter panel is also less susceptible to strain from atmospheric loading during evacuation of the CRT envelope.
It will be appreciated that the described arrangement does not exactly balance the panel distorting forces. For example, the support means has a metal rail cap 23 attached, whereas the distortion compensation means does not, leading to some mismatch in the tensile forces applied to the glass beneath each rail. By careful selection of the uncapped rail 32 composition, size, and placement, further reductions in panel distortion may be possible through a more complete balancing of the distortion forces applied by the mask supports. For example, the uncapped compensating rail 32, if placed on the panel outer surface 33, may be moved closer to the edge of the panel outer surface 33, and/or reduced in size, to be more easily hidden beneath a covering plate, or bezel, (not shown) commonly used with CRTs. In such a case, the magnesia content of the compensating ceramic composition may be decreased, e.g. to 24 or 26 percent, to lower the CTE of the compensating means 30 and provide additional counteracting tensile forces since the compensating rail 32 will not be directly beneath or opposite the mask supports 19.
As shown in FIG. 6, other faceplate configurations capable of utilizing a tensioned shadow mask, such as a cylindrical faceplate 39 with curved mask supports 41 attached thereto, may utilize compensating rails 43 according to the present invention, to maintain the desired radius of curvature of the panel upon application of the mask supports 41, with panel-to-panel consistency.
As illustrated in the block diagram of FIG. 7, a typical sequence for processing CRT front panels to attain a repeatable panel-to-panel curvature may include an initial panel flatness or distortion, measurement 111 prior to attaching the mask support rails or the counter-rails to aid in the selection of counter-rail composition or placement. The panel flatness may be measured by a commercially available machine such as a Cordax 3000 manufactured by Sheffield Co. of Dayton, Ohio. At the next step 113 the counter-rails 32 will be affixed to the panel 11 opposite the mask support rails 21 to over-warp the panel 11 outwardly. The panel 11 will then be measured as at 115 to make an initial determination of the amount of grinding to be done on the counter rail 21 to produce a balanced strain on the panel and produce the desired panel curvature or flatness.
The counter-rails 21 will then be ground as per box 117, as further discussed below. The measuring and grinding may be repeated as necessary 119. Also, should the counter rail be over-ground to an out-of-tolerance condition, as per FIG. 8, a bead of frit 27 may be reapplied to the counter rail 32 and devitrified to bring the panel 11 back to an outward distortion. The panel 11 would be remeasured and the frit bead 27 would then be ground to attain the desired degree of panel curvature. This process would eliminate the need to salvage the panel by removing all frit, a process which may damage the panel and render it useless.
The counter rail 32 is of a known height and in a known position to give a predetermined deformation strain to the panel. A known amount of counter rail mass is then removed by grinding the counter rail 32 with a grinding wheel 125 and measuring the rail height, "h", with a known device 127 such as disclosed in U.S. Pat. No. 4,828,524; commonly owned herewith, or other suitable means; as necessary. By removing a known amount of counter rail mass, according to its predictable behavior, a flat, or other desired, curvature of the panel 11 will be attained. It will be noted that where the counter-rails are placed on the outer surface 33 of panel 11, the grinding thereof may take place at any time during CRT assembly.
As seen in FIG. 9, an alternative embodiment of the present invention includes mask support means 19 incorporated into a unitary cross "U"-shaped rail structure 45, or U-rail, which surrounds the edge 47 of the panel 11. The U-rail 45 is preferably composed of a ceramic material and is affixed over and to the panel edge 47 with a known devitrifying frit 27.
The U-rail 45 has first and second legs 49 and 51, respectively connected by a bight 53. Attached to the first leg 49, which is adjacent to the inner panel surface 13, is a metal strip, or wire 23 constructed and arranged for attachment of the shadow mask thereto as disclosed in the copending U.S. applications Ser. Nos. 07/566,721 and 07634,644, commonly owned herewith. It will be evident, from the foregoing disclosure, that the second leg 51, which is adjacent the outer panel surface 33, may be constructed and, if necessary, ground to counteract any undesirable panel distorting strain imparted to the panel 11 by the first leg 49 during attachment of the U-rail 45.
An advantage of the U-rail 45 embodiment of the present invention may include a savings of surface area on the panel inner surface 13 by locating the mask support means 19 outwardly from its normal position as shown in FIG. 3. A further advantage is the formation of a protective barrier around the panel edge 47, which is sensitive to physical contact during thermal processing of the panel 11 as disclosed and claimed in the aforementioned U.S. patent application Ser. No. 07/685,352; filing date, Apr. 15, 1991.
As seen in FIG. 10, a third embodiment of the invention includes a high magnesia content ceramic rail 57 affixed by frit 27 onto the panel inner surface 13 next to the mask support means 19. By raising the magnesia content of the rail 57 from the preferred 28% up to approximately 34%, the strain produced by the rail will tend to bow the panel outwardly instead of inwardly as will the standard rails 21. Thus the high magnesia content rail 57 may be used on the inner panel surface 13 as means to counteract the undesirable panel distortion caused by the mask support means. Such a placement of the counteracting means, while making the panel more susceptible to damage from thermal shock, and taking up space on the screen side of the panel, may be desirable where conditions do not allow placing the counteracting means on the outer surface 33, or front of the panel.
As seen in FIG. 10, a grinding apparatus 125 having a small grinding wheel 129 with an active surface 131 not significantly wider than the width 133 of the counter rail 32 may be constructed and arranged to traverse the counter-rails 32 and grind them without adversely affecting the mask support rails 21.
Alternatively, as seen in FIG. 11, the mask support rail 21 may be equipped with extensions, or shoulders 135, of the same, or substantially similar, composition as the main rail 21 and located on the same side of the panel 11, which will produce a panel deflection of greater magnitude than ultimately desired for the finished panel. The shoulders 135 may then be ground with e.g., the small grinding wheel apparatus of FIG. 10, and measured, until the desired panel curvature is attained.
This arrangement is most suitable for use where a repeatable panel curvature of a fixed radius is desired, rather than a true flat faceplate illustrated in the other embodiments.
While the ceramic rails or their counterparts are described herein as distortion counteracting means, it will be evident to the artisan that rails may be constructed and arranged as the sole strain inducers and acted upon so as to more consistently control the panel curvature and not merely counteract undesirable distortion induced in the panel by the mask support rails and may be, used alone on in combination with other CRT elements or manufacturing apparatus to achieve their desired affect.
While the present invention has been illustrated and described in connection with the preferred embodiments, it is not to be limited to the particular structure shown, because many variations thereof will be evident to one skilled in the art and are intended to be encompassed in the present invention as set forth in the following claims: | A means for attaining a predetermined CRT front panel configuration is disclosed as being particularly suitable for use with tensioned-mask CRTs having mask support means affixed to the front panel. A ceramic rail or the like is affixed to the front panel in opposition to the mask support to produce panel deformation forces counteracting those produced by the mask supports. In one embodiment, the panel is deformed more than is ultimately desired and the deformation structures are then ground to produce the desired panel configuration. Repeatability of screen curvature is thereby attained, allowing for interchangeable shadow mask and screen construction of the CRT. | 7 |
BACKGROUND
[0001] 1. Technical Field
[0002] The present invention relates to a method, a system, a mobile terminal and a computer program product.
[0003] 2. Description of the Related Art
[0004] In Japan, a 3G mobile phone service called Third Generation was started in 2002. At first, exchange of small packets such as voice and mail was the main application. However, with the introduction of High Speed Downlink Packet Access (HSDPA) and the like, download of larger packets, such as download of a music file or watching of a shared video, has come to be performed.
[0005] Furthermore, since a communication infrastructure can be structured cheaply and also since a user preference is shifting to packet transmission, shift to IP core network using IP Multimedia Subsystem (IMS) is taking place.
[0006] However, although it is a well-known fact that a fixed network typified by the Internet has grown into a communication infrastructure indispensable to life, there are many issues relating to ensuring of security, stable Quality of Service (QoS), and the like. Thus, Next Generation Network (NGN) aims to ensure security and stable QoS by introducing IMS standardized by the Third Generation Partnership Project (3GPP). Furthermore, realization of Fixed Mobile Convergence (FMC) which uses the same IMS method and which enables to seamlessly use a mobile network and a fixed network is anticipated.
[0007] Furthermore, in recent years, a mobile phone with Global Positioning System (GPS) has become widespread. Also, a mobile phone compliant with a plurality of wireless access methods and the introduction of a mechanism allowing a user to select a wireless access method in accordance with his/her preference are desired in the future. Additionally, JP-A-2008-298484 discloses a mobile terminal with GPS.
[0008] A user preference includes preference relating to communication cost and preference relating to communication speed. For example, there may be a user who prefers high communication speed to low communication cost and a user who prefers low communication cost to high communication speed. The communication speed here is dependent on a wireless status (available wireless capacity) of a user. Accordingly, a technology of grasping the wireless status changing every moment becomes important.
[0000] In light of the foregoing, it is desirable to provide a method, a system, a mobile terminal and a computer program product which are novel and improved, and which are for grasping the wireless status of the wireless communication device.
SUMMARY
[0009] In one embodiment, a method is provided for estimating an available capacity of a base station within a wireless communication access network. The method comprises receiving an indication, generated by a mobile terminal, of the quality of communication between the base station and the mobile terminal, and estimating the available capacity of the base station based on the received indication.
[0010] In another embodiment, a system is provided for estimating an available capacity of a base station within a wireless communication access network. The system comprises a communication unit for receiving an indication, generated by a mobile terminal, of the quality of communication between the base station and the mobile terminal, and a capacity estimation unit for estimating the available capacity of the base station based on the received indication.
[0011] In another embodiment, a mobile terminal comprises a correlation detection unit for calculating a correlation output based on signals received by the mobile terminal, an indicator calculation unit for calculating, using the correlation output, an indication of the quality of communication between a base station and the mobile terminal, and a communication unit for transmitting, to the base station, the indication of the quality of communication is provided.
[0012] In another embodiment, a method is provided for estimating an available capacity of a base station within a wireless communication access network. The method comprises receiving correlation outputs, generated by a mobile terminal, of a plurality of scrambling codes forming a specific scrambling code group, calculating, based on the received correlation outputs, an indication of the quality of communication between the base station and the mobile terminal, and estimating the available capacity of the base station based on the calculated indication of the quality of communication.
[0013] In another embodiment, a tangible computer-readable medium is provided. The computer-readable medium includes program instructions for performing, when executed by a processor, a method comprising calculating a correlation output based on signals received by a mobile terminal, calculating, using the correlation output, an indication of the quality of communication between a base station and the mobile terminal, and transmitting, to the base station, the indication of the quality of communication.
[0014] In another embodiment, a mobile terminal comprises a subcarrier rate detection unit for calculating an indication of the quality of communication between a base station and the mobile terminal using a detected ratio of a number of subcarriers not used as a communication resource among a total number of subcarriers available as a communication resource, and a communication unit for transmitting, to the base station, the indication of the quality of communication is provided.
[0015] It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as described. Further features and/or variations may be provided in addition to those set forth herein. For example, the present invention may be directed to various combinations and subcombinations of several further features disclosed below in the detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] FIG. 1 is an explanatory diagram showing a first configuration example of a wireless communication system;
[0017] FIG. 2 is an explanatory diagram showing a second configuration example of the wireless communication system;
[0018] FIG. 3 is an explanatory diagram showing a third configuration example of the wireless communication system;
[0019] FIG. 4 is a block diagram showing a hardware configuration of a mobile terminal;
[0020] FIG. 5 is a functional block diagram showing a mobile terminal according to a first configuration example.;
[0021] FIG. 6 is a functional block diagram showing a mobile terminal according to a second configuration example;
[0022] FIG. 7 is a functional block diagram showing a mobile terminal according to a third configuration example;
[0023] FIG. 8 is a functional block diagram showing a mobile terminal according to a fourth configuration example;
[0024] FIG. 9 is a functional block diagram showing a mobile terminal according to a fifth configuration example;
[0025] FIG. 10 is a flow chart showing a flow of a wireless communication method performed by a mobile terminal;
[0026] FIG. 11 is an explanatory diagram showing a configuration of an estimation server;
[0027] FIG. 12 is a diagram for illustrating a method of identifying a current location based on a reception intensity from each of a plurality of base stations;
[0028] FIG. 13 is a flow chart showing a first operation example of the estimation server,
[0029] FIG. 14 is a flow chart showing a second operation example of the estimation server;
[0030] FIG. 15 is a flow chart showing a third operation example of the estimation server; and
[0031] FIG. 16 is a flow chart showing a fourth operation example of the estimation server.
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0032] Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the appended drawings. Note that, in this specification and the appended drawings, structural elements that have substantially the same function and structure are denoted with the same reference numerals, and repeated explanation of these structural elements is omitted.
[0033] Additionally, in this specification and drawings, a plurality of structural elements having substantially the same functional configuration are sometimes distinguished from each other by a different alphabet letter added to a same numeral. For example, a plurality of structures having substantially the same functional configuration are distinguished from each other as necessary by being referred to as base stations 30 A, 30 B and 30 C. However, in case it is not necessary to distinguish between a plurality of structural elements having substantially the same functional configuration, only a same numeral is added thereto. For example, in case it is not particularly necessary to distinguish between the base stations 30 A, 30 B and 30 C, they will be collectively referred to as the base stations 30 .
[0034] Furthermore, “DETAILED DESCRIPTION OF THE EMBODIMENTS” will be described in the order shown below.
[0035] 1. Configuration of Wireless Communication System
1-1. First Configuration Example 1-2. Second Configuration Example 1-3. Third Configuration Example
[0039] 2. Hardware Configuration of Mobile Terminal
[0040] 3. Functional Configuration of Mobile Terminal
3-1. First Configuration Example 3-2. Second Configuration Example 3.3. Third Configuration Example 3-4. Fourth Configuration Example 3-5. Fifth Configuration Example
[0046] 4. Operation of Mobile Terminal
[0047] 5. Configuration of Estimation Server
[0048] 6. Operation of Estimation Server
6-1. First Operation Example 6-2. Second Operation Example 6-3. Third Operation Example 6-4. Fourth Operation Example
[0053] 7. Conclusion
1. CONFIGURATION OF WIRELESS COMMUNICATION SYSTEM
[0054] First, referring to FIGS. 1 to 3 , first to third configuration examples of a wireless communication system, which is an embodiment of the present invention, will be described.
1-1. First Configuration Example
[0055] FIG. 1 is an explanatory diagram showing a wireless communication system 1 of a first configuration example. As shown in FIG. 1 , the wireless communication system 1 according to the first configuration example includes an estimation server 10 , a mobile terminal 20 , a plurality of base stations 30 A to 30 C, and an access network 40 .
[0056] The access network 40 includes a core network of a telecommunications carrier, and a line connecting the core network and the base station 30 . The base station 30 can communicate with the estimation server 10 via a gateway 42 included in the access network 40 .
[0057] The base station 30 controls the communication by the mobile terminal 20 . For example, the base station 30 relays data received from the mobile terminal 20 to an addressed destination, and when data addressed to the mobile terminal 20 is received, transmits the data to the mobile terminal 20 . Furthermore, the base station 30 can communicate with the mobile terminal 20 by using wireless multiple access such as frequency division multiple access (FDMA), time division multiple access (TDMA), and code division multiple access (CDMA). The code division multiple access will be briefly described in the following.
[0058] According to the code division multiple access, 512 types of scrambling codes are defined, and any of the scrambling codes is assigned to each base station 30 . The base station 30 frequency-spreads a transmission signal by a spreading code (for example, a channelization code) in accordance with the type of the transmission signal or the mobile terminal 20 , and further frequency-spreads the transmission signal by using the assigned scrambling code and transmits the same. Additionally, the type of the transmission signal may be a common pilot channel (CPICH), a primary common control physical channel (P-CCPCH), a dedicated physical channel (DPCH), a synchronization channel (SCH), or the like.
[0059] Furthermore, the SCH includes a primary SCH and a secondary SCH. The primary SCH and the secondary SCH are arranged at the beginning portion of each of 15 slots configuring one frame, and the primary SCH is spread by a C PSC (Primary Synchronization Code) and the secondary SCH is spread by a C SSC (Secondary Synchronization Code).
[0060] There are 16 types of C SSC , and 64 combination patterns are prepared to be assigned to the 15 slots. Each base station 30 is assigned with any of the 64 patterns, and the base station 30 frequency-spreads and transmits the secondary SCH in each slot according to the assigned pattern. Additionally, the 512 types of scrambling codes are divided into 64 groups, and each group is associated with any of the 64 C SSC combination patterns.
[0061] The mobile terminal 20 can communicate various data with other device via the base station 30 . The various data may be audio data such as music, a lecture, a radio program, or the like, image data such as a motion picture, a television program, a video program, a photograph, a document, a painting, a diagram, or the like, a game, software, or the like.
[0062] Furthermore, in case of the mobile terminal 20 communicating with the base station 30 A as shown in FIG. 1 , the mobile terminal 20 calculates an indicator of a quality of communication, the value of which can be used by the estimation server 10 , along with location identification information for identifying the current location of the mobile terminal 20 , to generate an estimate of available capacity of the base station 30 A. The detailed function of such mobile terminal 20 will be described in “I Functional Configuration of Mobile Terminal.”
[0063] Additionally; although the mobile terminal 20 is shown as an example of a wireless communication device in FIG. 1 , the wireless communication device is not limited to such example. For example, the wireless communication device may be an information processing apparatus such as a personal computer (PC), a home video processing device (a DVD recorder, a video cassette recorder, or the like), a personal digital assistant (PDA), a home game machine, a home appliance, or the like. Also, the wireless communication device may be an information processing apparatus such as a mobile phone, a Personal Handyphone System (PHS), a portable audio playback device, a portable video processing device, a portable game machine, or the like.
[0064] The estimation server 10 receives the indicator of the quality of communication and the location identification information from the mobile terminal 20 via the base station 30 and the gateway 42 . The estimation server 10 can estimate the available capacity of the base station 30 by using the indicator of the quality of communication and the location identification information that are received. The detailed configuration and operation of such estimation server 10 will be described later.
1-2. Second Configuration Example
[0065] FIG. 2 is an explanatory diagram showing a wireless communication system 2 of a second configuration example. As shown in FIG. 2 , the wireless communication system 2 according to the second configuration example includes the estimation server 10 , the mobile terminal 20 , a plurality of first base stations 30 A and 30 B, a first access network 40 , a plurality of second base stations 50 A and 50 B, and a second access network 60 .
[0066] The first base station 30 is connected with the first access network 40 , and the second base station 50 is connected with the second access network 60 . Also, the estimation server 10 is connected with the first access network 40 via a gateway 42 arranged in a core network to which the first base station 30 belongs, and is connected with the second access network 60 via a gateway 62 arranged in a core network to which the second base station 50 belongs.
[0067] This wireless communication system 2 according to the second configuration example allows the mobile terminal 20 to register location with the first base station 30 A and the second base station 50 A belonging to different core networks. Accordingly, the mobile terminal 20 can transmit the indicator of the quality of communication and the location identification information to the estimation server 10 via the gateway 42 or the gateway 62 .
[0068] The estimation server 10 estimates the available capacity of the first base station 30 A and the available capacity of the second base station 50 A by using the indicator of the quality of communication and the location identification information that are received. Furthermore, as will be described in detail later, the estimation server 10 can select which of the first access network 40 and the second access network 60 is suitably used for the mobile terminal 20 .
1-3. Third Configuration Example
[0069] FIG. 3 is an explanatory diagram showing a wireless communication system 3 of a third configuration example. As shown in FIG. 3 , the wireless communication system 3 according to the third configuration example is configured based on the IMS. Specifically, the wireless communication system 3 according to the third configuration example includes the mobile terminal 20 , a plurality of base stations 30 A to 30 C, the access network 40 , a proxy-call session control function (P-CSCF) 72 , an interrogating-CSCF (I-CSCF) 74 , a serving-CSCF (S-CSCF) 75 , a home subscriber server (HSS) 76 , and an application server (AS) 78 .
[0070] This wireless communication system 3 according to the third configuration example allows the mobile terminal 20 to perform communication via the base station 30 according to the IMS. Furthermore, according to the wireless communication system 3 , the S-CSCF 75 , the HSS 76 and the AS 78 , for example, function as the estimation server 10 .
2. HARDWARE CONFIGURATION OF MOBILE TERMINAL
[0071] Next, a hardware configuration of the mobile terminal 20 will be described with reference to FIG. 4 .
[0072] FIG. 4 is a block diagram showing the hardware configuration of the mobile terminal 20 . The mobile terminal 20 includes a central processing unit (CPU) 201 , a read only memory (ROM) 202 , as random access memory (RAM) 203 , and a host bus 204 . Furthermore, the mobile terminal 20 includes a bridge 205 , an external bus 206 , an interface 207 , an input device 208 , an output device 210 , a storage device (HDD) 211 , a drive 212 , and a communication device 215 .
[0073] The CPU 201 functions as an arithmetic processing device and a control device, and controls the entire operations of the mobile terminal 20 according to various programs. Furthermore, the CPU 201 may be a microprocessor. The ROM 202 stores programs, arithmetic parameters or the like to be used by the CPU 201 . The RAM 203 temporarily stores a program to be used by the CPU 201 in its execution, parameters that change appropriately in the execution, or the like. These are interconnected through the host bus 204 configured from a CPU bus or the like.
[0074] The host bus 204 is connected to the external bus 206 such as a peripheral component interconnect/interface (PCI) bus through the bridge 205 . Moreover, the host bus 204 , the bridge 205 and the external bus 206 do not necessarily have to be configured separately, and the functions may be implemented in a single bus.
[0075] The input device 208 is configured from input means to be used by a user to input information, such as a mouse, a keyboard, a touch panel, a button, a microphone, a switch or a lever, an input control circuit that generates an input signal based on the input by the user and outputs the input signal to the CPU 201 , and the like. The user of the mobile terminal 20 can input various types of data to the mobile terminal 20 or issue an instruction for a processing operation by operating this input device 208 .
[0076] The output device 210 includes, for example, a display device such as a liquid crystal display (LCD) device, an organic light emitting diode (OLED) device, or a lamp. Furthermore, the output device 210 includes an audio output device such as a speaker, a head phone, or the like. The output device 210 outputs reproduced content; for example. Specifically, the display device displays various types of information of reproduced image data or the like in the form of text or image. For its part, the audio output device converts reproduced audio data or the like to sound and outputs the sound.
[0077] The storage device 211 is a data storage device configured as an example of a storage unit of the mobile terminal 20 . The storage device 211 may include a storage medium, a recording device for recording data on the storage medium, a read device for reading data out of the storage medium, a deletion device for deleting data recorded on the storage medium, or the like. The storage device 211 is configured from a hard disk drive (HDD), for example. The storage device 211 drives a hard disk, and stores programs to be executed by the CPU 201 and various types of data.
[0078] The drive 212 is a reader/writer for the storage medium, and is built in or externally attached to the mobile terminal 20 . The drive 212 reads out information stored in an attached removable recording medium 24 such as a magnetic disk, an optical disk, a magneto-optical disk, a semiconductor memory or the like, and outputs the information to the RAM 203 .
[0079] The communication device 215 is an interface for communicating with the outside, for example. The communication device 215 may include a function of communicating with the base station 30 and a function of communicating with a GPS.
3. FUNCTIONAL CONFIGURATION OF MOBILE TERMINAL
[0080] Next, a mobile terminal 20 - 1 according to a first configuration example will be described with reference to FIG. 5 , a mobile terminal 20 - 2 according to a second configuration example will be described with reference to FIG. 6 , a mobile terminal 20 - 3 according to a third configuration example will be described with reference to FIG. 7 , a mobile terminal 20 - 4 according to a fourth configuration example will be described with reference to FIG. 8 , and a mobile terminal 20 - 5 according to a fifth configuration example will be described with reference to FIG. 9 .
3-1. First Configuration Example
[0081] FIG. 5 is a functional block diagram showing the mobile terminal 20 - 1 according to the first configuration example. As shown in FIG. 5 , the mobile terminal 20 - 1 according to the first configuration example includes a communication unit 220 , a correlation detection unit 230 for cell search, an indicator calculation unit 240 , a GPS receiving unit 250 , and a packet communication control unit 260 . The mobile terminal 20 - 1 according to the first configuration is applicable to the wireless communication system 1 according to the lust configuration example, for example.
[0082] The communication unit 220 is an interface to the base station 30 , and has a function of a receiving unit for receiving a wireless signal transmitted from the base station 30 and a function of a transmitting unit for transmitting a wireless signal to the base station 30 . Additionally, this configuration example assumes a case where the communication unit 220 receives, from the base station 30 , a wireless signal that is frequency-spread according to CDMA. Furthermore, wireless signals received by the communication unit 220 from k base stations 30 are expressed by the following formula 1.
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S k,0 , c k,0 , d k,0 : Transmission power of CPICH, spreading code waveform, data modulated signal waveform
S k,1 , c d,1 , d k,1 : Transmission power of Primary-CCPCH, spreading code waveform, data modulated signal waveform
S k,i : Transmission power of DPCH spread by an i-th channelization code from k-th base station
[0086] The first term of the right-hand side of formula 1 indicates the CPICHs from the k base stations 30 , the second term indicates the Primary-CCPCHs from the k base stations, the third term indicates the DPCHs in C channels, the fourth term indicates the SCHs, and the fifth term indicates a background noise. Furthermore, C k,0 is a composite spreading code, and is spread by a scrambling code C sc,k and a channelization code C ch,0 .
[0087] The correlation detection unit 230 for cell search (correlation detection unit) can identify a scrambling code having the highest correlation output, i.e. the base station 30 with the smallest propagation loss, by performing a three-step cell search based on a wireless signal received by the communication unit 220 . In the following, the there-step cell search will be briefly described.
[0088] First, the correlation detection unit 230 for cell search detects a correlation between a received signal and the C psc , and detects a timing of receiving a primary SCH (first step). Then the correlation detection unit 230 for cell search detects a pattern having the highest correlation with the received signal among the 64 C SSC combination patterns by using the timing of receiving a primary SCH detected in the first step (second step). As a result, a scrambling code group is identified, and frame-based synchronization is secured. Then the correlation detection unit 230 for cell search detects the correlation between the received signal and each of 8 types of scrambling codes included in the identified scrambling code group, and identifies a scrambling code with the highest correlation output (third step). Additionally, the Primary-CCPCH and the DPCH are spread by a different channelization code, and thus they remain frequency-spread.
[0089] The indicator calculation unit 240 (calculation unit) uses the correlation output obtained in the process of the cell search by the correlation detection unit 230 for cell search to calculate an indicator of the quality of communication for estimating the available capacity of the base station 30 . An example of calculation by the indicator calculation unit 240 will be described below
[0090] In the third step of the cell search, the CPICH, the Primary-CCPCH, and the DPCH are detected as signals that are multiplexed while still being spread, with regard to the correlation outputs for the other 7 types of scrambling codes. Here, taking the ratio of the chip rate of the spreading code to the symbol rate as a spreading factor (SF), an average value of 1/SF is detected as the correlation output due to the spreading.
[0091] Here, when the number of DPCHs (i.e. the number of users of the base station 30 ) to be multiplexed grows, or when the number of HS-DSCHs (i.e. the number of high-speed downlink shared channels to be shared by a plurality of users in HSDPA) grows, the correlation output is greatly increased in spite of each DPCH or each HS-DSCH being spread, and thus, the correlation outputs for the other 7 types of scrambling codes are considered to become high. Similarly, when the interference from other cell grows, the interference wave from such other cell also increases the correlation output, and thus, the correlation outputs for the other 7 types of scrambling codes are also considered to become high. Accordingly, when the correlation output for the identified scrambling code is taken as a and the minimum value of the correlation outputs for the other 7 types of scrambling codes is taken as b, b/a is considered to become larger as the available capacity of the base station 30 decreases due to the increase in the number of users of the base station 30 or as the interference from other cell grows.
[0092] Thus, the indicator calculation unit 240 calculates the above b/a as the indicator of the quality of communication for estimating the available capacity. Additionally, an indicator is effective as the indicator of the quality of communication as long as it indicates the relationship between the highest correlation output and other correlation output, and thus the indicator of the quality of communication is not limited to the above b/a. For example, the indicator calculation unit 24 may calculate c/a as the indicator of the quality of communication, where c is an average value of the correlation outputs for the other 7 types of scrambling codes.
[0093] The GPS receiving unit 250 functions as an acquisition unit for acquiring location information indicating the current location of the mobile terminal 20 by receiving and decoding a GPS signal transmitted from a satellite. Additionally, the location information obtained by the GPS receiving unit 250 corresponds to a subordinate concept of the location identification information enabling the identification of a location.
[0094] The packet communication control unit 260 transmits the indicator of the quality of communication obtained by the indicator calculation unit 240 and the location identification information obtained by the GPS receiving unit 250 to the estimation server 10 outside the core network to which the base station 30 belongs via the gateway 42 of the core network. As a result, the estimation server 10 can estimate the available capacity of the base station 30 , for example, based on the indicator of the quality of communication and the location identification information.
3-2. Second Configuration Example
[0095] FIG. 6 is a functional block diagram showing a mobile terminal 20 - 2 according to the second configuration example. As shown in FIG. 6 , the mobile terminal 20 - 2 according to the second configuration example includes the communication unit 220 , the correlation detection unit 230 for cell search, the indicator calculation unit 240 , and the packet communication control unit 260 . The mobile terminal 20 - 2 according to the second configuration is applicable the wireless communication system 1 according to the first configuration example, for example.
[0096] The correlation detection unit 230 for cell search performs the three-step cell search as with the first configuration example, and the indicator calculation unit 240 calculates the indicator of the quality of communication based on the correlation output for each scrambling code obtained in the process of the three-step cell search.
[0097] Furthermore, during the initial cell search and neighbouring cell search at the time of intermittent reception, the mobile terminal 20 - 2 is provided with scrambling codes of the neighbouring cells and the timing difference by a broadcast channel (BCH) or a paging channel (PCH).
[0098] Thus, by performing correlation detection for each of scrambling codes assigned to the neighbouring cells, the correlation detection unit 230 for cell search can obtain a correlation output for each of the plurality of scrambling codes as a reception intensity from each of a plurality of base stations 30 .
[0099] Here, the combination of the reception intensities from the plurality of base stations 30 is different depending on the location of the mobile terminal 20 - 2 . That is, since the location of the mobile terminal 20 - 2 can be identified based on the reception intensity from each of the plurality of base stations 30 , the reception intensity from each of the plurality of base stations 30 can be used as the location identification information. Additionally, a concrete method of location estimation based on the reception intensity from each of the plurality of base stations 30 will be described in “5. Configuration of Estimation Server.”
[0100] The packet communication control unit 260 transmits the indicator of the quality of communication obtained by the indicator calculation unit 240 and the reception intensity from each of the plurality of base stations 30 obtained by the correlation detection unit 230 for cell search as the location identification information to the estimation server 10 outside the core network to which the base stations 30 belongs via the gateway 42 of the core network. As a result, the estimation server 10 can estimate the available capacity of the base stations 30 , for example, based on the indicator of the quality of communication and the location identification information.
3-3. Third Configuration Example
[0101] Recently, Long Term Evolution (LTE) designed to increase the packet transmission/reception rate of a 3G mobile phone was developed, and the service is planned to start around 2010. LIE employs OFDM for downlink, SC(Single Carrier)-FDM for uplink, and further employs MIMO (Multiple Input Multiple Output), and thereby achieves a maximum 100 Mbps for downlink and maximum 50 Mbps for uplink. Accordingly, it is hoped for as a system that realizes a full-fledged high-speed wireless packet communication.
[0102] A mobile terminal 20 - 3 according to a third configuration example described below is applicable the wireless communication system 1 according to the first configuration example which uses the LTE mentioned above, for example.
[0103] FIG. 7 is a functional block diagram showing the mobile terminal 20 - 3 according to the third configuration example. As shown in FIG. 7 , the mobile terminal 20 - 3 according to the third configuration example includes the communication unit 220 , the GPS receiving unit 250 , the packet communication control unit 260 , and an unused subcarrier rate detection unit 270 .
[0104] The communication unit 220 is an interface to the base station 30 , and has a function of a receiving unit for receiving a wireless signal transmitted from the base station 30 and a function of a transmitting unit for transmitting a wireless signal to the base station 30 . Additionally, as described above, this configuration example assumes a case where the communication unit 220 receives an OFDMA signal from the base station 30 .
[0105] As with the first configuration example, the GPS receiving unit 250 functions as an acquisition unit for acquiring location information indicating the current location of the mobile terminal 20 - 3 by receiving and decoding a GPS signal transmitted from a satellite. Additionally, the location information obtained by the GPS receiving unit 250 corresponds to a subordinate concept of the location identification information enabling the identification of a location.
[0106] The unused subcarrier rate detection unit 270 detects the ratio of the number of subcarriers not used as a communication resource (unused subcarrier rate) among the total number of subcarriers in an OFDM symbol to which a physical downlink shared channel (PDSCH) is mapped. The frequency of detection of the unused subcarrier rate by the unused subcarrier rate detection unit 270 is determined by the tradeoff between power consumption and detection accuracy.
[0107] Additionally, to alleviate the issue of interference, the base station 30 is assumed to make use of unused resources by milling the subcarriers. Accordingly, the unused subcarrier rate detection unit 270 is assumed to be able to distinguish an unused resource by detecting power of each subcarrier.
[0108] Here, the flow of basic operation by the mobile terminal 20 - 3 will be described. The mobile terminal 20 - 3 can identify a physical cell ID during the process of performing cell search for a base station 30 with the smallest propagation loss and acquiring synchronization between a primary synchronization signal (PSS) and a secondary synchronization signal (SSS).
[0109] Furthermore, the mobile terminal 20 - 3 obtains information such as a system bandwidth notified by the base station 30 by decoding a physical broadcast channel (PBCH). Then, after performing location registration and the like to the base station 30 , the mobile terminal 20 - 3 starts communication by itself or goes into an idle state. (RRC_IDLE state) until a paging is received. Additionally, when in the idle state, the mobile terminal 20 - 3 may, during the intermittent reception period, periodically search for a cell in a better condition or check whether there is a paging notified by a PDCCH.
[0110] Furthermore, to reselect a cell, the mobile terminal 20 - 3 measures the reception quality of a serving cell (an already camped cell) and a neighbouring cell. Specifically, the mobile terminal 20 - 3 measures the reception quality by receiving a reference signal (RS) unique to a cell and obtaining the average reference signal received power. Furthermore, an indicator R-criterion is defined, and R-criteria R s and R n for the serving cell and the neighbouring cell are expressed by the following formulae 2 and 3.
[0000] [Equation 2]
[0000] R s =Q meas,s +Q hyst,s (Formula 2)
[0000] [Equation 3]
[0000] R n =Q meas,n +Q off — s,n (Formula 3)
[0111] The Q hyst,s is a parameter for controlling the degree of hysteresis to prioritize the R-criteria. The Q off — s,n is an offset amount to be applied between the serving cell and the neighbouring cell.
[0112] Next, the mobile terminal 20 - 3 decodes the PDCCH, which is a physical channel for transmitting control information, to check whether there is a paging. The PDCCH is assigned to 3 symbols at the beginning of each subframe configured by 14 symbols, and the mobile terminal 20 - 3 in the idle state can check whether there is a paging by decoding these 3 symbols in the intermittent period.
[0113] To efficiently decode the PDCCH, a Common search space in which a PDCCH to be transmitted to all the mobile terminals is mapped and a UE-Specific search space in which a PDCCH to be transmitted to a specific mobile terminal is mapped are defined in the 3-symbol resource block. Paging information is transmitted being mapped to the Common search space, and thus it is considered sufficient that an idle mobile terminal 20 - 3 decodes at least the Common search space.
[0114] Additionally, a cycle DRX of the intermittent reception is determined by the mobile terminal 20 - 3 by processing a paging parameter notified by the serving cell. The mobile terminal 20 - 3 can detect whether there is the above-described paging and also, can reselect a cell, according to the cycle DRX. For example, when the quality of the serving cell falls below a certain threshold value, the mobile terminal 20 - 3 performs measurement of the neighbouring cell more frequently than the cycle DRX, and reduces the risk of going out of service range.
[0115] Furthermore, with regard to the measurement of the RSRP, the specification only defines the use of the RS unique to a cell, and how many RSs among RSs mapped in the frequency domain are to he used and how many RSs are among RSs mapped in the time domain are to be used depend on the application.
[0116] Accordingly, the unused subcarrier rate detection unit 270 basically periodically detects the unused subcarrier rate separately from the measurement of the RSRP while taking power consumption into consideration. On the other hand, in case of measuring the RSRP in a region in which a PDSCH is mapped and by using all the RSs mapped in the frequency domain, the unused subcarrier rate detection unit 270 can also perform detection of the unused subcarrier rate together with the RSRP measurement.
[0117] The packet communication control unit 260 transmits the location identification information obtained by the GPS receiving unit 250 and the unused subcarrier rate obtained by the unused subcarrier rate detection unit 270 as the indicator of the quality of communication to the estimation server 10 outside the core network to which the base station 30 belongs via the gateway 42 of the core network. As a result, the estimation server 10 can estimate the available capacity of the base station 30 , for example, based on the indicator of the quality of communication and the location identification information.
[0118] Additionally, if the packet communication control unit 260 is replaced by an IMS-compliant unit that functions to comply with IMS, the mobile terminal 20 - 3 can be applied to the wireless communication system 3 according to the third configuration example shown in FIG. 3 .
3-4. Fourth Configuration Example
[0119] FIG. 8 is a functional block diagram showing a mobile terminal 204 according to a fourth configuration example. As shown in FIG. 8 , the mobile terminal 20 - 4 according to the fourth configuration example includes the communication unit 220 , the correlation detection unit 230 for cell search, the indicator calculation unit 240 , the GPS receiving unit 250 , and the packet communication control unit 260 . The mobile terminal 20 - 4 according to the fourth configuration is applicable the wireless communication system 2 according to the second configuration example, for example.
[0120] The mobile terminal 20 - 4 can register location with either of the first base station 30 and the second base station 50 . Accordingly, the correlation detection unit 230 for cell search and the indicator calculation unit 240 can acquire the indicator of the quality of communication for estimating the available capacity of the first base station 30 at the time of performing cell search for the first base station 30 , and can acquire the indicator of the quality of communication for estimating the available capacity of the second base station 50 at the time of performing cell search for the second base station 50 .
[0121] As with the first configuration example, the GPS receiving unit 250 functions as an acquisition unit for acquiring location information (location identification information) indicating the current location of the mobile terminal 20 - 4 by receiving and decoding a GPS signal transmitted from a satellite.
[0122] The packet communication control unit 260 transmits the location identification information obtained by the GPS receiving unit 250 and the indicator of the quality of communication for estimating the available capacity of the first base station 30 obtained by the indicator calculation unit 240 to the estimation server 10 via the gateway 42 of the core. network to which the base station 30 belongs. Similarly, the packet communication control unit 260 transmits the location identification information obtained by the GPS receiving unit 250 and the indicator of the quality of communication for estimating the available capacity of the second base station 50 obtained by the indicator calculation unit 240 to the estimation server 10 via the gateway 62 of the core network to which the base station 50 belongs. As a result, the estimation server 10 can estimate the available capacity of both the base station 30 and the base station 50 based on the indicator of the quality of communication and the location identification information.
3-5. Fifth Configuration Example
[0123] FIG. 9 is a functional block diagram showing a mobile terminal 20 - 5 according to a fifth configuration example. As shown in FIG. 9 , the mobile terminal 20 - 5 according to the fifth configuration example includes the communication unit 220 , the correlation detection unit 230 for cell search, the indicator calculation unit 240 , the OPS receiving unit 250 , and an IMS-compliant unit 280 . The mobile terminal 20 - 5 according to the fifth configuration is applicable the wireless communication system 3 according to the third configuration example, for example.
[0124] The correlation detection unit 230 for cell search performs the three-step cell search as with the first configuration example, and the indicator calculation unit 240 calculates the indicator of the quality of communication based on the correlation output for each scrambling code obtained in the process of the three-step cell search.
[0125] As with the first configuration example, the GPS receiving unit 250 functions as an acquisition unit for acquiring location information (location identification information) indicating the current location of the mobile terminal 20 - 5 by receiving and decoding a GPS signal transmitted from a satellite.
[0126] The IMS-compliant unit 280 controls communication by SIP message, for example. According to the EMS, a control communication network and a media communication network are completely separated, and, after IMS authentication, a radio resource is allocated at all times to the control communication network for exchanging SIP messages. That is, according to the IMS, a SIP message reaches the S-CSCF 75 from the mobile terminal 20 - 5 with high reliability. Also, a plurality of various types of message bodies, such as a message in a text format, can be included in the SIP message.
[0127] Accordingly, the IMS-compliant unit 280 may add to the message body of the SIP message the location identification information obtained by the GPS receiving unit 250 and the indicator of the quality of communication obtained by the indicator calculation unit 240 . Then, the IMS-compliant unit 280 can transmit the SIP message to the S-CSCF 75 , the HSS 76 or the AS 78 on the home network side via the base station 30 and the P-CSCF 72 . Additionally, the EMS-compliant unit 280 may also encrypt the location identification information and the indicator of the quality of communication and add the same to the message body of the SIP message.
4. OPERATION OF MOBILE TERMINAL
[0128] Heretofore, configuration examples of the mobile terminal 20 have been described with reference to FIGS. 5 to 9 . Subsequently, the flow of a wireless communication method to be performed by the mobile terminal 20 will be described with reference to FIG. 10 .
[0129] FIG. 10 is a flow chart showing a flow of a wireless communication method performed by the mobile terminal 20 . As shown in FIG. 10 , the communication unit 220 receives a wireless signal from the base station 30 (S 282 ), and the correlation detection unit 230 for cell search performs the three-step cell search based on the wireless signal received by the communication unit 220 (S 284 ).
[0130] Then, the indicator calculation unit 240 calculates the indicator of the quality of communication for estimating the available capacity of the base station 30 , based on the size of the correlation outputs of a plurality of scrambling codes obtained in the process of the three-step cell search (S 286 ). For its part, the GPS receiving unit 250 acquires the location information (location identification information) indicating the current location of the mobile terminal 20 by receiving and decoding a GPS signal transmitted from a satellite (S 288 ).
[0131] The packet communication control unit 280 transmits the indicator of the quality of communication obtained by the indicator calculation unit 240 and the location identification information obtained by the UPS receiving unit 250 in this manner to the estimation server 10 via the communication unit 220 (S 290 ).
5. CONFIGURATION OF ESTIMATION SERVER
[0132] Next, the configuration of the estimation server 10 will be described with reference to FIGS. 11 and 12 .
[0133] FIG. 11 is an explanatory diagram showing the configuration of the estimation server 10 . As shown in FIG. 11 , the estimation server 10 includes a communication unit 110 , a primary available capacity estimation unit 120 , a location identification unit 130 , an available capacity correction unit 140 , a storage unit 150 , and an access network selection unit 160 . This estimation server 10 is applicable the first to third configuration examples of the wireless communication system shown in FIGS. 1 to 3 .
[0134] The communication unit 110 is an interface to the mobile terminal 20 , and functions as a receiving unit for receiving the indicator of the quality of communication, the location identification information and the like transmitted from the mobile terminal 20 , for example, via the access network 40 .
[0135] The primary available capacity estimation unit 120 (estimation unit) primarily estimates, from the indicator of the quality of communication received by the communication unit 110 , the available capacity of a cell (base station 30 ) with which the location of the mobile terminal 20 is registered. For example, when the indicator of the quality of communication is the b/a described above, the indicator of the quality of communication grows larger as the number of multiplexed DPCHs, which are channels allocated to other mobile terminals, increases. Accordingly, the primary available capacity estimation unit 120 can primarily estimate the available capacity of the base station 30 based on the indicator of the quality of communication b/a. More specifically, the primary available capacity estimation unit 120 may estimate the available capacity of the base station 30 to be at a level that is higher as the indicator of the quality of communication b/a is smaller (the available capacity is higher), among a plurality of digital levels.
[0136] Additionally, the indicator of the quality of communication b/a is expected to be a constant value which is not dependent on the distance between the base station 30 and the mobile terminal 20 - 1 . For example, in case an AGC is not operating in a receiving circuit, each of the correlation outputs a and b will have a smaller value as the distance between the base station 30 and the mobile terminal 20 - 1 becomes greater. However, the values will become smaller at the same rate, and thus, the indicator of the quality of communication b/a is assumed to be constant, without being dependent on the distance between the base station 30 and the mobile terminal 20 - 1 . On the other hand, in case the AGC is operating in the receiving circuit, if the base station 30 is transmitting the same signal, the correlation outputs a and b ideally become constant, and thus, the indicator of the quality of communication b/a will also be a constant value.
[0137] Furthermore, the influence of noise floor of the receiving circuit of the mobile terminal 20 - 1 on the available capacity of the base station 30 that is to be estimated based on the indicator of the quality of communication b/a is different depending on the distance between the mobile terminal 20 - 1 and the base station 30 . Specifically, as the mobile terminal 20 - 1 gets farther away from the base station 30 , the available capacity of the base station 30 will be estimated to be less than the actual available capacity due to the noise floor of the receiving circuit. This is because, since the noise floor of the receiving circuit is a random signal, the noise floor acts to increase the value of b as the mobile terminal 204 gets farther away from the base station 30 . However, the communication environment of the mobile terminal 204 existing at the cell edge far from the base station 30 is significantly poor, and thus, it is assumed that, even if the available capacity of the base station 30 is estimated to be less than the actual available capacity, the had influence is restrictive.
[0138] The location identification unit 130 identifies the current location of the mobile terminal 20 based on the location identification information received by the communication unit 110 . For example, when the location identification information is the reception intensity from each of the plurality of base stations 30 described in “3-2. Second Configuration Example,” the location identification unit 130 identifies the current location of the mobile terminal 20 by the method described below.
[0139] FIG. 12 is a diagram for illustrating the method of identifying the current location based on the reception intensity from each of the plurality of base stations 30 . Additionally, for the sake of explanation, the concept of a sector is not included. As shown in FIG. 12 , the transmission power and the absolute gain of the transmission antenna of the base station 30 A are respectively referred to as W A and G A , the transmission power and the absolute gain of the transmission antenna of the base station 30 B are respectively referred to as W B and G B , and the transmission power and the absolute gain of the transmission antenna of the base station 30 C are respectively referred to as W C and G C .
[0140] Also, the coordinates of the base stations 30 A to 30 C are known, and the coordinate of the base station 30 A is A(0, 0), the coordinate of the base station 30 B is B(a, b), the coordinate of the base station 30 C is C(c, d), and the coordinate at which the mobile terminal 20 is located is X(x, y). Also, it is assumed that the ratio of distances from point A, point B and point C to point X is known. Furthermore, when taking the distance from point A to point X as variable z, the ratio of the square of the distance between point B and point X to z 2 as α, and the ratio of the square of the distance between point C and point X to z 2 as β, the following formulae 4 to 6 are obtained.
[0000] [Equation 4]
[0000] x 2 +y 2 =z 2 (Formula 4)
[0000] [Equation 5]
[0000] ( x−a ) 2 +( y−b ) 2 αz 2 (Formula 5)
[0000] [Equation 6]
[0000] ( x−c ) 2 +( y−d ) 2 =βz 2 (Formula 6)
[0141] Here, a, b, c, d, α (>1), and β (>1) are known values, and x, y, and z are variables. The following formula 7 is obtained from the formulae 4 and 5, and the following formula 8 is obtained from the formulae 5 and 6.
[0000]
[
Equation
7
]
(
x
-
a
1
-
α
)
2
+
(
y
-
b
1
-
α
)
2
=
(
1
(
1
-
α
)
2
-
1
1
-
α
)
·
(
a
2
+
b
2
)
(
Formula
7
)
[
Equation
8
]
(
x
-
c
1
-
β
)
2
+
(
y
-
d
1
-
β
)
2
=
(
1
(
1
-
β
)
2
-
1
1
-
β
)
·
(
c
2
+
d
2
)
(
Formula
8
)
[0142] The formula 7 indicates the locus of a circle whose centre is (a/(1−α), b/(1−α)) and whose radius is a square root of the right-hand side. Similarly, the formula 8 indicates the locus of a circle whose centre is (c/(1−β), d(1−β)) and whose radius is a square root of the right-hand side. Accordingly, (x, y) satisfying the formulae 4 to 6 corresponds to the intersection of the loci of the two circles indicated by the formulae 7 and 8.
[0143] On the other hand, received power densities P A , P B , and P C from the base stations 30 A, 30 B and 30 C at X(x, y) are expressed by the following formulae 9 to 11.
[0000]
[
Equation
9
]
P
A
=
W
A
G
A
4
π
d
2
(
Formula
9
)
[
Equation
10
]
P
B
=
W
B
G
B
4
π
α
d
2
(
Formula
10
)
[
Equation
11
]
P
C
=
W
C
G
C
4
π
β
d
2
(
Formula
11
)
[0144] When W A =W B =W C and G A =G B =G C , the following formulae 12 and 13 are obtained from the formulae 9 to 11.
[0000]
[
Equation
12
]
α
=
P
A
P
B
(
Formula
12
)
[
Equation
13
]
β
=
P
A
P
C
(
Formula
13
)
[0145] The α and β will be known values by the above formulae 12 and 13. Additionally, even if the transmission outputs W A , W B and W C of the base stations 30 A to 30 C are different, the ratio of distances from respective base stations 30 to X(x, y) can be obtained, provided that information relating to the transmission outputs of the base stations 30 A to 30 C is notified by the BCH. The same can be said for a case where the transmission output of the CPICH is notified by the BCH.
[0146] The location identification unit 130 can identify the current location of the mobile terminal 20 from the reception intensity, as the location identification information, from each of the plurality of base stations 30 by the above calculations. Additionally, when the location identification information is location information indicating latitude and longitude, the location identification unit 130 does not have to perform any special calculation.
[0147] We will return to the description of the configuration of the estimation server 10 with reference to FIG. 11 . As has been described, the primary available capacity estimation unit 120 estimates the available capacity of the base station 30 based on, for example, the indicator of the quality of communication b/a. However, as the mobile terminal 20 gets farther away from the base station 30 , the base station 30 will set the amplitude of the DPCH allocated to the mobile terminal 20 to be larger, and thus the value of b will become larger. That is, the indicator of the quality of communication b/a will have a different meaning with regard to the available capacity of the base station 30 depending on the location of the mobile terminal 20 .
[0148] In the following, the influence of the distance. between the mobile terminal 20 and the base station 30 on the available capacity of the base station 30 that is estimated based on the indicator of the quality of communication b/a will be described in greater detail. Let us assume that the estimation server 10 has estimated the available capacity of the base station 30 based on an indicator of the quality of communication b1/a1 received from the mobile terminal 20 that is attempting to start communication. Here, in case the mobile terminal 20 exists near the base station 30 , the base station 30 can multiple-transmit a DPCH for the mobile terminal 20 with low power. Accordingly, the influence on the available capacity (degree of congestion) of the base station 30 due to the start of signal transmission to this mobile terminal 20 existing near the base station 30 is small. That is, the amount of reduction in the available capacity of the base station 30 caused by the start of signal transmission to the mobile terminal 20 existing near the base station 30 is small.
[0149] On the other hand, in case the mobile terminal 20 exists far from the base station 30 , the base station 30 will multiple-transmit a DPCH for this mobile terminal 20 with high power. Accordingly, the influence on the available capacity (degree of congestion) of the base station 30 due to the start of signal transmission to this mobile terminal 20 existing far from the base station 30 is large. That is, the amount of reduction in the available capacity of the base station 30 caused by the start of signal transmission to the mobile terminal 20 existing far from the base station 30 is large.
[0150] Thus, the available capacity correction unit 140 (correction unit) corrects the available capacity of the base station 30 estimated by the primary available capacity estimation unit 120 by using the distance between the mobile terminal 20 and the base station 30 . Specifically, the available capacity correction unit 140 may correct the available capacity of the base station 30 estimated by the primary available capacity estimation unit 120 to a value smaller as the distance between the mobile terminal 20 and the base station 30 is increased. Additionally, the distance between the mobile terminal 20 and the base station 30 can be obtained from the difference between the location of the mobile terminal 20 identified by the location identification unit 130 and the known installation location of the base station 30 .
[0151] The storage unit 150 is a storage medium storing user information, history information, communication cost information, available capacity information, and the like. Additionally, the storage unit 150 (user information storage unit, communication cost storage unit) may be a storage medium such as a non-volatile memory, a magnetic disk, an optical disk, a magneto optical (MO) disk, and the like. The non-volatile memory may be an electrically erasable programmable read-only memory (EEPROM), and an erasable programmable ROM (EPROM), for example. Also, the magnetic disk may be a hard disk, a discoid magnetic disk, and the like. Also, the optical disk may be a compact disc (CD), a digital versatile disc recordable (DVD-R), a Blu-ray disc (ED; registered trademark), and the like.
[0152] When a plurality of access networks can be used by the mobile terminal 20 as shown in FIG. 2 , the access network selection unit 160 (selection unit) selects an access network suitable for the mobile terminal 20 based on the available capacity corrected by the available capacity correction unit 140 and various types of information stored in the storage unit 150 . Concrete example of this selection will be described in “6-3. Third Operation Example” and “6-4. Fourth Operation Example.”
6. OPERATION OF ESTIMATION SERVER
[0153] Heretofore, the configuration of the estimation server 10 has been described with reference to FIGS. 11 and 12 . Subsequently, the first to fourth configuration examples of the estimation server 10 will be described with reference to FIGS. 13 to 16 .
6-1. First Operation Example
[0154] FIG. 13 is a flow chart showing the first operation example of the estimation server 10 . As shown in FIG. 13 , first, when the communication unit 110 of the estimation server 10 receives the indicator of the quality of communication and the location identification information from the mobile. terminal 20 (S 310 ), the primary available capacity estimation unit 120 primarily estimates the available capacity of the base station 30 based on the indicator of the quality of communication (S 320 ). Also, when the location identification information is not information directly indicating the latitude and longitude, the location identification unit 130 identifies the current location of the mobile terminal 20 based on the location identification information (S 330 ). Then, the available capacity correction unit 140 corrects the available capacity estimated by the primary available estimation unit 120 by using the distance between the mobile terminal 20 and the base station 30 (S 340 ).
6-2. Second Operation Example
[0155] FIG. 14 is a flow chart showing the second operation example of the estimation server 10 . As shown in FIG. 14 , the second operation example includes, after the processes of S 310 to S 340 shown in the first operation example, a process of further correcting the available capacity based on history information (S 350 ). The history information is stored in the storage unit 150 , and is information relating to the history of influences of the location information of many mobile terminals on the available capacity, information relating to the history of the QoSs that are actually obtained, and the like. The available capacity correction unit 140 further corrects, by using the history information, the available capacity that has been corrected in S 340 by using the location information. Let us assume, for example, that the history information includes the relationship between a previously estimated available capacity and the QoS, and that the QoS is less than the QoS expected from the estimated available capacity. In this case, the actual available capacity is considered to be less than the estimated available capacity, and thus, the available capacity correction unit 140 may correct the available capacity to be less.
6-3. Third Operation Example
[0156] FIG. 15 is a flow chart showing the third operation example of the estimation server 10 . As shown in FIG. 15 , the third operation example includes, after the processes of S 310 to S 340 shown in the first operation example, storing of the available capacity (S 360 ) and selection of an access network (S 370 ).
[0157] Specifically, the available capacity corrected by the available capacity correction unit 140 in S 340 is stored in the storage unit 150 (S 360 ). The storage unit 150 also stores user information indicating the preference of a user of the mobile terminal 20 on communication. Weighting on cost indicating that a user desires low cost, weighting on high communication speed indicating that a user desires high-speed communication, and the like, are set as the user information. This user information may be set based on a user operation on the mobile terminal 20 . Furthermore, the storage unit 150 stores communication cost information indicating the communication cost for each access network. For example, information indicating the communication cost per unit time, information indicating the communication cost per unit data amount, and the like, are assumed as the communication cost information, for example.
[0158] Then, the access network selection unit 160 selects an access network suitable for the user of the mobile terminal 20 based on the available capacity stored in the storage unit 150 , the user information and the communication cost information (S 370 ). For example, when preference for cost is set in the user information of the mobile terminal 20 , the access network selection unit 160 refers to the communication cost information, selects an access network with the lowest communication cost, and notifies the mobile terminal 20 . On the other hand, when preference for high communication speed is set in the user information of the mobile terminal 20 , the access network selection unit 160 refers to the available capacity for each access network stored in the storage unit 150 , selects an access network with the highest available capacity, and notifies the mobile terminal 20 . Additionally, preference of a user may be set in the user information according to conditions. For example, preference for high communication speed is set in case of downloading a packet having a certain size or more, and preference for cost is set in other cases.
6-4. Fourth Operation Example
[0159] FIG. 16 is a flow chart showing the fourth operation example of the estimation server 10 . As shown in FIG. 16 , the fourth operation example includes, after the processes of S 310 to S 340 shown in the first operation example, storing of the available capacity (S 360 ) and selection of an access network (S 380 ).
[0160] Specifically, the available capacity corrected by the available capacity correction unit 140 in S 340 is stored in the storage unit 150 (S 360 ). Furthermore, in this operation example, the communication cost is assumed to change depending on the available capacity, and the storage unit 150 stores variable cost information indicating the communication cost per available capacity.
[0161] Then, the access network selection unit 160 selects an access network suitable for the user of the mobile terminal 20 based on the available capacity stored in the storage unit 150 , the user information and the variable cost information (S 380 ). Specifically, the access network selection unit 160 acquires communication costs in accordance with the available capacities of respective access networks, and in case preference for cost is set in the user information of the mobile terminal 20 , selects an access network with the lowest communication cost, and notifies the mobile terminal 20 . On the other hand, when preference for high communication speed is set in the user information of the mobile terminal 20 , the access network selection unit 160 refers to the available capacity of each access network stored in the storage unit 150 , selects an access network with the highest available capacity, and notifies the mobile. terminal 20 .
7. CONCLUSION
[0162] As has been explained, according to the embodiments of the present invention, the following effects can be obtained.
The estimation server 10 can estimate the available capacity of the base station 30 with which the location of the mobile terminal 20 is registered based on an approximate value of an relative amplitude ratio (b/a) of DPCHs allocated to other mobile terminals. Furthermore, the estimation server 10 notifies the mobile terminal 20 of the estimated available capacity of the base station 30 , thereby enabling the mobile terminal 20 to grasp the available capacity of the base station 30 with which the location of the mobile terminal 20 is registered. Furthermore, the estimation server 10 can identify the location of the mobile terminal 20 even when a GPS function is not provided to the mobile terminal 20 as shown in the second configuration example or even when the mobile terminal 20 is at a location where it is hard to use the GPS function. Furthermore, the estimation server 10 can select an access network best suited to a user at the time, according to the preference of the user of the mobile terminal 20 . Furthermore, even in a case of the communication cost changing depending on the relationship between supply and demand, the estimation server 10 can select an appropriate access network according to the changing communication cost. Furthermore, by configuring the system according to IMS, as with the wireless communication system 3 according to the third configuration example, the mobile terminal 20 is enabled to communicate with the estimation server 10 (S-CSCF 75 , AS 78 , and the like) by using a SIP message.
[0168] It should be understood by those skilled in the art that various modifications, combinations, sub-combinations and alterations may occur depending on design requirements and other factors insofar as they are within the scope of the appended claims or the equivalents thereof.
[0169] For example, an example has been described above where the mobile terminal 20 calculates the indicator of the quality of communication based on the correlation output of a scrambling code and notifies the estimation server 10 of this indicator of the quality of communication. However, the present invention is not limited to such an example. As a modified example, the mobile terminal 20 may notify the estimation server 10 of correlation outputs of a plurality of scrambling codes forming a specific scrambling code group, and the estimation server 10 may calculate the indicator of the quality of communication based on the notified correlation outputs and estimate the available capacity of the base station 30 from the indicator of the quality of communication.
[0170] Furthermore, it is not necessary to perform each step in the processing of the estimation server 10 and the mobile terminal 20 in chronological order according to the sequence shown in the sequence chart or the flow chart. For example, each step in the processing of the estimation server 10 and the mobile terminal 20 may include the processing which is performed in parallel or individually (e.g. parallel processing or object processing).
[0171] Furthermore, it is also possible to create a computer program for causing hardware such as the CPU 201 , the ROM 202 , and the RAM 203 that are built in the estimation server 10 and the mobile terminal 20 to perform functions that are the same as each structural element of the estimation server 10 and the mobile terminal 20 described above. A storage medium storing the computer program is also provided.
[0172] The present application contains subject matter related to that disclosed in Japanese Priority Patent Application JP 2009-126951 filed in the Japan Patent Office on May 26, 2009, the entire content of which is hereby incorporated by reference. | Systems, methods, and computer program products are provided for calculating an indicator of a quality of communication within a wireless communication access network and for estimating the available capacity of a base station within the wireless communication access network. In one exemplary embodiment, a method comprises receiving an indication, generated by a mobile terminal, of the quality of communication between the base station and the mobile terminal, and estimating the available capacity of the base station based on the received indication. | 7 |
CROSS-REFERENCE TO RELATED APPLICATION
The present application claims priority on U.S. provisional application No. 60/635,015 filed on Dec. 13, 2004, which is incorporated herein by reference in its entirety.
TECHNICAL FIELD
The present invention relates to improvements in the field of electrochemistry. In particular, this invention relates to compositions that can be used for various purposes such as anti-static agents or for preparing redox couples or reversible switchable systems.
BACKGROUND OF THE INVENTION
Sun is a free and unlimited renewable source of energy. It can be converted directly to electricity by using p-n heterojunction solar cells (like silicon-based devices), electrochemical photovoltaic cells (EPC's) or dye-sensitized solar cells (DSSC's). EPC's are systems based on a junction between a semiconductor (p-type or n-type) and an electrolyte containing one redox couple; an auxiliary electrode completes the device. Owing to the built-in potential developed at the semiconductor/electrolyte interface, the photogenerated electrons and holes are separated and used to undergo oxidation and reduction reactions at the electrodes, respectively with the reduced and oxidized species of the redox couple. On the other hand, DSSC's are systems based on a junction between dye-chemisorbed nanocristalline TiO 2 particles, deposited on a conductive glass substrate, and a non-aqueous electrolyte containing the I − /I 3 − redox couple; a platinum-coated conductive glass electrode completes the device. In such systems, the light absorption (by the dye molecules) and charge-carrier transport (in the conduction band of the semiconductor to the charge collector) processes are separated. Homogeneous oxidation of I − species serves to regenerate the photoexcited dye molecules whereas the heterogeneous reduction of I 3 − species takes place at the platinum-coated electrode.
There is extensive prior art on EPC's and DSSC's. However, one main issue still to resolve is to find a redox couple that is electrochemically stable, non-corrosive, with a high degree of reversibility and a high electropositive (in conjunction with n-type semiconductors) or electronegative (in conjunction with p-type semiconductors) potential, and colorless when used in concentrations allowing high electrolyte ionic conductivities.
I − /I 3 − is the most investigated redox couple for DSSC's. Cations may be alkali metals or organic cations containing quaternary ammonium groups such as dialkylimidazolium (Stathatos et al., Chem. Mater., 15, 1825 (2003)). The main limitations of this system are (i) the fact that it absorbs a significant part of the visible light of the solar spectrum when used in the concentration range giving reasonably good ionic conductivities (which leads to a decrease in the energy conversion efficiency); (ii) its too low redox potential (which limits the device photovoltage); (iii) its reactivity towards silver (which prevents the use of this metal as a current collector); and (iv) the high volatility of the electrolyte when usual organic solvents are employed (which causes an irreversible instability of the device).
Nusbaumer et al. in Chem. Eur. J., 9, 3756 (2003) studied alternative redox couples for DSSC's based on much more expensive cobalt complexes. Although the fact that these systems are less colored and possess more positive potential than the I − /I 3 − redox couple, the oxidized species (Co III ) may be reduced at the conductive glass acting as a substrate for the TiO 2 particles, in which case the energy conversion efficiency is decreased. Moreover, regeneration of the dye molecules by the reduced species (Co II ) (absolutely necessary to the operation of the device) may become more difficult due to association of the oxidized species (Co III ) with the sensitizer.
In EPC's, various redox couples dissolved in water were studied, such as Fe(CN) 6 4− /Fe(CN) 6 3− , I − /I 3 − Fe 2+ /Fe 3+ , S 2− /S n 2− , Se 2− /Se n 2− and V 2+ /V 3+ , and devices exhibiting a good energy conversion efficiency were generally unstable under sustained white light illumination due to photocorrosion of the semiconductor electrode. The use of non-aqueous electrolytic media (liquid, gel or polymer) could eliminate the photocorrosion process, but in these cases the number of redox couples is very limited. For examples, the I − /I 3 − (Skotheim and Inganäs, J. Electrochem. Soc., 132, 2116 (1985)) and S 2− /S n 2− (Vijh and Marsan, Bull. Electrochem., 5, 456 (1989)) redox couples were dissolved in polyethylene oxide (PEO) and modified PEO, respectively, and investigated in EPC's. In addition to the coloration and potential problems occurring with the I − /I 3 − couple, as mentioned above, the device stability has not been demonstrated. Regarding the S 2− /S n 2− redox couple, the same problems were observed but in this case the stability under white light illumination has been reported.
A cesium thiolate (CsT)/disulfide (T 2 ) redox couple, where T − stands for 5-mercapto-1-methyltetrazolate ion and T 2 for the corresponding disulfide, was dissolved in modified PEO and studied in an EPC (Philias and Marsan, Electrochim. Acta, 44, 2915 (1999)). Its more positive potential than that of the S 2− /S n 2− redox couple, its better dissociation in organic media including polymers (giving much more conductive electrolytes) and its much less intense coloration are responsible for the significant increase of the device energy conversion efficiency. Despite this improvement, the T − /T 2 redox couple is quite electrochemically irreversible, with a difference between the anodic (E pa ) and cathodic (E pc ) peak potentials, symbolized as ΔE p , of 1.70 V at a platinum electrode (scanning speed of 100 mV/s), even when put in a more conductive gel electrolyte comprising 50 mM of T − and 5 mM of T 2 dissolved in 80% DMF/DMSO (60/40) and incorporated in 20% poly(vinylidene fluoride), PVdF. Furthermore, its solubility is not very good in organic media.
Smith et al. in J. Org. Chem., 65, 8831 (2000) studied the redox hydrogen-bonded system formed from host-guest interactions with organic molecules that can bind through hydrogen bond and found that the redox couple of phenanthrenequinone (host) and urea (guest) undergoes a reversible one-electron reduction in aprotic medium. Collinson et al. gave more details about different kinds of redox-switched binding compounds (Collinson et al., Chem., soc., Rev. 31, 147-156, 2002). The articles of Smith et al. and Collinson et al. are hereby incorporated by reference.
Thus, based on prior art relative to redox couples for EPC's and DSSC'S, there are no redox couples permitting to considerably optimize the device energy conversion efficiency.
Therefore, new redox couples having improved properties with respect to the redox couples of the prior art would be highly desired. Moreover, redox couples permitting to avoid the drawbacks of the prior art are also highly desired. Finally, compositions or precursors that permit to easily prepare such redox couples would also highly be desired.
SUMMARY OF THE INVENTION
According to one aspect of the invention, there is provided a composition comprising a first compound selected from the group consisting of compounds of formulas (I), (III), (V), and (VII), and a second compound selected from the group consisting of compounds of formulas (II), (IV), (VI), and (VIII):
wherein
R 1 , R 2 and R 3 are the same or different and are selected from the group consisting of a hydrogen atom, C 1 -C 12 alkyl which is linear or branched, C 3 -C 12 cycloalkyl, C 1 -C 12 heterocyclyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 6 -C 12 aryl, C 6 -C 20 aralkyl, C 6 -C 20 alkylaryl, C 1 -C 12 heteroaryl, and part of polymer chain or network, or
R 1 and R 2 are joined together to form a 5 to 14 membered heterocyclyl in which R 3 is absent, a hydrogen atom, or a bond between N and R 1 or between N and R 2 ; or to form a 5 to 14 membered heteroaryl in which R 3 is absent, a hydrogen atom, a bond between N and R 1 or between N and R 2 , or is a part of polymer chain or network;
R 4 , R 5 and R 6 are the same or different and are selected from the group consisting of a hydrogen atom, C 1 -C 12 alkyl which is linear or branched, C 3 -C 12 cycloalkyl, C 1 -C 12 heterocyclyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 6 -C 12 aryl, C 6 -C 20 aralkyl, C 6 -C 20 alkylaryl, C 1 -C 12 heteroaryl, (CH 3 ) 2 N—, (C 2 H 5 ) 2 N—, (C 3 H 7 ) 2 N—, (C 4 H 9 ) 2 N—, (i-Pr) 2 N—, C n H 2n+1 , Ph 2 P(O)—, Ph 2 P—, Me 2 P(O)—, Me 2 P, Ph 2 P(S), Me 2 P(S), Ph 3 P═N—, Me 3 P═N—, and part of polymer chain or network, or
R 4 and R 5 are joined together to form a 5 to 14 membered heterocyclyl in which R 6 is absent, a hydrogen atom, or a bond between P and R 4 or between P and R 5 ; or to form a 5 to 14 membered heteroaryl ring in which R 6 is absent, a hydrogen atom, a bond between P and R 4 or between P and R 5 , or is a part of polymer chain or network;
R 7 and R 8 are the same or different and are selected from the group consisting of H, CF 3 , C n F 2n+1 , SO 2 H—, —SO 2 CF 3 , —NSO 2 CF 3 —, —SO 2 CH 3 , —NSO 2 CH 3 , C 1 -C 12 alkyl which is linear or branched, C 6 -C 12 aryl, C n H 2n+1 , CN, NO 2 , Ph 2 P(O)—, Ph 2 P—, Me 2 P(O)—, Me 2 P, Ph 2 P(S), Me 2 P(S), Ph 3 P═N—, Me 3 P═N—, C 6 H 5 C p H 2p —, C p H 2p+1 C 6 H 4 —, C p H 2p+1 C 6 H 4 C n H 2n —, CH 2 ═CHC p H 2p —, CH 2 ═CHC 6 H 5 —, CH 2 ═CHC 6 H 4 C p H 2p+1 —, CH 2 ═CHC p H 2p C 6 H 4 —,
and part of polymer chain or network;
R 9 and R 10 are the same or different and are selected from the group consisting of a hydrogen atom, C 1 -C 12 alkyl which is linear or branched, C 3 -C 12 cycloalkyl, C 1 -C 12 heterocyclyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 6 -C 12 aryl, C 6 -C 20 aralkyl, C 6 -C 20 alkylaryl, C 1 -C 12 heteroaryl, and part of polymer chain or network, or R 9 and R 10 are joined together to form a 5 to 7 membered heterocyclyl or heteroaryl; and
X − is (FSO 2 ) 2 N − , (CF 3 SO 2 ) 2 N − , (C 2 F 5 SO 2 ) 2 N − , (CF 3 SO 2 ) 3 C − , CF 3 SO 3 − , CF 3 COO − , AsF 6 − , CH 3 COO − , (CN) 2 N − , NO 3 − , 2.3HF, Cl − , Br − , I − , PF 6 − , BF 4 − , ClO 4 − , saccharin(o-benzoic sulfimide), (C 8 H 16 SO 2 ) 2 N − , or C 3 H 3 N 2 − ;
Z is C, N or As;
the alkyl, cycloalkyl, heterocyclyl, alkenyl, alkynyl, aryl, aralkyl, alkylaryl, and heteroaryl being unsubstituted or substituted with 1 to 3 substituents selected from the group consisting of F, Cl, Br, I, OH, a C 1 -C 6 alkoxy, a C 1 -C 6 hydroxy alkyl, NO 2 , CN, CF 3 , SO 3 − , C n F 2n+1 , C 1 -C 12 alkyl which is linear or branched, C 6 -C 12 aryl, C n H 2n+1 , Ph 2 P(O)—, Ph 2 P—, Me 2 P(O)—, Me 2 P, Ph 2 P(S), Me 2 P(S), Ph 3 P═N—, Me 3 P═N—, C 6 H 5 C p H 2p —, C p H 2p+1 C 6 H 4 —, C p H 2p+1 C 6 H 4 C n H 2n —, CH 2 ═CHC p H 2p —, CH 2 ═CHC 6 H 5 —, CH 2 ═CHC 6 H 4 C p H 2p+1 —, and CH 2 ═CHC p H 2p C 6 H 4 —, where n is an integer having a value from 1 to 48 (preferably 1 to 12) and p is an integer having a value from 1 to 48 (preferably 1 to 12).
According to another aspect of the present invention, there is provided a composition comprising a compound of formula (I) and a compound of formula (II); a compound of formula (III) and a compound of formula (IV); a compound of formula (V) and a compound of formula (VI); or a compound of formula (VII) and a compound of formula (VIII), the compounds of formulas (I), (II), (III), (IV), (V), (VI), (VII) or (VIII) being as previously defined.
It was found that the compositions of the present invention can be useful as precursors to redox couples. In fact, it was shown that such compositions can be easily activated so as to be converted into a redox couple. These compositions are simple, easy to prepare and to convert into redox couples. It was also found that such compositions can be used to efficiently prepare redox couples without involving tedious tasks. Moreover, it has been found that these compositions have a good thermal stability, a good solubility in various solvents. It also has been found that these compositions are substantially colorless at concentrations permitting a good conductivity. Finally, it was found that such compositions can be used as anti-static agents or in the manufacture of articles having anti-static properties.
According to another aspect of the invention, there is provided a kit for preparing a redox couple, the kit comprising a composition according to the present invention, together with instructions indicating how to convert at least a part of the composition into a redox couple.
According to another aspect of the invention, there is provided a kit for preparing a redox couple, the kit comprising:
a compound of formula (I), (III), (V), or (VII); instructions indicating how to convert at least a part of the compound of formula (I), (III), (V), or (VII) into its conjugated acid of formula (II), (IV), (VI), or (VII), respectively, so as to obtain a composition comprising a compound of formula (I) and a compound of formula (II); a compound of formula (III) and a compound of formula (IV); a compound of formula (V) and a compound of formula (VI); or a compound of formula (VII) and a compound of formula (VIII); and instructions indicating how to convert at least a part of the composition into a redox couple, wherein the compounds of formulas (I), (II), (III), (IV) (V), (VI), (VII) or (VIII) are as previously defined. Such a kit preferably further comprises a proton source such as a compound of formula HX, where X is as previously defined. Alternatively, the kit can also comprise another type of proton source such as a catalyst, or a proton exchange resin so as to convert the compound of formula (I), (III), (V), or (VII).
According to another aspect of the invention, there is provided a kit comprising:
a first compound selected from the group consisting of compounds of formulas (I), (III), (V), and (VII), and a second compound selected from the group consisting of compounds of formulas (II), (IV), (VI), and (VIII); and instructions indicating how to prepare a redox couple from the compounds, wherein the compounds of formulas (I), (II), (III), (IV), (V), (VI), (VII) or (VIII) are as previously defined. Such a kit preferably comprises a compound of formula (I) and a compound of formula (II); a compound of formula (III) and a compound of formula (IV); a compound of formula (V) and a compound of formula (VI); or a compound of formula (VII) and a compound of formula (VIII).
It was found that the kits of the present invention can be useful for expediently prepare redox couples. In fact, these kits can be used to simply, rapidly and at low costs prepare redox couples. By using, these kits, redox couples can be prepared without having recourse to tedious or complicated tasks.
According to another aspect of the invention, there is provided a process for preparing a redox couple comprising the step of activating a composition as defined in the present invention so as to convert at least a part of the composition into the redox couple. The activating step can be carried out by withdrawing at least one electron to a compound of the composition. The activating step is preferably carried out by means of an electron source. The composition can be prepared by reacting a selected amount of the first compound of formula (I), (III), (V), or (VII) with a proton source so as to obtain the second compound and then mixing together another selected amount of the first compound with the second compound so as to obtain the composition. Alternatively, a proton source, in an equimolar ratio less than 1, can be added to the first compound (i.e. if as example 1 mole of the first compound is used, less than 1 mole of proton will be used) so that such an addition of proton to the first compound permits to obtain the composition comprising the first and second compounds.
It was found that such a process can be very efficient in the preparation of a redox couple. Such a process implies only simple reagents and can be easily and rapidly carried out.
According to another aspect of the invention, there is provided a redox couple according to any one of schemes 1 to 4:
wherein
R 1 , R 2 and R 3 are the same or different and are selected from the group consisting of a hydrogen atom, C 1 -C 12 alkyl which is linear or branched, C 3 -C 12 cycloalkyl, C 1 -C 12 heterocyclyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 6 -C 12 aryl, C 6 -C 20 aralkyl, C 6 -C 20 alkylaryl, C 1 -C 12 heteroaryl, and part of polymer chain or network, or
R 1 and R 2 are joined together to form a 5 to 14 membered heterocyclyl in which R 3 is absent, a hydrogen atom, or a bond between N and R 1 or between N and R 2 ; or to form a 5 to 14 membered heteroaryl in which R 3 is absent, a hydrogen atom, a bond between N and R 1 or between N and R 2 , or is a part of polymer chain or network;
R 4 , R 5 and R 6 are the same or different and are selected from the group consisting of a hydrogen atom, C 1 -C 12 alkyl which is linear or branched, C 3 -C 12 cycloalkyl, C 1 -C 12 heterocyclyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 6 -C 12 aryl, C 6 -C 20 aralkyl, C 6 -C 20 alkylaryl, C 1 -C 12 heteroaryl, (CH 3 ) 2 N—, (C 2 H 5 ) 2 N—, (C 3 H 7 ) 2 N—, (C 4 H 9 ) 2 N—, (i-Pr) 2 N—, C n H 2n+1 , Ph 2 P(O)—, Ph 2 P—, Me 2 P(O)—, Me 2 P, Ph 2 P(S), Me 2 P(S), Ph 3 P═N—, Me 3 P═N—, and part of polymer chain or network, or
R 4 and R 5 are joined together to form a 5 to 14 membered heterocyclyl in which R 6 is absent, a hydrogen atom, or a bond between P and R 4 or between P and R 5 ; or to form a 5 to 14 membered heteroaryl ring in which R 6 is a absent, a hydrogen atom, a bond between P and R 4 or between P and R 5 , or is a part of polymer chain or network;
R 7 and R 8 are the same or different and are selected from the group consisting of H, CF 3 , C n F 2n+1 , SO 2 H—, —SO 2 CF 3 , —NSO 2 CF 3 —, —SO 2 CH 3 , —NSO 2 CH 3 , C 1 -C 12 alkyl which is linear or branched, C 6 -C 12 aryl, C n H 2n+1 , CN, NO 2 , Ph 2 P(O)—, Ph 2 P—, Me 2 P(O)—, Me 2 P, Ph 2 P(S), Me 2 P(S), Ph 3 P═N—, Me 3 P═N—, C 6 H 5 C p H 2p —, C p H 2p+1 C 6 H 4 —, C p H 2+1 C 6 H 4 C n H 2n —, CH 2 ═CHC p H 2p —, CH 2 ═CHC 6 H 5 —, CH 2 ═CHC 6 H 4 C p H 2p+1 —, CH 2 ═CHC p H 2p C 6 H 4 —,
and a part of polymer chain or network;
R 9 and R 10 are the same or different and are selected from the group consisting of a hydrogen atom, C 1 -C 12 alkyl which is linear or branched, C 3 -C 12 cycloalkyl, C 1 -C 12 heterocyclyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 6 -C 12 aryl, C 6 -C 20 aralkyl, C 6 -C 20 alkylaryl, C 1 -C 12 heteroaryl, and a part of polymer chain or network, or
R 9 and R 10 are joined together to form a 5 to 7 membered heterocyclyl or heteroaryl; and
X − is (FSO 2 ) 2 N − , (CF 3 SO 2 ) 2 N − , (C 2 F 5 SO 2 ) 2 N—, (CF 3 SO 2 ) 3 C − , CF 3 SO 3 − , CF 3 COO − , AsF 6 − , CH 3 COO − , (CN) 2 N − , NO 3 − , 2.3HF, Cl − , Br − , I − , PF 6 − , BF 4 − , ClO 4 − , saccharin(o-benzoic sulfimide), (C 8 H 16 SO 2 ) 2 N − , or C 3 H 3 N 2 − ;
Z is C, N or As;
the alkyl, cycloalkyl, heterocyclyl, alkenyl, alkynyl, aryl, aralkyl, alkylaryl, and heteroaryl being unsubstituted or substituted with 1 to 3 substituents selected from the group consisting of F, Cl, Br, I, OH, a C 1 -C 6 alkoxy, a C 1 -C 6 hydroxy alkyl, NO 2 , CN, CF 3 , SO 3 − , C n F 2n+1 , C 1 -C 12 alkyl which is linear or branched, C 6 -C 12 aryl, C n H 2n+1 , Ph 2 P(O)—, Ph 2 P—, Me 2 P(O)—, Me 2 P, Ph 2 P(S), Me 2 P(S), Ph 3 P═N—, Me 3 P═N—, C 6 H 5 C p H 2p —, C p H 2p+1 C 6 H 4 —, C p H 2p+1 C 6 H 4 C n H 2n —, CH 2 ═CHC p H 2p —, CH 2 ═CHC 6 H 5 —, CH 2 ═CHC 6 H 4 C p H 2p+1 —, and CH 2 ═CHC p H 2p C 6 H 4 —.
where n is an integer having a value from 1 to 48 (preferably 1 to 12) and p is an integer having a value from 1 to 48 (preferably 1 to 12).
It was found that the redox couples of the present invention can have a high reversibility since they have a very small ΔE p . Moreover, it has been found that these redox couples have a good thermal stability, a good solubility in various solvents and an excellent ionic conductivity in a non-aqueous medium. It also has been found that these redox couples are substantially colorless at concentrations permitting a good conductivity. Such characteristics make them particularly interesting in various applications like solar cells or photovoltaic cells. It also has been found that some members of these couples are highly electropositive and some others are highly electronegative. It also has been found that these redox couples do not have tendency to corrode other components when used in devices such as solar cells or photovoltaic cells.
According to another aspect of the invention, there is provided a redox-switchable system according to any one of schemes 10 to 13:
wherein
R 1 , R 2 and R 3 are the same or different and are selected from the group consisting of a hydrogen atom, C 1 -C 12 alkyl which is linear or branched, C 3 -C 12 cycloalkyl, C 1 -C 12 heterocyclyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 6 -C 12 aryl, C 6 -C 20 aralkyl, C 6 -C 20 alkylaryl, C 1 -C 12 heteroaryl, and part of polymer chain or network, or
R 1 and R 2 are joined together to form a 5 to 14 membered heterocyclyl in which R 3 is absent, a hydrogen atom, or a bond between N and R 1 or between N and R 2 ; or to form a 5 to 14 membered heteroaryl in which R 3 is absent, a hydrogen atom, a bond between N and R 1 or between N and R 2 , or is a part of polymer chain or network;
R 4 , R 5 and R 6 are the same or different and are selected from the group consisting of a hydrogen atom, C 1 -C 12 alkyl which is linear or branched, C 3 -C 12 cycloalkyl, C 1 -C 12 heterocyclyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 6 -C 12 aryl, C 6 -C 20 aralkyl, C 6 -C 20 alkylaryl, C 1 -C 12 heteroaryl, (CH 3 ) 2 N—, (C 2 H 5 ) 2 N—, (C 3 H 7 ) 2 N—, (C 4 H 9 ) 2 N—, (i-Pr) 2 N—, C n H 2n+1 , Ph 2 P(O)—, Ph 2 P—, Me 2 P(O)—, Me 2 P, Ph 2 P(S), Me 2 P(S), Ph 3 P═N—, Me 3 P═N—, and part of polymer chain or network, or
R 4 and R 5 are joined together to form a 5 to 14 membered heterocyclyl in which R 6 is absent, a hydrogen atom, or a bond between P and R 4 or between P and R 5 ; or to form a 5 to 14 membered heteroaryl ring in which R 6 is absent, a hydrogen atom, a bond between P and R 4 or between P and R 5 , or is a part of polymer chain or network;
R 7 and R 8 are the same or different and are selected from the group consisting of H, CF 3 , C n F 2n+1 , —SO 2 H, —SO 2 CF 3 , —NSO 2 CF 3 , —SO 2 CH 3 , —NSO 2 CH 3 , C 1 -C 12 alkyl which is linear or branched, C 6 -C 12 aryl, C n H 2n+1 , CN, NO 2 , Ph 2 P(O)—, Ph 2 P—, Me 2 P(O)—, Me 2 P, Ph 2 P(S), Me 2 P(S), Ph 3 P═N—, Me 3 P═N—, C 6 H 5 C p H 2p —, C p H 2p+1 C 6 H 4 —, C p H 2p+1 C 6 H 4 C n H 2n —, CH 2 ═CHC p H 2p —, CH 2 ═CHC 6 H 5 —, CH 2 ═CHC 6 H 4 C p H 2p+1 —, CH 2 ═CHC p H 2p C 6 H 4 —,
and part of polymer chain or network,
R 9 and R 10 are the same or different and are selected from the group consisting of a hydrogen atom, C 1 -C 12 alkyl which is linear or branched, C 3 -C 12 cycloalkyl, C 1 -C 12 heterocyclyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 6 -C 12 aryl, C 6 -C 20 aralkyl, C 6 -C 20 alkylaryl, C 1 -C 12 heteroaryl, and part of polymer chain or network, or R 9 and R 10 are joined together to form a 5 to 7 membered heterocyclyl or heteroaryl; and
X is (FSO 2 ) 2 N − , (CF 3 SO 2 ) 2 N − , (C 2 F 5 SO 2 ) 2 N − , (CF 3 SO 2 ) 3 C − , CF 3 SO 3 − , CF 3 COO − , AsF 6 − , CH 3 COO − , (CN) 2 N − , NO 3 − , 2.3HF, Cl − , Br − , I − , PF 6 − , BF 4 − , ClO 4 − , saccharin(o-benzoic sulfimide), (C 8 H 16 SO 2 ) 2 N − , or C 3 H 3 N 2 − ;
Z is C, N or As;
the alkyl, cycloalkyl, heterocyclyl, alkenyl, alkynyl, aryl, aralkyl, alkylaryl, and heteroaryl being unsubstituted or substituted with 1 to 3 substituents selected from the group consisting of F, Cl, Br, I, OH, a C 1 -C 6 alkoxy, a C 1 -C 6 hydroxy alkyl, NO 2 , CN, CF 3 , SO 3 − , C n F 2n+1 , C 1 -C 12 alkyl which is linear or branched, C 6 -C 12 aryl, C n H 2n+1 , Ph 2 P(O)—, Ph 2 P—, Me 2 P(O)—, Me 2 P, Ph 2 P(S), Me 2 P(S), Ph 3 P═N—, Me 3 P═N—, C 6 H 5 C p H 2p —, C p H 2p+1 C 6 H 4 —, C p H 2p+1 C 6 H 4 C n H 2n —, CH 2 ═CHC p H 2p —, CH 2 ═CHC 6 H 5 —, CH 2 ═CHC 6 H 4 C p H 2p+1 —, and CH 2 ═CHC p H 2p C 6 H 4 —.
where n is an integer having a value from 1 to 48 (preferably 1 to 12) and p is an integer having a value from 1 to 48 (preferably 1 to 12).
The expression “electron activation” is used herein as a synonym of “electron transfer”.
The expression “part of polymer chain or network” as used herein when referring to a particular group, such as a R group, means that such a R group is part of a polymer matrix, chain or resin or that such a R group is linked to a polymer matrix, chain or resin.
The term “aryl” as used herein refers to a cyclic or polycyclic aromatic ring. Preferably, the aryl group is phenyl or napthyl.
The term “heteroaryl” as used herein refers to an aromatic cyclic or fused polycyclic ring system having at least one heteroatom selected from the group consisting of N, O, and S. Preferred heteroaryl groups are furyl, thienyl, pyridyl, quinolinyl, isoquinolinyl, indolyl, isoindolyl, triazolyl, pyrrolyl, tetrazolyl, imidazolyl, pyrazolyl, oxazolyl, thiazolyl, benzofuranyl, benzothiophenyl, carbazolyl, benzoxazolyl, pyrimidinyl, benzimidazolyl, quinoxalinyl, benzothiazolyl, naphthyridinyl, isoxazolyl, isothiazolyl, purinyl, quinazolinyl, and so on.
The term “heterocyclyl” includes non-aromatic rings or ring systems that contain at least one ring having at least one hetero atom (such as nitrogen, oxygen or sulfur). Preferably, this term includes all of the fully saturated and partially unsaturated derivatives of the above mentioned heteroaryl groups. Examples of heterocyclic groups include pyrrolidinyl, tetrahydrofuranyl, morpholinyl, thiomorpholinyl, piperidinyl, piperazinyl, thiazolidinyl, isothiazolidinyl, and imidazolidinyl.
The compositions of the present invention can be suitable as electron activable precursors for various redox couples. These compositions, upon electron activation, can be suitable for acting as redox couples. Alternatively, upon electron activation, these compositions can be at least partially converted into redox couples. Preferably, the electron activation is carried out by withdrawing at least one electron to a compound of composition. The compositions of the invention can be effective as precursors to a redox couples, the precursors being electron activable in order to be converted into the redox couples. The compositions of the present invention preferably comprise a compound of formula (I) and a compound of formula (II); a compound of formula (III) and a compound of formula (IV); a compound of formula (V) and a compound of formula (VI); or a compound of formula (VII) and a compound of formula (VIII).
In the compositions of the present invention, the first compound can be present in a molar ratio of about 0.1 to about 99.9% and the second compound can be present in a molar ratio of about 99.9 to about 0.1%. The first compound is preferably present in the composition in a molar ratio of about 10.0 to about 90.0% and the second compound is preferably present in a molar ratio of about 90.0 to about 10.0%.
The compositions, upon electron activation, can have a conductivity of at least 10 −7 S/cm (preferably at least 10 −6 S/cm, more preferably at least 10 −4 S/cm) at 250° C. at a 1 mM concentration for each of the first and second compounds. Alternatively, the conductivity can be of about 10 −7 S/cm to about 1 S/cm at 25° C. and at a 1 mM concentration for each of the first and second compounds.
The unactivated compositions (without any electron activation) can have a conductivity of at least 10 −12 S/cm (preferably at least 10 −7 S/cm, more preferably at least 10 −6 S/cm) at 25° C. at a concentration of about 1 mM to 100 mM for each of the first and second compounds. Alternatively, the conductivity can be of about 10 −12 S/cm to about 10 −6 S/cm at 25° C. and at a 1 mM concentration for each of the first and second compounds.
The compositions of the present invention can be in a solid form and/or in a liquid form at room temperature. The compositions can be used as precursors to redox couples or as anti-static agents. They can also be used for preparing corresponding redox couples or in the manufacture of redox couples, wherein the compositions are electron activated in order to obtain the redox couples. Alternatively, they can be used in the manufacture of articles having anti-static properties. Such articles can be papers, textiles, polymers, clothes, inks, waxes, cleaning compositions, softening compositions or agents, petroleum-based compositions, compositions comprising volatile or flammable ingredients, molded objects, shaped articles, various articles comprising a polymer, a part of an electronic device (such as a computer, TV, DVD, CD player, etc.)
The compositions of the present invention can also be used as non-aqueous proton donor-acceptors to support ionic conduction in proton conducting membranes. They can also be used as proton donor-acceptors to support ionic conduction in proton conducting membranes or as anti-static agents effective in a non-polar medium. The non-polar medium can be petroleum or a derivative thereof, a polymer (such as polyurethanes, polyvinyl chlorides, polystyrenes, polyesters, polyethylenes, polypropylenes, or polyethylenetherephtalates), a textile or an ink. The non-polar medium can also be a non-polar solvent such as hydrocarbons and particularly alkanes, preferably C 5 -C 15 alkanes.
In the compositions, kits, and redox-switchable systems of the present invention comprising a compound of formula (I), preferably no more than one of R 1 , R 2 and R 3 represents an hydrogen atom. When they comprise a compound of formula (II), preferably no more than one of R 1 , R 2 and R 3 represents an hydrogen atom. When they comprise a compound of formula (III), preferably no more than one of R 4 , R 5 and R 6 represents an hydrogen atom. When they comprise a compound of formula (IV), preferably no more than one of R 4 , R 5 and R 6 represents an hydrogen atom. When they comprise a compound of formula (V), preferably no more than one of R 4 , R 5 and R 6 represents an hydrogen atom. When they comprise a compound of formula (VI), preferably no more than one of R 4 , R 5 and R 6 represents an hydrogen atom. When they comprise a compound of formula (VII), preferably no more than one of R 9 and R 10 represents an hydrogen atom. When they comprise a compound of formula (VIII), preferably no more than one of R 9 and R 10 represents an hydrogen atom.
In the redox couples of scheme 1, preferably no more than one of R 1 , R 2 and R 3 (connected to a same nitrogen atom) represents an hydrogen atom. In the redox couples of scheme 2, preferably no more than one of R 4 , R 5 and R 6 (connected to a same phosphorus atom) represents an hydrogen atom. In the redox couples of scheme 3, preferably no more than one of R 4 , R 5 and R 6 (connected to a same phosphorus atom) represents an hydrogen atom. In the redox couples of scheme 4, preferably no more than one of R 9 and R 10 (connected to a same sulphur atom) represents an hydrogen atom.
The redox couples of the present invention can be used in a solar cell, a fuel cell, a battery, a sensor or a display. They can also be used as electronic conductors in a non-polar medium.
The redox-switchable systems of the invention can be used in a solar cell, a fuel cell, a battery, a sensor or a display. They can also be used as a proton donor-acceptor to support ionic conduction in proton conducting membranes or as anti-static agents. These anti-static agents are preferably used in a non-polar medium. Such a medium is preferably petroleum or a derivative thereof, a polymer (such as polyurethanes, polyvinyl chlorides, polystyrenes, polyesters, polyethylenes, polypropylenes, or polyethylenetherephtalates), a textile, or an ink. The non-polar medium can be a non-polar solvent such as hydrocarbons, preferably alkanes, and more preferably C 5 -C 15 alkanes.
The redox couples and the redox-switchable systems of the invention can have a ΔE p lower than 1000 mV at 100 mV/s, preferably lower than 500 mV at 100 mV/s, more preferably lower than 300 mV at 100 mV/s, even more preferably lower than 200 mV at 100 mV/s, and still even more preferably lower than 150 mV at 100 mV/s. Alternatively, the ΔE p can be of about 100 to about 500 mV at 100 mV/s or about 150 to about 250 mV at 100 mV/s.
The compounds, compositions, redox couples, and redox-switchable systems of the present invention can be soluble in a solvent selected from the group consisting of CH 3 CN, CH 2 Cl 2 , EtOH, isopropanol, DMSO, amides (such as DMF), hexane, heptane, linear carbonates (such as dimethylcarbonate, diethylcarbonate, ethylmethylcarbonate), cyclic esters (such as ethylene carbonate, propylene carbonate), urea (tetramethylurea), ionic liquids such as dialkylimidazolium, trialkylsulfonium, and quaternary amine (such as C 1 -C 20 tetraalkylammonium) and quaternary phosphonium (such as C 1 -C 20 tetraalkylphosphonium or C 6 -C 12 tetraarylphosphonium) salts associated with stable anion such as (FSO 2 ) 2 N − , (CF 3 SO 2 ) 2 N − , (C 2 F 5 SO 2 ) 2 N − , (CF 3 SO 2 ) 3 C − , CF 3 SO 3 − , CF 3 COO − , AsF 6 − , CH 3 COO − , (CN) 2 N − , NO 3 − , 2.3HF, Cl − , Br − , I − , PF 6 − , BF 4 − , ClO 4 − and mixtures of these solvents. Preferably, the compounds, compositions, redox couples, and redox-switchable systems of the present invention are soluble in a solvent selected from the group consisting of CH 3 CN, amides (such as DMF), linear carbonates (such as dimethylcarbonate, diethylcarbonate, ethylmethylcarbonate), cyclic esters (such as ethylene carbonate, propylene carbonate), ionic liquids such as dialkylimidazolium, trialkylsulfonium, and quaternary amine (such as C 1 -C 20 tetraalkylammonium) and quaternary phosphonium (such as C 1 -C 20 tetraalkylphosphonium or C 6 -C 12 tetraarylphosphonium) salts associated with stable anion such as (FSO 2 ) 2 N − , (CF 3 SO 2 ) 2 N − , (C 2 F 5 SO 2 ) 2 N − , (CF 3 SO 2 ) 3 C − , CF 3 SO 3 − , CF 3 COO − , AsF 6 − , CH 3 COO − , (CN) 2 N − , NO 3 − , 2.3HF, Cl − , Br − , I − , PF 6 − , BF 4 − , ClO 4 − and mixture of these solvents. The compounds, compositions, redox couples, and redox-switchable systems of the present invention can be in a solid form or powder form at room temperature, preferably at 25° C. They can also be liquid at room temperature, preferably at 25° C.
The redox couples and redox-switchable systems of the present invention can further comprise a supporting electrolyte (such as TBAP (tetrabutylammoniumperchlorate) K + TFSI − , K + FSI − , tetraalkylammonium with PF 6 − , BF 4 − or ClO 4 − , or imidazolium with PF 6 − , BF 4 − or ClO 4 ).
The compositions of the present invention, when dissolved into a solvent as previously defined, are preferably solutions and more preferably homogeneous solutions.
In the compounds, compositions, kits, redox couples, and redox-switchable systems of the present invention, X − is preferably (CF 3 SO 2 ) 2 N − , (FSO 2 ) 2 N − , (CF 3 SO 2 ) 3 C − , CF 3 SO 3 − , (CN) 2 N − , PF 6 − , BF 4 or ClO 4 − . More preferably, X − is (CF 3 SO 2 ) 2 N − . (CF 3 SO 2 ) 2 N − is also called TFSI or bis(trifluoromethanesulfinimide) ion.
The compositions and the redox-switchable systems are preferably in the form of uncolored and/or translucent solutions. They can have, in the visible region of the light spectrum, i.e. 400 nm to 700 nm, an absorbance of about 0.01 to about 0.50 (preferably of about 0.02 to about 0.10). In such a region of the spectrum, the composition of the present invention can have an absorption below 1.0, preferably below 0.75, more preferably below 0.50, even more preferably below 0.25, and still even more preferably below 0.1. An absorbance below 0.05 is particularly preferred and an absorbance below 0.03 is even more particularly preferred.
In accordance with a preferred embodiment of the invention, the compositions and the kits of the present invention can comprise a compound of formula (Ia) and a compound of formula (IIa):
wherein R 11 is a C 1 -C 12 alkyl which is linear or branched, C 3 -C 12 cycloalkyl, C 6 H 5 —, C n H 2n+1 , C 6 H 5 C p H 2p —, C p H 2p+1 C 6 H 4 —, C p H 2p+1 C 6 H 4 C n H 2n —, CH 2 ═CHC p H 2p —, CH 2 ═CHC 6 H 5 —, CH 2 ═CHCH 2 —, CH 2 ═CHCH 2 CH 2 —, CH 2 ═CHC 6 H 4 C p H 2p+1 —, CH 2 ═CHC p H 2p C 6 H 4 —,
and X − is as previously defined,
where n is an integer having a value from 1 to 48 (preferably 1 to 12), and p is an integer having a value from 1 to 48 (preferably 1 to 12). R 11 is preferably CH 3 .
In accordance with another preferred embodiment of the invention, the compositions and the kits of the present invention can comprise a compound of formula (Ib) and a compound of formula (IIb):
wherein R 11 and X − are as previously defined for (Ia) and (IIa).
In accordance with another preferred embodiment of the invention, the compositions and the kits of the present invention can comprise a compound of formula (Ic) and a compound of formula (IIc):
wherein X − is as previously defined.
In accordance with another preferred embodiment of the invention, the compositions and the kits of the present invention can comprise a compound of formula (IIIa) and a compound of formula (IVa):
wherein R 12 is phenyl, naphtyl, pyridyl, furyl, or thiophenyl, R 12 being unsubstituted or substituted with 1 to 3 substituents selected from the group consisting of F, Cl, Br, I, OH, a C 1 -C 6 alkoxy, a C 1 -C 6 hydroxy alkyl, NO 2 , CN, (CH 3 ) 2 N—, (C 2 H 5 ) 2 N—, (C 3 H 7 ) 2 N—, (C 4 H 9 ) 2 N—, (i-Pr) 2 N—, C 1 -C 12 alkyl which is linear or branched, C n H 2n+1 , Ph 2 P(O)—, Ph 2 P—, Me 2 P(O)—, Me 2 P, Ph 2 P(S), Me 2 P(S), Ph 3 P═N—, and Me 3 P═N—; and X − is as previously defined,
where n is an integer having a value from 1 to 48 (preferably 1 to 12).
In accordance with another preferred embodiment of the invention, the compositions and the kits of the present invention can comprise a compound of formula (IIIb) and a compound of formula (IVb):
wherein X − is as previously defined.
In accordance with another preferred embodiment of the invention, the compositions and the kits of the present invention can comprise a compound of formula (Va) and a compound of formula (VIa):
wherein
R 12 is phenyl, naphtyl, pyridyl, furyl, or thiophenyl, R 12 being unsubstituted or substituted with 1 to 3 substituents selected from the group consisting of F, Cl, Br, I, OH, a C 1 -C 6 alkoxy, a C 1 -C 6 hydroxy alkyl, NO 2 , CN, C 1 -C 12 alkyl which is linear or branched, C 1 -C 6 hydroxy alkyl, C 1 -C 6 alkoxy, OC 6 H 5 , and OCH 2 —C 6 H 5 ;
R 13 and R 14 are the same or different and are selected from the group consisting of a hydrogen atom, H, CN, NO 2 , (CH 3 ) 2 N—, (C 2 H 5 ) 2 N—, (C 3 H 7 ) 2 N—, (C 4 H 9 ) 2 N—, (i-Pr) 2 N—, C 1 -C 12 alkyl which is linear or branched, C n H 2n+1 , Ph 2 P(O)—, Ph 2 P—, Me 2 P(O)—, Me 2 P, Ph 2 P(S), Me 2 P(S), Ph 3 P═N—, Me 3 P═N—, —SO 2 H, —SO 2 CF 3 , —NSO 2 CF 3 , —SO 2 CH 3 , and —NSO 2 CH 3 ; and X − is as previously defined;
where n is an integer having a value from 1 to 48 (preferably 1 to 12).
In accordance with another preferred embodiment of the invention, the compositions and the kits of the present invention can comprise a compound of formula (Vb) and a compound of formula (VIb):
wherein X − is as previously defined.
In accordance with another preferred embodiment of the invention, the compositions and the kits of the present invention can comprise a compound of formula (VIIa) and a compound of formula (VIIIa):
wherein R 12 is phenyl, naphtyl, pyridyl, furyl, or thiophenyl, R 12 being unsubstituted or substituted with 1 to 3 substituents selected from the group consisting of F, Cl, Br, I, OH, C 1 -C 12 alkyl which is linear or branched, a C 1 -C 6 alkoxy, a C 1 -C 6 hydroxy alkyl, NO 2 , CN, OC 6 H 5 , OCH 2 —C 6 H 5 , CF 3 , and C 2 F 5 ; and X − is as previously defined.
In accordance with another preferred embodiment of the invention, the compositions and the kits of the present invention can comprise a compound of formula (VIIb) and a compound of formula (VIIIb):
wherein X − is as previously defined.
The person skilled in the art would clearly recognize that in the compositions or kits of the present invention, in the formulas as previously defined, the basic member (or base) is at the left side and the protonated member (or conjugated acid) is at the right side.
In accordance with another preferred embodiment of the invention, the redox couples can be as defined in scheme (5):
wherein R 11 is a C 1 -C 12 alkyl which is linear or branched, C 3 -C 12 cycloalkyl, C 6 H 5 —, C n H 2n+1 , C 6 H 5 C p H 2p —, C p H 2p+1 C 6 H 4 —, C p H 2p+1 C 6 H 4 C n H 2n —, CH 2 ═CHC p H 2p —, CH 2 ═CHC 6 H 5 —, CH 2 ═CHCH 2 —, CH 2 ═CHCH 2 CH 2 —, CH 2 ═CHC 6 H 4 C p H 2p+1 —, CH 2 ═CHC p H 2p C 6 H 4 —,
and X is as previously defined,
where n is an integer having a value from 1 to 48 (preferably 1 to 12), and p is an integer having a value from 1 to 48 (preferably 1 to 12). R 11 is preferably CH 3 .
In accordance with another preferred embodiment of the invention, the redox couple can be as defined in scheme (6):
wherein R 11 and X − are as previously defined in scheme (5). R 11 is preferably CH 3 .
In accordance with another preferred embodiment of the invention, the redox couples can be as defined in scheme (7):
wherein R 12 is phenyl, naphtyl, pyridyl, furyl, or thiophenyl, R 12 being unsubstituted or substituted with F, Cl, Br, I, OH, a C 1 -C 6 alkoxy, a C 1 -C 6 hydroxy alkyl, NO 2 , CN, (CH 3 ) 2 N—, (C 2 H 5 ) 2 N—, (C 3 H 7 ) 2 N—, (C 4 H 9 ) 2 N—, (i-Pr) 2 N—, C 1 -C 12 alkyl which is linear or branched, C n H 2n+1 , Ph 2 P(O)—, Ph 2 P—, Me 2 P(O)—, Me 2 P, Ph 2 P(S), Me 2 P(S), Ph 3 P═N—, or Me 3 P═N—; X − is as previously defined,
where n is an integer having a value from 1 to 48 (preferably from 1 to 12). R 12 is preferably phenyl.
In accordance with another preferred embodiment of the invention, the redox couples can be as defined in scheme (8):
wherein
R 12 is phenyl, naphtyl, pyridyl, furyl, or thiophenyl, R 12 being unsubstituted or substituted with 1 to 3 substituents selected from the group consisting of F, Cl, Br, I, OH, a C 1 -C 6 alkoxy, a C 1 -C 6 hydroxy alkyl, NO 2 , CN, C 1 -C 12 alkyl which is linear or branched, C 1 -C 6 hydroxy alkyl, C 1 -C 6 alkoxy, OC 6 H 5 , and OCH 2 —C 6 H 5 ;
R 13 and R 14 are the same or different and are selected from the group consisting of a hydrogen atom, H, CN, NO 2 , (CH 3 ) 2 N—, (C 2 H 5 ) 2 N—, (C 3 H 7 ) 2 N—, (C 4 H 9 ) 2 N—, (i-Pr) 2 N—, C 1 -C 12 alkyl which is linear or branched, C n H 2n+1 , Ph 2 P(O)—, Ph 2 P—, Me 2 P(O)—, Me 2 P, Ph 2 P(S), Me 2 P(S), Ph 3 P═N—, Me 3 P═N—, —SO 2 H, —SO 2 CF 3 , —NSO 2 CF 3 , —SO 2 CH 3 , and —NSO 2 CH 3 ; and X − is as previously defined;
where n is an integer having a value from 1 to 48 (preferably 1 to 12). Preferably, R 12 is phenyl, R 13 is CN, and R 14 is H.
In accordance with another preferred embodiment of the invention, the redox couples can be as defined in scheme (9):
wherein R 12 is phenyl, naphtyl, pyridyl, furyl, or thiophenyl, R 12 being unsubstituted or substituted with 1 to 3 substituents selected from the group consisting of F, Cl, Br, I, OH, C 1 -C 12 alkyl which is linear or branched, a C 1 -C 6 alkoxy, a C 1 -C 6 hydroxy alkyl, NO 2 , CN, OC 6 H 5 , OCH 2 —C 6 H 5 , CF 3 , or C 2 F 5 , and X − is as previously defined. R 12 is preferably phenyl.
The person skilled in the art would clearly recognize that in the redox couples of the present invention, as defined in any one of the previously presented schemes, the reduced member is at the left side of the arrow and the oxidized member is at the right side of the arrow. The person skilled in the art will also understand that each of the schemes represents a family of redox couples covering several possibilities.
In accordance with another preferred embodiment of the invention, the redox-switchable systems can be as defined in scheme (14):
wherein R 11 is a C 1 -C 12 alkyl which is linear or branched, C 3 -C 12 cycloalkyl, C 6 H 5 —, C n H 2n+1 , C 6 H 5 C p H 2p —, C p H 2p+1 C 6 H 4 —, C p H 2p+1 C 6 H 4 C n H 2n —, CH 2 ═CHC p H 2p —, CH 2 ═CHC 6 H 5 —, CH 2 ═CHCH 2 —, CH 2 ═CHCH 2 CH 2 —, CH 2 ═CHC 6 H 4 C p H 2p+1 —, CH 2 ═CHC p H 2p C 6 H 4 —,
and X − is as previously defined,
where n is an integer having a value from 1 to 48 (preferably from 1 to 12), and p is an integer having a value from 1 to 48 (preferably from 1 to 12). R 11 is preferably CH 3 .
In accordance with another preferred embodiment of the invention, the redox-switchable systems can be as defined in scheme (15):
wherein R 11 and X − are as previously defined in scheme (14). R 11 is preferably CH 3 .
In accordance with another preferred embodiment of the invention, the redox-switchable systems can be as defined in scheme (16):
wherein R 12 is phenyl, naphtyl, pyridyl, furyl, or thiophenyl, R 12 being unsubstituted or substituted with 1 to 3 substituents selected from the group consisting of F, Cl, Br, I, OH, a C 1 -C 6 alkoxy, a C 1 -C 6 hydroxy alkyl, NO 2 , CN, (CH 3 ) 2 N—, (C 2 H 5 ) 2 N—, (C 3 H 7 ) 2 N—, (C 4 H 9 ) 2 N—, (i-Pr) 2 N—, C 1 -C 12 alkyl which is linear or branched, C n H 2n+1 , Ph 2 P(O)—, Ph 2 P—, Me 2 P(O)—, Me 2 P, Ph 2 P(S), Me 2 P(S), Ph 3 P═N—, and Me 3 P═N—; X is as previously defined,
where n is an integer having a value from 1 to 48 (preferably 1 to 12). R 12 is preferably phenyl.
In accordance with another preferred embodiment of the invention, the redox-switchable systems can be as defined in scheme (17):
wherein
R 12 is phenyl, naphtyl, pyridyl, furyl, or thiophenyl, R 12 being unsubstituted or substituted with 1 to 3 substituents selected from the group consisting of F, Cl, Br, I, OH, a C 1 -C 6 alkoxy, a C 1 -C 6 hydroxy alkyl, NO 2 , CN, C 1 -C 12 alkyl which is linear or branched, C 1 -C 6 hydroxy alkyl, C 1 -C 6 alkoxy, OC 6 H 5 , and OCH 2 —C 6 H 5 ;
R 13 and R 14 are the same or different and are selected from the group consisting of a hydrogen atom, H, CN, NO 2 , (CH 3 ) 2 N—, (C 2 H 5 ) 2 N—, (C 3 H 7 ) 2 N—, (C 4 H 9 ) 2 N—, (i-Pr) 2 N—, C 1 -C 12 alkyl which is linear or branched, C n H 2n+1 , Ph 2 P(O)—, Ph 2 P—, Me 2 P(O)—, Me 2 P, Ph 2 P(S), Me 2 P(S), Ph 3 P═N—, Me 3 P═N—, —SO 2 H, —SO 2 CF 3 , —NSO 2 CF 3 , —SO 2 CH 3 , and —NSO 2 CH 3 ; and X − is as previously defined;
where n is an integer having a value from 1 to 48 (preferably 1 to 12). Preferably, R 12 is phenyl, R 13 is CN, and R 14 is H.
In accordance with another preferred embodiment of the invention, the redox-switchable systems can be as defined in scheme (18):
wherein R 12 is phenyl, naphtyl, pyridyl, furyl, or thiophenyl, R 12 being unsubstituted or substituted with F, Cl, Br, I, OH, C 1 -C 12 alkyl which is linear or branched, a C 1 -C 6 alkoxy, a C 1 -C 6 hydroxy alkyl, NO 2 , CN, OC 6 H 5 , OCH 2 —C 6 H 5 , CF 3 , or C 2 F 5 , and X − is as previously defined. R 12 is preferably phenyl.
The person skilled in the art would clearly recognize that the redox-switchable systems of the present invention can include the compositions and the redox couples of the invention. The person skilled in the art would also clearly recognize that in the redox-switchable systems of the present invention, as defined in any one of the previously presented schemes, the compounds represented in brackets “[ ]” nare redox couples as previously defined in the present invention, and that the compounds which are not in brackets represent the compounds as found in the compositions according to the present invention.
The compositions and the redox-switchable systems can further comprise a polymer (such as polyurethanes, polyvinyl chlorides, polystyrenes, polyesters, polyethylenes, polypropylenes, or polyethylenetherephtalates), a solvent (such as those previously defined in the present invention), a molten salt, an ionic liquid, a gel or a combination thereof.
According to another aspect of the invention, there is provided a photovoltaic cell comprising an anode, a cathode, and a redox couple as defined in the present invention.
According to another aspect of the invention, there is provided a photovoltaic cell comprising an anode, a cathode, and a redox-switchable system as defined in the present invention.
According to another aspect of the invention, there is provided a photovoltaic cell comprising an anode, a cathode, a redox couple as defined in the present invention, and a solvent (such as those previously defined), a polymer (such as polyethyleneoxides, polyphosphazenes, etc.), a molten salt, an ionic liquid, a gel or any combination thereof.
According to another aspect of the invention there is provided an anti-static agent comprising any one of the compositions defined in the present invention. The anti-static agent is preferably comprised within a matrix. The matrix can be a polymer (such as polyurethanes, polyvinyl chlorides, polystyrenes, polyesters, polyethylenes, polypropylenes, or polyethylenetherephtalates), a solvent (such as those previously defined in the present invention), a paper, a textile, clothes, an ink, a wax, a cleaning composition, a softening agent or composition, a petroleum-based composition, a composition comprising volatile or flammable ingredients, molded objects, shaped articles, articles comprising a polymer, electronic devices (such as a computer, TV, DVD, CD player, etc.).
According to another aspect of the invention there is provided an anti-static agent comprising a first compound selected from the group consisting of compounds of formulas (I), (III), (V), and (VII), and a second compound selected from the group consisting of compounds of formulas (II), (IV), (VI), and (VIII) wherein the compounds are as previously defined. The anti-static agent is preferably comprised within a matrix. The matrix can be a polymer (such as polyurethanes, polyvinyl chlorides, polystyrenes, polyesters, polyethylenes, polypropylenes, or polyethylenetherephtalates), a solvent (such as those previously defined in the present invention), a textile, clothes, an ink, a wax, a cleaning composition, a softening composition or agent, a petroleum-based composition, a composition comprising volatile or flammable ingredients, molded objects, shaped articles, articles comprising a polymer, electronic devices (such as a computer, TV, DVD, CD player, etc.).
The person skilled in the art will understand that, when possible, all the preferred embodiments mentioned concerning the compositions of the invention also apply to the anti-static agents of the present invention.
BRIEF DESCRIPTION OF FIGURES
Further features and advantages of the invention will become more readily apparent from the following description of preferred embodiments as illustrated by way of examples in the appended figures wherein:
FIG. 1 shows UV-visible absorption spectra comparing a 1,3-ethylmethylimidazolium bis(trifluoromethanesulfinimide) (EMI-TFSI) solution comprising 600 mM of EMI-I and 20 mM of I 2 , and a EMI-TFSI solution comprising 100 mM of 1-methylimidazole (MI) and 100 mM of 1-methylimidazolium-TFSI (MI + H TFSI − ) according to a preferred embodiment of the invention;
FIG. 2 shows a cyclic voltammogram at a platinum electrode of an acetonitrile solution comprising 60 mM of triphenylphosphine (Ph 3 P), 20 mM of triphenylphosphonium-TFSI (Ph 3 P + H TFSI − ) and 20 mM of tetrabutylammoniumperchlorate (TBAP) according to a preferred embodiment of the invention;
FIG. 3 shows another cyclic voltammogram at a platinum electrode of a EMI-TFSI solution comprising 28 mM of MI and 28 mM of MI + H TFSI − according to a preferred embodiment of the invention;
FIG. 4 shows still another cyclic voltammogram at a glassy carbon electrode of an acetonitrile solution comprising 40 mM of triphenyl(phosphranylidene)acetonitrile (Ph 3 P═CHCN), 40 mM of triphenylphosphoniumacetonitrile-TFSI (Ph 3 P + —CH 2 CN TFSI − ) and 40 mM of TBAP according to a preferred embodiment of the invention; and
FIG. 5 shows still another cyclic voltammogram at a glassy carbon electrode of an acetonitrile solution comprising 50 mM of diphenylsulfide (Ph 2 S), 50 mM of diphenylsulfonium-TFSI (Ph 2 S + H TFSI − ) and 50 mM of TBAP according to a preferred embodiment of the invention.
DESCRIPTION OF PREFERRED EMBODIMENTS
The following non-limiting examples further illustrate the invention.
Ph 3 P/Ph 3 P + H(TFSI − ), MI/MI + H(TFSI − ), Ph 3 P═CHCN/Ph 3 P + —CH 2 CN(TFSI − ) and Ph 2 S/Ph 2 S + H(TFSI − ) compositions (or electron activable precursors to redox couples) have been prepared according to the following general method. These compositions are indicated using the following nomenclature: basic member/protonated member.
General Procedure
The same general procedure was applied to prepare all the above mentioned compositions. 0.1 mole of the basic member (Ph 3 P, MI, Ph 3 P═CHCN or Ph 2 S) was charged into a two-neck flask with magnetic stirrer. Hydrochloric acid (0.1 N) was slowly added into the flask until the total solubility of the product. Then, 30 mL of a solution of one equivalent of KTFSI in distilled water was added to the reaction mixture. A white precipitate was appearing. The corresponding target salt for each of the previously mentioned basic members, i.e. the corresponding protonated members were isolated by filtration and dried under vacuum.
The protonated members, Ph 3 P + H(TFSI − ), MI + H(TFSI − ), Ph 3 P + —CH 2 CN(TFSI − ) and Ph 2 S + H(TFSI − ), have been confirmed using 13 C, 1 H and 31 P-NMR.
Then, for a given composition, the basic member and the protonated member have been mixed together and dissolved into a solvent so as to obtain the aforementioned compositions. In certain tests (cyclic voltammograms), these compositions are electron-activated so as to be converted into the corresponding redox couples and redox-switchable systems. Alternatively, the compositions of the present invention can be prepared by adding, to the basic member, a quantity of an acid (HTFSI), which is less than 1 equimolar of the basic member, so as to directly obtain the desired composition.
FIG. 1 represents UV-visible absorption spectra of a EMI-TFSI solution comprising 600 mM EMI-I and 20 mM of 12 (typical of the redox electrolyte used in dye-sensitized solar cells) and of a EMI-TFSI solution comprising 100 mM of MI and 100 mM of MI + H TFSI − (as prepared following the general procedure).
The absorption spectra are analyzed in Table 1, which give the absorbance of the two solutions from 300 nm (near-UV) to 700 nm as obtained using a UV-Visible spectrophotometer; the scanning speed was 150 nm/s.
TABLE 1
Absorbance
Wavelength (nm)
I − /I 2
MI/MI + H
300
2.817
0.810
350
2.361
0.243
400
2.895
0.102
450
2.921
0.045
500
2.829
0.033
550
1.667
0.026
600
0.640
0.022
650
0.127
0.020
700
0.023
0.017
As it can be seen from FIG. 1 and Table 1, the I − /I 2 composition strongly absorbs in the visible region of the light spectrum, particularly between 400 and 600 nm, whereas the MI/MI + H composition does not show any significant absorption in this wavelength range. Thus, this clearly demonstrates that the MI/MI + H composition would permit to considerably avoid the decrease in the energy conversion efficiency.
FIG. 2 represents a cyclic voltammogram at a platinum electrode having a surface area of 0.020 cm 2 with a Ag wire and a platinum electrode (0.5 cm 2 ) as the reference and counter electrode, respectively. The electrodes were immersed in an acetonitrile solution comprising 60 mM of Ph 3 P, 20 mM of Ph 3 P + H TFSI − (as prepared following the general procedure) and 20 mM of TBAP according to a preferred embodiment of the invention. The scanning speed was 100 mV/s. As it can be seen from FIG. 2 , the redox couple generated from the Ph 3 P/Ph 3 P + H composition was tested in order to determine its electrochemical properties at a platinum electrode. The analysis shows that the redox couple obtained from the composition Ph 3 P/Ph 3 P + H possesses a very good electrochemical behavior at this electrode. In particular, the difference between the anodic (E pa ) and cathodic (E pc ) peak potentials, symbolized as ΔE p , is 0.48 V. The redox potential is about +0.13 V.
FIG. 3 represents a cyclic voltammogram at a platinum electrode having a surface area of 0.020 cm 2 with a Ag wire and a platinum electrode (0.5 cm 2 ) as the reference and counter electrode, respectively. The electrodes were immersed in a EMI-TFSI solution comprising 28 mM of MI and 28 mM of MI + H TFSI − according to a preferred embodiment of the invention. The scanning speed was 100 mV/s.
As it can be seen from FIG. 3 , the redox couple obtained from the MI/MI + H composition was tested in order to determine its electrochemical properties at a platinum electrode. The analysis shows that such a redox couple possesses an outstanding electrochemical behavior at this electrode; in particular, the ΔE p value is only 0.12 V. The redox potential is about +0.30 V.
FIG. 4 represents a cyclic voltammogram at a glassy carbon electrode having a surface area of 0.071 cm 2 with a Ag wire and a platinum electrode (0.5 cm 2 ) as the reference and counter electrode, respectively. The electrodes were immersed in an acetonitrile solution comprising 40 mM of Ph 3 P═CHCN, 40 mM of Ph 3 P + —CH 2 CN TFSI − (as prepared following the general procedure) and 40 mM of TBAP according to a preferred embodiment of the invention. The scanning speed was 100 mV/s.
As it can be seen from FIG. 4 , the redox couple obtained from the Ph 3 P═CHCN/Ph 3 P + —CH 2 CN composition was tested in order to determine its electrochemical properties at a platinum electrode. The analysis shows that such a redox couple possesses an excellent electrochemical behavior at this electrode; in particular, the AEp value is only 0.19 V. The redox potential is about +0.68 V.
FIG. 5 represents a cyclic voltammogram at a glassy carbon electrode having a surface area of 0.071 cm 2 with a Ag wire and a platinum electrode (0.5 cm 2 ) as the reference and counter electrode, respectively. The electrodes were immersed in an acetonitrile solution comprising 50 mM of Ph 2 S, 50 mM of Ph 2 S + H TFSI − (as prepared following the general procedure) and 50 mM of TBAP according to a preferred embodiment of the invention. The scanning speed was 100 mV/s.
As it can be seen from FIG. 5 , the redox couple obtained from the Ph 2 S/Ph 2 S + H composition was tested in order to determine its electrochemical properties at a platinum electrode. The analysis shows that the redox couple possesses an outstanding electrochemical behavior at this electrode; in particular, the ΔE p value is only 0.15 V. Moreover, the redox potential is highly electronegative with an unusual value of −0.86 V.
Table 2 gives the ionic conductivity values, at 25° C., of hexane solutions comprising trioctylphosphine (basic member) and trioctylphosphonium-TFSI (protonated member as prepared following the general procedure) at various concentrations. In these case both members of the solution have the same concentration. The measurements were carried out using a conductivity cell and electrochemical impedance spectroscopy.
TABLE 2
Concentration (mM)
500
250
125
61.3
30.0
15.0
7.50
3.75
Ionic
92.4
66.4
20.3
6.64
2.26
0.20
0.19
0.01
conductivity
(μS/cm)
As it can be seen from Table 2, the trioctylphosphine/trioctylphosphonium composition was tested in order to determine its ionic conductivity values as a function of concentration in a non-polar solvent (hexane) to evaluate its anti-static properties. The analyses show that this composition of the two aforesaid compounds acts as an excellent anti-static agent with very high ionic conductivity values even at concentrations below 4 mM. It is noteworthy that compounds with conductivity values greater than 10 −3 μS/cm in such non-polar solvents are considered as very interesting anti-static agents. Moreover, for the utilization as anti-static agents more than one composition can be mixed together. Alternatively, the protonated member of a particular composition can be used in combination with the basic member of another composition so as to obtain different compositions (or crossed compositions), e.g. MI/Ph 3 P + H(TFSI − ), Ph 3 P/MI + H(TFSI − ), Ph 3 P═CHCN/Ph 3 P + H(TFSI − ), Ph 3 P/Ph 2 S + H(TFSI − ), MI/Ph 2 S + H(TFSI − ), etc.
While the invention has been described in connection with specific embodiments thereof, it will be understood that it is capable of further modifications and this application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains and as may be applied to the essential features hereinbefore set forth, and as follows in the scope of the appended claims. | There are provided compositions comprising a first compound selected from the group consisting of compounds of formulas (Ib), (III), (V), and (VII), and a second compound selected from the group consisting of compounds of formulas (IIb), (IV), (VI), and (VIII):
Various chemical entities can be used for R 4 to R 11 . These compositions can be particularly useful as anti-static agents or as electron activable precursors to a redox couple. | 8 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a method of and an apparatus for recycling perfluorocompounds. More particularly, the present invention relates to a method of and an apparatus for recycling perfluorocompounds using adsorption separation technology.
[0003] 2. Description of the Related Art
[0004] Perfluorocompounds (PFCs) are widely used throughout the semiconductor device manufacturing industry. In particular, perfluorocompounds (PFCs) are used in chemical vapor deposition (CVD), etching, and chamber cleaning processes. For example, CF 4 or C 2 F 6 gas is widely used in the etching of semiconductor substrates. Most of these PFC gases are nonvolatile and thus are very stable. Also, the PFC gases have a long retention time in the atmosphere and absorb ultraviolet rays radiating from the Earth. Thus, the PFC gases have a very high global warming potential (GWP). Despite this, the use of PFCs is increasing in the semiconductor device manufacturing industry.
[0005] Several techniques, though, have been developed to reduce PFC emissions. One method for preventing PFC gas from being emitted into the atmosphere is to burn the PFC component of gas being discharged from semiconductor device manufacturing equipment. This method decomposes PFC gas effectively and thus, prevents environmental pollution. However, hydrogen fluoride is generated as a byproduct of the combustion process. Therefore, this method has problems in terms of its duration and stability. Also, the combustion process requires fuel and oxygen. Thus, additional operational costs are incurred when the combustion method is incorporated into the overall manufacturing process. Another method of suppressing the discharge of PFC gas is a distillation method. However, it is difficult to separate PFC gas from the discharge gas using distillation because of the physical properties of PFC gas. In addition, distillation requires specialized equipment which, again, adds to the cost of the manufacturing process.
SUMMARY OF THE INVENTION
[0006] Objects of the present invention are to provide a recycling method and apparatus in which high-purity PFC gas can be obtained from a gas mixture having a low-concentration of the PFC gas.
[0007] Another object of the present invention is to provide a low cost and efficient way to handle exhaust gas containing a PFC gas without emitting the PFC gas into the atmosphere.
[0008] Still another object of the present invention is to provide a semiconductor device manufacturing facility that curbs the emission of PFCs without the use of expensive auxiliary equipment.
[0009] Still another object of the present invention is to provide a semiconductor device manufacturing facility that efficiently recycles PFCs used in the facility.
[0010] According to one aspect of the present invention, PFC is recycled from an exhaust gas using adsorption and desorption cycles.
[0011] According to another aspect of the present invention, an apparatus is provided in which the adsorption and desorption cycles can be executed simultaneously.
[0012] The present invention provides a method of recycling a PFC in which initially a gas mixture including a PFC gas is selectively supplied to the first of first and second adsorption units each including an adsorbent. At this time, the PFC gas is adsorbed in the first adsorption unit. The PFC is desorbed in the first adsorption unit once the adsorbent is saturated. The gas mixture is also selectively supplied to and adsorbed in the second adsorption unit. The PFC gas is then desorbed in the second adsorption unit once the adsorbent of the second adsorption unit is saturated. Finally, the desorbed PFC gas is recollected.
[0013] The steps may be repeated after the PFC gas is desorbed in the second adsorption unit. Also, the gas mixture may be selectively supplied to and adsorbed in the second adsorption unit while PFC gas is being desorbed in the first adsorption unit. Similarly, the gas mixture may be selectively supplied to and adsorbed in the first adsorption unit while PFC gas is being desorbed in the second adsorption unit. In addition, the first adsorption unit may be kept at room temperature and atmospheric pressure while the PFC gas is being adsorbed therein. Alternatively, a relatively low temperature and high pressure may be maintained in the first adsorption unit to facilitate the adsorption of the PFC gas. On the other hand, a relatively high temperature and low pressure are maintained in the first adsorption unit to facilitate the desorbing of the PFC gas. Likewise, the second adsorption unit may be kept at room temperature and atmospheric pressure while the PFC gas is being adsorbed therein. Alternatively, a relatively low temperature and high pressure may be maintained in the second adsorption unit to facilitate the adsorption of the PFC gas. On the other hand, a relatively high temperature and low pressure are maintained in the second adsorption unit to facilitate the desorbing of the PFC gas.
[0014] Also, the first adsorption unit may be pressurized before the gas mixture containing the PFC gas is introduced into the first adsorption unit. Similarly, the second adsorption unit may be pressurized before the gas mixture containing the PFC gas is introduced into the second adsorption unit. To this end, the non-adsorbed gas in one adsorption unit may be supplied from that unit to the other unit in which the adsorption of PFC gas is about to take place.
[0015] The present invention also provides a method of recycling perfluorocompound (PFC) in which a gas mixture containing PFC gas is supplied to a first adsorption unit and the PFC gas is adsorbed in the first adsorption unit, and the PFC gas is then desorbed in the first adsorption unit while the second adsorption unit is pressurized and the gas mixture is supplied to the second adsorption unit. Thus, PFC gas is adsorbed in the second unit while PFC gas is being desorbed in the first adsorption unit. Next, the PFC gas is desorbed in the second adsorption unit while the first adsorption unit is pressurized and the gas mixture is selectively supplied to the first adsorption unit. Thus, PFC gas is adsorbed in the first adsorption unit while PFC gas is being desorbed in the second adsorption unit.
[0016] The first adsorption unit may be initially pressurized with nitrogen. Then, the second adsorption unit is pressurized by supplying it with the non-adsorbed gas from the first adsorption unit. Similarly, in subsequent cycles in which PFC gas is to be adsorbed in the first adsorption unit, the first adsorption unit is pressurized by supplying it with non-adsorbed gas from the second adsorption unit.
[0017] The present invention also provide an adsorption apparatus for recycling a perfluorocompound (PFC), which includes first and second adsorption units, a first pipe to which inlets of the first and second adsorption units are commonly connected, valves disposed in-line between the first pipe and the inlets of the first and second adsorption units, respectively, second and third pipes respectively connected to outlets of the first and second adsorption units, valves disposed in-line with the second and third pipes, respectively, a fourth pipe interconnecting the first and second adsorption units, and a valve disposed in-line with the fourth pipe. The valves are movable to positions at which gas that is not adsorbed by an adsorbent of the first adsorption unit flows through the fourth pipe into the second adsorption unit, and to positions at which gas that is not adsorbed by an adsorbent of the second adsorption unit flows through the fourth pipe into the first adsorption unit the adsorption apparatus may also includes a storage tank connected to the second and third pipes for storing the PFC desorbed in the first and second adsorption units.
[0018] The adsorbent may be silica gel, activated alumina, zeolite or activated carbon. Preferably, the adsorbent is activated carbon because activated carbon has a relatively great ability to adsorb PFCs.
[0019] The present invention also provides a semiconductor manufacturing facility in which the adsorption apparatus is connected to the exhaust line of a reaction chamber of a processing apparatus in which substrates are processed using PFC gas.
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] These and other objects, features and advantages of the invention will be better understood from the following detailed description of the preferred embodiments thereof made with reference to the accompanying drawings. In the drawings:
[0021] FIG. 1 is a schematic diagram of an embodiment of a semiconductor device manufacturing facility including an adsorption apparatus according to the present invention;
[0022] FIG. 2 is a flowchart of a method of recycling PFCs according to the present invention; and
[0023] FIG. 3 is a schematic diagram of another embodiment of a semiconductor device manufacturing facility including an adsorption apparatus according to the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0024] Referring to FIG. 1 , an adsorption apparatus 100 for recycling PFC gas according to the present invention includes at least two adsorption devices 110 and 120 , such as adsorption towers or adsorption beds. For the sake of simplicity, the present invention will be described hereinafter with respect to the adsorption devices 110 and 120 being adsorption towers.
[0025] A reaction chamber 192 of a semiconductor device processing apparatus 190 , such as an etch apparatus, is connected to inlets of the two adsorption towers 110 and 120 through main gas feed pipe 102 and branch pipes 103 and 104 . More specifically, an exhaust line 194 extends between and connects the reaction chamber 192 and the main gas feed pipe 102 . Gas including PFC is introduced into the reaction chamber 192 through a gas supply line 191 . A semiconductor substrate W is processed in the reaction chamber 192 and gas is discharged from the reaction chamber through the exhaust line 194 . The gas thus flows into the main gas feed pipe 102 . The branch pipes 103 and 104 are commonly connected to the main gas feed pipe 102 , and are respectively connected to the adsorption towers 110 and 120 . Valves 101 , 112 and 122 are disposed in the pipes 102 , 103 and 104 , respectively. Each of the valves can be moved between open and closed positions to selectively allow and block the flow of gas through the pipe in which the valve is disposed. Thus, a mixture of gas discharged from the semiconductor device processing apparatus 190 is supplied to the first adsorption tower 110 or the second adsorption tower 120 through the pipe 103 or 104 , respectively, depending on whether valves 112 and 122 are open or closed. The exhaust gas contains PFC gas. For example, the exhaust gas includes excess CF 4 or C 2 F 6 , used as an etching gas in a process of etching a semiconductor substrate W.
[0026] The adsorption towers 110 and 120 are filled with an adsorbent, such as silica gel, activated alumina, zeolite, or activated carbon that will adsorb PFC gas with a relatively high selectivity with respect to other gases that may make up the exhaust gas. Preferably, the adsorbent is activated carbon because among the above-mentioned adsorbents, activated carbon has the greatest ability to adsorb PFC gas. Therefore, PFC gas can adsorbed in the adsorption towers 110 and 120 until the adsorbent is saturated with the gas. Also, PFC will be adsorbed or desorbed by the adsorbent (e.g., activated carbon) depending on the pressure and temperature in the adsorption tower. Therefore, the apparatus also includes a first temperature regulating device 111 for controlling the temperature of the first adsorption tower 110 , and a second temperature regulating device 121 for controlling the temperature of the second adsorption tower 120 .
[0027] The other component(s) of the exhaust gas, that is gas other than the PFC, is not adsorbed in the adsorption towers 110 and 120 but it is emitted into the atmosphere. Such gas will be referred to as non-adsorbed gas. Also, the adsorption towers 110 and 120 are connected to one another by a pipe 108 . A valve 113 is disposed in the pipe. The valve may be opened and closed to selectively place the adsorption towers 110 and 120 in communication with each other. Thus, the non-adsorbed gas can be discharged from one adsorption tower to the other through pipe 108 .
[0028] Pipes 105 and 106 are connected to outlets of the adsorption towers 110 and 120 , respectively. The pipes 105 and 106 are commonly connected to a main collection pipe 107 . Valves 114 , 124 and 132 are disposed in the pipes 105 , 106 and 107 , respectively. Each of the valves can be moved between open and closed positions to selectively allow and block the flow of PFC gas through the pipe in which the valve is disposed. Thus, PFC gas desorbed in the first adsorption tower 110 flows through the pipes 105 and 107 when the valves 114 and 132 are opened. Likewise, PFC desorbed in the second adsorption tower 120 flows through the pipes 106 and 107 when the valves 124 and 132 . The main recollection pipe 107 is connected to a gas storage tank 130 . Therefore, the PFC gas desorbed in the first and second adsorption towers 110 and 120 may be recollected and stored in the storage tank 130 .
[0029] The concentration of PFC gas is relatively low in the exhaust gas discharged during a typical semiconductor device manufacturing process, such as an etch process. Accordingly, the adsorption towers 110 and 120 can be pressurized to cause the adsorbent to more efficiently adsorb the PFC gas. To this end, a source of nitrogen (N 2 ) is connected to the adsorption towers 110 and 120 . The source of nitrogen (N 2 ) may be connected to the towers 110 and 120 through the main gas feed pipe 102 . Alternatively, the adsorption towers 110 and 120 can be pressurized using non-adsorbed gas that is fed through the pipe 108 .
[0030] A method of recycling PFC gas using the apparatus of FIG. 1 will now be described in more detail with reference to FIG. 2 . At the start of the process, a PFC gas is introduced into a reaction chamber of a substrate processing apparatus. For example, CF 4 and/or C 2 F 6 is introduced into a reaction chamber 192 of an etch apparatus 190 as an etching gas. An excess amount of the PFC gas does not react with the substrate W in the reaction chamber 192 . Gas is discharged from the reaction chamber 192 during and after the etching process. This exhaust gas thus contains the excess PFC gas. The exhaust gas containing PFC gas, e.g., CF 4 and/or C 2 F 6 , is discharged from the reaction chamber 192 of the etch apparatus 190 to the pipe 102 via exhaust line 194 . The exhaust gas is first supplied to the first adsorption tower 110 by opening the valve 112 and closing the valve 122 .
[0031] The PFC component of the exhaust gas has a relatively low concentration. Therefore, the first adsorption tower 110 may be pre-pressurized so that the adsorbent will adsorb the low concentration of PFC gas more effectively. Specifically, the first adsorption tower 110 may be pre-pressurized by introducing nitrogen gas into the first adsorption tower 110 through pipes 102 and 103 .
[0032] The PFC component of the exhaust gas introduced into the first adsorption tower 110 will be adsorbed or desorbed by the adsorbent (preferably activated carbon) depending on the pressure and temperature in the adsorption tower. Specifically, in this type of separation process, the concentration of PFC gas in the adsorbent increases (adsorption) as the gas pressure increases and temperature decreases, and the concentration of PFC gas in the adsorbent decreases (desorption) when the gas pressure decreases and temperature increases.
[0033] A condition is established in the first adsorption unit so that the gas comprising a PFC will be adsorbed by the adsorbent of the first adsorption unit. For example, the first adsorption unit may be maintained at room temperature and atmospheric pressure. However, alternatively, a relatively high pressure and low temperature condition is established in the first adsorption tower 110 . The exhaust gas is injected into the first adsorption tower 110 through branch pipe 103 . Therefore, the PFC component of the exhaust gas is selectively adsorbed by the adsorbent (e.g., activated carbon) in the first adsorption tower 110 (S 100 ). On the other hand, the non-adsorbed gas passes through the adsorption tower 110 to the second adsorption tower 120 through the pipe 108 to pre-pressurize the second adsorption tower 120 .
[0034] The exhaust gas is fed into the first adsorption tower 110 until the adsorbent is saturated with the PFC gas (S 110 ). Then, the PFC gas is desorbed (S 120 ) by establishing a condition in the first adsorption tower 110 , that is, a low pressure (e.g., close to a vacuum level) and high temperature condition (e.g., 100° C.), under which the absorbent will give up PFC gas. At this time, the valves 114 and 132 are opened. As a result, the desorbed PFC gas flows through the pipe 105 so as to be recollected. The recollected PFC gas may be stored in the storage tank 130 .
[0035] In addition, the valve 122 is opened while desorption is taking place in the first adsorption tower 110 . Accordingly, the exhaust gas is supplied to the second adsorption tower 120 through the pipe 104 . As a result, the PFC component of the exhaust gas is adsorbed in the second adsorption tower 120 (S 200 ). To this end, the condition that was established in the first adsorption tower 110 to facilitate the adsorption of PFC gas by the adsorbent, e.g., a high pressure and low temperature condition, is established in the second adsorption tower 120 . Also, if the second adsorption tower is pre-pressurized by the non-adsorbed gas flowing from the first adsorption tower 110 , the PFC gas is adsorbed more effectively.
[0036] The exhaust gas is fed into the second adsorption tower 120 until the adsorbent in the second adsorption tower 120 is saturated (S 210 ). At this time, the conditions under which PFC is desorbed from the adsorbent are established in the second adsorption tower 120 (S 220 ). That is, again, a low pressure and high temperature condition is established in the second adsorption tower 120 . Then, the PFC gas flows through the pipe 106 and is recollected, e.g., is stored in the storage tank 130 along with PFC gas desorbed in the first adsorption tower 110 . The valve 112 is opened while the desorption is taking place in the second adsorption tower 120 so that the exhaust gas is introduced into the first adsorption tower 110 , whereby another cycle in which PFC gas is adsorbed in the first adsorption tower 110 takes place.
[0037] Also, during the time in which the PFC gas is being adsorbed in the second adsorption tower 120 (S 200 ), the non-adsorbed gas in the second adsorption tower 120 is introduced into the first adsorption tower 110 through the pipe 108 . In this way, the first adsorption tower 110 is pre-pressurized. That is, the first adsorption tower 110 is initially pressurized by supplying nitrogen gas into the first adsorption tower 10 ; then, for each cycle after that in which adsorption is to take place in the first adsorption tower 110 , the first adsorption tower 110 is pre-pressurized with non-adsorbed gas from the second adsorption tower 120 .
[0038] As is clear from the description above, PFC gas is efficiently recollected because the adsorption/desorption processes are continuously and simultaneously taking place. Specifically, after the initial adsorption process, adsorption is always taking place in one of the first and second adsorption towers 110 and 120 while desorption is taking place in the other of the first and second adsorption towers 110 and 120 . The recollected gas may contain a slight amount of gas other than pure PFC gas. In this case, the recollected gas is again supplied to the first adsorption tower and the second adsorption tower, and the adsorption and desorption processes are repeated on the recollected gas. Consequently, PFC gas of a higher purity can be obtained. To this end, an adsorption apparatus as shown in FIG. 3 may be used.
[0039] Referring to FIG. 3 , the adsorption apparatus 200 includes two adsorption towers 210 and 220 , a main exhaust gas feed pipe 202 connected to the reaction chamber 292 of a processing apparatus 290 of semiconductor device manufacturing equipment so as to receive exhaust gas discharged from the reaction chamber, and branch pipes 203 , 204 . A temperature regulating device 211 controls the temperature of the first adsorption tower 210 . Likewise, a second temperature regulating device 221 controls the temperature of the second adsorption tower 220 .
[0040] A semiconductor device processing apparatus 290 is connected to the adsorption apparatus. More specifically, an exhaust line 294 extends between and connects a reaction chamber 292 of the processing apparatus 290 and the main gas feed pipe 202 . Gas including PFC is introduced into the reaction chamber 292 through a gas supply line 291 . A semiconductor substrate W is processed in the reaction chamber 292 and gas is discharged from the reaction chamber through the exhaust line 294 . Thus, the discharged gas will flow to the main exhaust gas feed pipe 202 . The branch pipes 203 , 204 are commonly connected to the main exhaust gas feed pipe 202 and are connected to the adsorption towers 210 and 220 , respectively.
[0041] In addition, valves 212 , 222 are disposed in-line in the branch pipes 203 , 204 , respectively. The valves 212 and 222 are movable between open and closed positions to selectively allow and block the flow of gas to the adsorption towers 210 and 220 . That is, gas selectively flows through pipes 203 and 204 according to the positions of the valves 212 and 222 .
[0042] Pipes 205 and 206 are connected to outlets of the adsorption towers 210 and 220 , respectively. Thus, PFC adsorbed and then desorbed in the adsorption towers 210 and 220 flows through pipes 205 and 206 so as to be recollected. The pipes 205 and 206 are connected in common to a main recollection pipe 207 . The main recollection pipe 207 is, in turn, connected to a gas storage tank 208 . Thus, the gas may be stored in the storage tank 208 as it is recollected.
[0043] Furthermore, a return pipe 209 interconnects the pipes 205 and 206 . A valve 234 is disposed in the return pipe 209 to selectively allow and block the flow of gas through the pipe 209 . Also, valves 236 and 238 are disposed in the pipes 236 and 205 , 206 , respectively, between the locations at which the return pipe 209 interconnects the pipes 205 and 206 and the locations at which the pipes 205 and 206 are connected to the main recollection pipe 207 . Thus, the valve 234 may be opened and the valves 236 and 238 may be closed so that the recollected gas flowing from one of the adsorption towers 210 and 220 may be returned to the other of the adsorption towers 210 and 220 through the return pipe 209 , whereupon the adsorption and desorption processes are repeated on the recollected gas. In addition, valves 214 and 224 are disposed in series in-line in a return pipe 240 . The valves 214 and 224 may be opened so that recollected gas flowing from one of the adsorption towers 210 and 222 may be returned to the other of the adsorption towers 210 and 22 through the return pipe 240 .
[0044] Otherwise, the operation of the adsorption apparatus 200 is essentially the same as that described with reference to FIG. 2 . For instance, the adsorption towers 210 and 220 are connected to one another by a pipe 208 . A valve 213 is disposed in the pipe. The valve may be opened and closed to selectively place the adsorption towers 110 and 120 in communication with each other. Thus, the non-adsorbed gas can be introduced from one of the adsorption towers 210 and 220 to the other of the adsorption towers 210 and 220 through the pipe 208 to pressurize the other of the adsorption towers 210 and 220 .
[0045] According to the present invention, as described above, PFC gas can be separated from the exhaust gas of semiconductor device manufacturing equipment merely by controlling the pressure and temperature of an adsorption unit. Thus, the present invention provides an economical approach to handling exhaust gas of the type that typically has a low concentration of PFC gas, such as that of produced by semiconductor device manufacturing equipment. Also, the adsorption/desorption process itself is an effective way to separate out the PFC gas from the exhaust gas which typically contains a low concentration of the PFC gas. Moreover, PFC gas which is known to contribute to global warming is prevented from being emitted into the atmosphere. Also, the present invention recollects high purity PFC gas from the exhaust gas. Thus, its reuse is possible. Any non-adsorbed gas can be discharged with the use of a mass flow controller (MFC).
[0046] Finally, although the present invention has been described above in connection with the preferred embodiments thereof, the present invention is not so limited. Rather, various modifications of the disclosed embodiments will be apparent to those skilled in the art that. Thus, modifications of the disclosed embodiments are seen to be within the true spirit and scope of the invention as defined by the appended claims. | PFC is recycled from a gas mixture using adsorption technology and techniques. Two adsorption units each include an adsorbent having a selectivity by which the PFC is selectively adsorbed with respect to the other gas(es) that make up the mixture. The gas mixture is selectively supplied to one of the first and second adsorption units and a condition is created in the first adsorption unit so that the PFC is adsorbed in the first adsorption unit. Once the adsorbent is saturated in the first adsorption unit, a condition is created in the first adsorption unit that causes the PFC to be desorbed. At this time, the gas mixture is selectively supplied to the second adsorption unit, and a condition is created in the second adsorption unit so that the PFC is adsorbed. Once the adsorbent is saturated in the second adsorption unit, a condition is created in the second adsorption unit that causes the PFC to be desorbed. High-purity PFC gas can be obtained from the exhaust gas even if the gas mixture is exhaust gas of a semiconductor device manufacturing process having a low concentration of PFC. | 1 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] The present application is a continuation-in-part of U.S. Ser. No. 12/263,310, filed Nov. 6, 2008.
BACKGROUND OF THE INVENTION
[0002] The present invention relates generally to agricultural implements and, more particularly, to a seed boot for use with a disc opener that collectively provides a double-shoot, single pass deposition of fertilizer and seed onto a planting surface.
[0003] Fertilizer and seed are generally deposited onto a planting surface in either a single shoot or double shoot manner. With a single shoot planting technique, a mixture of seed and fertilizer is deposited into a single furrow and subsequently packed. With a double shoot planting technique, seed and fertilizer are deposited into separate furrows, which may or may not be closely spaced, and then packed.
[0004] A single shoot planting device typically has a single delivery hose through which the mixture of granular fertilizer and seed is delivered to the furrow. More particularly, a single shoot planting device will typically include a cutting tip that is dragged at a depth just below the planting surface. The delivery hose extends along a backside of the cutting tip, or knife, so that the fertilizer and seed mixture is deposited into the furrow immediately after the cutting tip cuts into the planting surface. Ideally, the mixture is deposited in to the furrow before the furrow collapses. The furrow is typically packed by a trailing packing or press wheel.
[0005] Another configuration of a single shoot planting device replaces the knife with a disc or coulter that rotates at an angle relative to a line of travel to form a furrow or trench in the planting surface. Because of the angling of the disc, the leading face of the disc pushes soil to one side and creates the furrow while the opposite, trailing face of the disc runs in the “shadow” of the leading face. The seed/fertilizer mixture is dropped to the bottom of the furrow while the furrow is held open by the disc and a cooperating plate (or scraper or seed boot) on the other side. The penetration depth of the disc controls the seed depth. A trailing packer wheel closes the furrow after the mixture is deposited and firms the planting surface (soil).
[0006] While single shoot planting units are less complex, it is generally preferred to use a double shoot planting unit which allows seed and fertilizer to be separately deposited into the furrow. When the fertilizer and seed are mixed, reduced concentrations of fertilizer must be used to prevent the seed from becoming damaged, i.e., “burnt”. In one exemplary double shoot planting unit, a knife has a side tip (side bander) that trails the leading knife as the planting unit is towed along the planting surface. The knife creates a furrow or fertilizer trench and the side bander forms a ledge in the sidewall of the furrow to effectively form a seed trench or seed bed. The fertilizer and seed trenches are separated from one another both horizontally and vertically. This separation provides a fertilizer/seed stratification that has been found to provide better growing conditions, i.e., higher concentrations of fertilizer may be used without seed “burning”.
[0007] In yet another type of double shoot planting unit a pair of rotating discs are used to form separate fertilizer and seed trenches having horizontal and vertical stratification. The leading disc cuts through the planting surface at an angle to cut a furrow or fertilizer trench. A trailing disc cuts through the side of the furrow formed by the leading disc to cut a seed trench that is generally horizontally and vertical offset from the fertilizer trench. U.S. Pat. No. 5,752,454 describes a dual disc, double shoot planting unit.
[0008] Dual disc units, such as that described in U.S. Pat. No. 5,752,454, are relatively complex structures with multiple rotating parts such as the discs themselves and associated bearings. This complexity also adds to the overall cost of the planting unit and the implement. Dual disc units, such as those described in the aforementioned patent, have also been found to perform unsatisfactorily in soft soil conditions. More particularly, the discs are generally angled to essentially “dig” into the soil surface to cut a furrow. Since the discs dig into the surface, less down pressure is needed. In harder soil conditions, the disc will effectively dig into the soil as the soil itself provides bias against which the disc can leverage. However, in soft soil conditions, the disc will essentially “plow” through the soil rather than cut an open furrow. Furthermore, to accommodate the space needed for two rotational elements, the distance between the leading and trailing discs is relatively substantial and can led to disturbance of the furrow before the seed is planted. That is, depending upon soil conditions, the furrow may collapse upon itself before the trailing disc cuts a seed bed into the furrow formed by the leading disc. The spacing between the discs also reduces seeding accuracy in rolling terrain, as well as adding to the overall size, weight, and cost of the carrying frame.
SUMMARY OF THE INVENTION
[0009] The present invention is directed to a planting unit for depositing fertilizer and seed in a single pass, double shoot manner in which a rotating disc cuts a furrow in a planting surface and a trailing seed boot, having a cutting edge, cuts a vertically and offset trench in the furrow to form a seed bed in the planting surface. The disc has a mounting frame for mounting the disc to a linkage assembly that is, in turn, coupled to a toolbar mount. The seed boot is also attached to the mounting frame. This common attachment provides a relatively short and compact device without sacrificing fertilizer and seed stratification.
[0010] In operation, the rotating disc, which sits at an angle relative to a line of travel, is pulled through the planting surface along the planting surface to cut a furrow into the planting surface. The furrow effectively defines a fertilizer trench into which fertilizer may be deposited from a fertilizer source through a fertilizer tube. The seed boot has a cutting edge that when pulled through the planting surface cuts a seeding trench in the furrow that is offset both vertically and horizontally from the fertilizer trench. Rearward of the cutting edge is a seed tube through which seed is passed and deposited into the seed trench. In one embodiment, a tab extends from a rearward edge of the seed tube that is designed to reduce the fall of seed into the fertilizer trench. In addition, the tab is also operative to reduce the ingress of soil or residue into the seed tube.
[0011] It is therefore an object of the invention to provide a planting unit that furrows a planting surface into separate fertilizer and seed trenches with minimal soil disturbance.
[0012] It is another object of the invention to provide fertilizer and seed stratification with a rotating disc and a seed boot having a cutting edge, wherein the seed boot and the rotating disc are coupled to a shared mount.
[0013] Therefore, in accordance with one aspect of the invention, a planting unit for use with a planting implement having a frame and configured to travel along a line of travel is disclosed. The planting unit has a disc mount configured to be coupled to the frame and a rotatable disc coupled to the disc mount and angled relative to the line of travel of the planting implement. The disc is configured to cut a furrow into a planting surface. A fertilizer tube is mounted to the disc mount and configured to deposit fertilizer into a fertilizer trench formed in the furrow. The planting unit further includes a seed boot coupled to the disc mount rearward of the fertilizer tube and the disc. The seed boot includes a hollow tubular member through which seed may be passed and deposited onto the planting surface, and a cutting edge configured to cut a ledge into the furrow onto which seed may be deposited.
[0014] In accordance with another aspect of the invention, a double-shoot, single pass implement for separately depositing fertilizer and seed with horizontal and vertical stratification onto a planting surface includes a toolbar configured to be coupled to a towing vehicle which is designed to pull the frame along the planting surface with a generally longitudinal line of travel. A plurality of disc openers are provided with each opener connected to the toolbar by a respective linkage assembly. Each disc opener includes a disc mount coupled to a corresponding linkage assembly and a rotatable disc mounted to the disc mount and configured to cut at an angle into the planting surface to form a fertilizer trench. A fertilizer tube is provided and is mounted to the disc mount generally adjacent the rotatable disc. Each opener also has a seed boot mounted to the disc mount and configured to cut a seed trench offset from the fertilizer trench. The seed boot includes a seed tube having a forward cutting edge and an outlet rearward of the fertilizer tube, and a tab connected to the seed tube generally opposite the forward cutting edge and extending rearward of the seed tube outlet.
[0015] According to yet another aspect of the invention, a furrowing and planting apparatus for use with an agricultural implement has a rotating disc configured to furrow a planting surface to define a fertilizer trench and a fertilizer source adapted to deposit fertilizer onto the fertilizer trench. The apparatus also has a seed boot disposed rearward of the rotating disc that includes a tubular member having a forward cutting edge that cuts a seed trench in the furrow. A deflector is mounted to a rearward edge of the seed boot and is operative to reduce the ingress of soil into the tubular member of the seed boot, particularly during roll back of the agricultural implement.
[0016] Other objects, features, aspects, and advantages of the invention will become apparent to those skilled in the art from the following detailed description and accompanying drawings. It should be understood, however, that the detailed description and specific examples, while indicating preferred embodiments of the present invention, are given by way of illustration and not of limitation. Many changes and modifications may be made within the scope of the present invention without departing from the spirit thereof, and the invention includes all such modifications.
BRIEF DESCRIPTION OF THE FIGURES
[0017] Preferred exemplary embodiments of the invention are illustrated in the accompanying drawings in which like reference numerals represent like parts throughout.
[0018] In the drawings:
[0019] FIG. 1 is a side elevation view of a planting unit according to one embodiment of the invention that includes a tool bar mount for coupling the planting unit to a toolbar of an agricultural implement;
[0020] FIG. 2 is a schematic view of the disc of the plating unit shown in FIG. 1 shown relative to a furrow formed along a line of travel;
[0021] FIG. 3 is a bottom view of the planting unit shown in FIG. 1 ;
[0022] FIG. 4 is a rear elevation view of the planting unit shown in FIG. 1 ;
[0023] FIG. 5 is a rear elevation view of the planting unit shown in FIG. 1 with a seed boot and packing system removed;
[0024] FIG. 6 is a partial exploded view of the planting unit shown in FIG. 1 ;
[0025] FIG. 7 is an isometric view of the seed boot of the planting unit shown in FIG. 1 ;
[0026] FIG. 8 is an end view of the seed boot shown in FIG. 7 ;
[0027] FIG. 9 is an exploded view of the depth adjustment assembly of the planting unit shown in FIG. 1 ;
[0028] FIG. 10 is an isometric view of a planting unit having a clamped on secondary seed boot according to another embodiment of the invention;
[0029] FIG. 11 is a side elevation view of a planting unit having a secondary seed boot clamped to a trailing arm according to a further embodiment of the invention; and
[0030] FIG. 12 is a side elevation view of a planting unit having a secondary seed boot fastened to a trailing arm according to yet another embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0031] The present invention is generally directed to a planting unit for us with an agricultural implement. While only one planting unit will be described, it is understood that the agricultural implement may include a plurality of such planting units
[0032] FIG. 1 shows a planting unit 10 according to one embodiment of the invention. The planting unit 10 generally includes a forward disc 12 that is angled relative to a line of travel. As known in the art, the forward disc 12 rotates about a center hub 14 to cut a furrow into the planting surface, S. A seed boot 16 is mounted rearward of the disc 12 , and as will be described, is designed to cut a seed trench into the furrow formed by the disc 12 . The disc 12 is coupled to a parallel linkage 18 by a disc mount 20 which has a mount arm 22 extending upwardly from the disc mount 20 . A trailing arm 24 is also coupled to the parallel linkage 18 and a press or packing wheel 26 is coupled to the trailing arm 24 . The press wheel 26 trails the disc 12 and the seed boot 16 , and as known in the art, applies a packing pressure to the furrow. The downward force is applied by spring 28 , but it is understood that other biasing devices may be used. In addition, the amount of downward force can be varied via lever 30 which has a selector member 32 that can be selectively positioned in one of a series of notches 34 of curved member 36 .
[0033] The parallel linkage 18 is also coupled to a toolbar mount 38 that is operative to couple the planting unit to a toolbar 40 of an agricultural implement. A hydraulic cylinder 42 is pivotably coupled to the toolbar mount 38 and the mount arm 22 by a bracket 44 , but it is understood other devices such as a spring or air bag could be used. The cylinder 42 is operative to apply a downward pressure on the disc 12 to force the disc 12 into contact with the planting surface. With additional reference to FIG. 9 , the depth at which the disc 12 cuts into the planting surface is variably set by a gauge wheel 46 and a cooperating gauge wheel arm 48 and a control lever 50 . The control lever 50 controls the gauge wheel arm 48 by a crankshaft 52 that extends through the center of the disc 12 . The gauge wheel arm 48 is held in place by teeth 54 that interface with a mating fan shaped member 56 , which includes a series of notches 58 that individually define a different depth the disc 12 can be set via positioning of the control lever 50 . Various fasteners 57 , e.g., nuts, bearing 59 , washers 61 and seal 63 are used to secure the crankshaft 52 to the disc 12 via a hub 65 that is coupled to the disc 12 by fasteners 67 .
[0034] In addition to setting the depth at which the disc 12 cuts into the planting surface, the depth gauge wheel 46 keeps the outer surface of the disc 12 generally clear of mud and debris. A scraper blade 60 is mounted opposite the depth gauge wheel 46 is designed to remove dirt, mud, and other debris from the inner surface of the disc 12 .
[0035] The planting unit 10 is designed to separately drop fertilizer and seed into the furrow in a single pass. In this regard, a fertilizer tube 62 is mounted rearward of the center hub of the disc 12 but forward of the seed boot 16 . The seed boot 16 generally includes a seed tube 64 and a cutting member 66 that is forward of the seed tube 64 . In operation, as the disc 12 forms a furrow having a relatively deep fertilizer trench in the planting surface, fertilizer is dropped into the fertilizer trench from a fertilizer source (not shown) that communicates with the aforementioned fertilizer tube 62 . The cutting member 66 is offset from the disc 12 and cuts into a sidewall of the furrow to form a ledge or seed bed. Seed is then dropped via the seed tube 64 onto the ledge. The seed is fed to the seed tube 64 from a seed source in a known manner.
[0036] The cutting member 66 cuts into the sidewall of the furrow such that the ledge is offset horizontally and vertically from the fertilizer trench, i.e., bottom of the furrow. In this regard, the seed is deposited at a position that is spaced horizontally and vertically from the fertilizer that is dropped into the fertilizer trench. As noted above, it is generally preferred to plant seed and drop fertilizer into a furrow with stratification between the fertilizer and the seed.
[0037] In one preferred embodiment, the cutting member 66 is angled to lift the soil as the cutting member 66 is urged through the sidewall of the furrow. Thus, as the disc 12 and the cutting member 66 cut through the planting surface, the soil is temporarily displaced and lifted to form trenches for the deposition of fertilizer and seed. However, when disc 12 and the cutting member 66 pass, the soil will tend to fall back onto itself and effectively fill-in the furrow and thus the fertilizer and seed trenches. The press wheel 26 , which trails the seed boot 16 , then packs the fertilizer and the seed. Alternately, the cutting member 66 may be angled downward to force the soil down onto the fertilizer before the seed is deposited onto the seed bed.
[0038] In one preferred embodiment, a defector tab 68 extends from the backside of the seed tube 64 . The deflector tab 68 generally provides two separate functions. First, the deflector tab 68 is angled, as shown in FIGS. 6 and 7 , as is the lower ends of the seed tube 64 and the cutting member 66 . With this angled orientation, the deflector tab 68 is operative to encourage seed toward the seed trench. Second, because of its proximity to the seed tube 64 , the deflector tab 68 reduces the ingress of soil and debris into the seed tube 64 during roll back of the planting unit 10 .
[0039] Referring now to FIG. 2 , the disc 12 is angled relative to the furrow F that is formed by the disc 12 as it is rotated. The furrow F is formed generally in-line with the line of travel for the agricultural implement. The disc 12 is angled such that the angle formed between the leading edge 12 a of the disc 12 and the line of travel, which generally bisects the furrow F, is approximately 7 degrees. While other angles are contemplated, it is generally preferred that the angle fall between 5 and 10 degrees, and more preferably between 6 and 8 degrees. It will be appreciated that while the disc is angled relative to the line of travel, the disc is normal to the plane of the planting surface.
[0040] Turning now to FIGS. 3-5 , the fertilizer tube 62 is arranged such that the fertilizer falls generally centered in the furrow. The seed tube 64 has an outlet 70 that is angled generally rearward and laterally offset from the outlet (not numbered) of the fertilizer tube. As noted above, the seed trench is formed laterally offset from the fertilizer trench. This offset is formed because the seed boot 16 is generally angled away from disc 12 , as particularly shown in FIG. 4 , such that the cutting member 66 forms a side bander. The angle defined between the leading edge 66 a of the cutting member 66 and an axis transverse to the line of travel is preferably between approximately 5 to approximately 45 degrees. The depth of the seed tube outlet 70 is less than the lower most edge of the disc 12 and the seed tube outlet 70 is laterally offset from the disc 12 clearly illustrating the vertical and horizontal spacing of the fertilizer and seed trenches.
[0041] As shown in FIGS. 6 and 7 , the seed boot 16 includes a header 72 that may be coupled to the disc mount 20 via fasteners 74 . Since the header 72 is mounted to the same mount 20 as the disc 12 , the combined assembly is relatively compact when compared to conventional double shoot, single pass planting units.
[0042] As shown in FIG. 8 , the seed boot 16 is constructed such that seed tube outlet 70 sits behind the cutting member 66 . With this construction, the cutting member 66 cuts a ledge into the sidewall of the furrow and seed is placed onto the ledge as the seed drops through the seed tube outlet 70 . The cutting member 66 generally includes an angled cutting face 76 that in one embodiment includes a wear resistant insert 78 , such as a carbide insert. In one preferred embodiment, the seed tube 64 and the cutting member 66 , and its header 72 are formed as a single assembly.
[0043] As described above, in one embodiment, the seed boot 16 has a generally flat header 72 with mounting holes (not numbered) formed therein that align with mounting holes in the disc mount 20 and fasteners 74 , such as bolts, may be used to couple the seed boot 16 to the disc mount 20 . It is understood however that the seed boot 16 could be mounted to the disc mount 20 in other ways. For example, as shown in FIG. 10 , a clamp 80 could be used. Similarly, as shown in FIG. 11 , clamp 80 could be used to mount the seed boot 16 to the trailing arm 24 of the press wheel 26 . In yet another embodiment and referring to FIG. 12 , holes (not shown) could be formed in the trailing arm 24 to allow the header 72 of the seed boot 16 to be fastened to the trailing arm 24 using fasteners 74 in a manner similar to the mounting to the disc mount 20 shown in FIG. 6 . Whether by a clamp or by fasteners, mounting the seed boot 16 to the trailing arm 24 would allow the seed depth (the depth at which seed or other particulate matter is deposited from the seed boot 16 ) to be set by the press wheel 26 . It will be appreciated that clamps other than the types shown in the figures could be used to clamp the seed boot 16 to either the disc mount 20 or the trailing arm 24 .
[0044] The present invention provides a planting unit of relatively compact design in which a seed boot and a rotatable disc are mounted to the same disc mount. The seed boot has an angled cutting tip that cuts a ledge into the sidewall of a furrow formed by the rotatable disc. A seed tube rearward of the cutting tip deposits seed onto the ledge. A trailing press wheel then packs the fertilizer and seed. The ledge is cut vertically and horizontally spaced from the bottom of the furrow (fertilizer trench). In this regard, seed and fertilizer are deposited with vertical and horizontal stratification allowing higher concentrations of fertilizer to be used. In addition to providing a compact design, the present invention avoids the complexities associated with double shoot planting units that have multiple discs to cut fertilizer and seed trenches. In addition, the present invention provides less soil disturbance compared to conventional knife style double shoot, single pass planting units, especially when furrowing at faster speeds, e.g., greater than 5 m.p.h.
[0045] Many changes and modifications could be made to the invention without departing from the spirit thereof. The scope of these changes will become apparent from the appended claims. | A planting unit for depositing fertilizer and seed in a single pass, double shoot manner includes a rotating disc that cuts a furrow in a planting surface and a trailing seed boot, having a cutting edge, that cuts a vertically and horizontally offset trench in the furrow to form a seed bed in the planting surface. The disc has a mounting frame for mounting the disc to a linkage assembly that is, in turn, coupled to a toolbar mount. The seed boot is also attached to the mounting frame. This common attachment provides a relatively short and compact device without sacrificing fertilizer and seed stratification. | 0 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional of U.S. application Ser. No. 11/150,549, filed Jun. 10, 2005, the specification of which is herein incorporated by reference.
TECHNICAL FIELD
[0002] This patent document pertains generally to medical device lead assemblies, and more particularly, but not by way of limitation, to porous polyethylene covers for a medical device lead assembly.
BACKGROUND
[0003] Medical devices such as pacers and defibrillators typically include at least one lead assembly. In a defibrillator, for example, a lead assembly typically includes at least one defibrillation electrode, such as a defibrillation coil. Some lead assemblies include a cover that extends over at least a portion of the outer surface of the lead assembly. A cover may extend over a defibrillation coil, for example. Covers are used, for example, to prevent tissue ingrowth.
[0004] United States Published Patent Application No. 2003/0023294A1 describes an expanded polytetrafluoroethylene (ePTFE) cover. Expanded polytetrafluoroethylene has a high melting point (over 300 degrees C.) and a high melt viscosity. The application of an ePTFE cover to a defibrillation electrode can involve sintering at high temperatures. Improved coverings for lead assemblies are needed.
SUMMARY
[0005] An example lead assembly includes a lead body, a conductor extending through the lead body, an electrode coupled to the conductor, and a cover formed from porous polyethylene extending over the electrode. In an example, the cover includes a first section having tissue ingrowth allowing pores and a second section having tissue ingrowth inhibiting pores. In an example, the cover is formed from at least one piece of polyethylene wrapped around at least a portion of the electrode, the first section of the cover wrapped with a first tension, and the second section wrapped with a second tension that is different from the first tension. In an example, the piece of porous polyethylene is laser-sintered to itself. In an example, the cover extends over substantially all of the lead body.
[0006] In another example, a lead assembly includes a lead body, a conductor extending through the lead body, an electrode coupled to the conductor, and a piece of mechanically stretched ultra high molecular weight polyethylene wrapped around at least a portion of the electrode. In an example, the piece of ultra high molecular weight polyethylene has a consistent pore size. In an example, the piece of mechanically stretched ultra high molecular weight polyethylene is hydrophilic.
[0007] An example method includes wrapping a first piece of porous polyethylene material around a first portion of a lead assembly, and fusing a first portion of the first piece of porous polyethylene material to a second portion of the first piece of porous polyethylene material. In an example, the wrapping includes wrapping the piece of porous polyethylene material under tension and controlling the size of the pores in the polyethylene. In an example, controlling the size of the pores in the polyethylene includes adjusting the tension. In an example, the method further includes wrapping a second piece of porous polyethylene material around a second portion of the lead assembly, the second portion having pores that are larger than pores in the first piece of porous polyethylene material. In an example, the method further includes joining the second piece of porous polyethylene to the first piece of porous polyethylene. In an example, fusing the piece of porous polyethylene includes heating the piece of porous polyethylene to between 80 and 150 degrees. In an example, the method further includes hydrophilicly treating at least a portion of the first piece of porous polyethylene.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] In the drawings, which are not necessarily drawn to scale, like numerals describe substantially similar components throughout the several views. The drawings illustrate generally, by way of example, but not by way of limitation, various embodiments discussed in the present document.
[0009] FIG. 1 shows an example system for monitoring and stimulating a heart.
[0010] FIG. 2A shows a medical device lead assembly that includes a cover over an electrode.
[0011] FIG. 2B shows a medical device lead assembly that includes a cover over two electrodes.
[0012] FIGS. 3A and 3B show a polyethylene cover wrapped around a portion of a medical device lead assembly.
[0013] FIG. 4 shows a piece of polyethylene material wrapped around a portion of a medical device lead assembly to form a cover.
[0014] FIG. 5 shows a porous cover having pores of different sizes in different regions of the cover.
[0015] FIG. 6A shows a lead assembly and porous covers that have pores of different sizes.
[0016] FIG. 6B shows a lead assembly and a porous cover that has pores in a distal portion of the cover that are larger than pores elsewhere in the cover.
[0017] FIG. 7 is a flow chart that illustrates a method of applying polyethylene material to a lead assembly.
DETAILED DESCRIPTION
[0018] The following detailed description includes references to the accompanying drawings, which form a part of the detailed description. The drawings show, by way of illustration, specific embodiments in which the invention may be practiced. These embodiments are also referred to herein as “examples.” The drawings and following detailed description is not to be taken in a limiting sense, and the scope of the present invention is defined by the appended claims and their equivalents.
[0019] A lead assembly includes a porous polyethylene cover extending over at least a portion of the length of the lead assembly. FIG. 1 shows an example system for monitoring and stimulating a heart that includes a lead assembly having a porous polyethylene cover. FIGS. 2 , 3 A- 3 B, 4 , 5 , and 6 A- 6 B show lead assemblies and example porous polyethylene covers. FIG. 7 is a flowchart that illustrates a method of applying a cover.
[0020] Referring now to FIG. 1 , an example system for monitoring and stimulating a heart 105 includes a medical device 110 and at least one lead assembly. In an example, the lead assembly is a pacing lead, defibrillation lead, or neurological lead. In an example, the medical device 110 is a pacer, defibrillator, or stimulator. In an example, the medical device 110 is coupled to two lead assemblies, as shown in FIG. 1 . In FIG. 1 , one lead assembly 115 extends into the right side of the heart. The other lead assembly 120 extends into the left side of the heart. Each lead assembly includes at least one porous polyethylene cover 125 , 130 . In another example, the medical device 110 is coupled to a single lead assembly that extends, for example, into either the right or left side of the heart. In other examples, a lead assembly extends on or around the heart, or on or around a nerve truck or other anatomical target.
[0021] FIG. 2A shows an example medical device lead assembly 205 . The lead assembly 205 includes one or more conductors extending through a lumen in a lead body 210 . In an example, the lead body 210 is made of silicone. In an example, the lead body is a silicone tube. A proximal end 215 of the lead assembly 205 is connectable to a medical device. A distal end portion 220 of the lead assembly is implantable in, on, or around a heart. The conductors in the lead assembly are electrically coupled to one or more electrodes. In an example, the lead assembly includes a first defibrillation electrode 230 , a second defibrillation electrode 235 , and a sensing/pacing electrode 240 . A porous polyethylene covering 245 extends over at least one of the defibrillation electrodes. In an example, a first covering 250 extends over the first defibrillation electrode 230 and a second covering 255 extends over the second defibrillation electrode 235 . The coverings are shown partially cut-away in FIG. 2A to show the electrodes beneath the coverings. In an example, the coverings are spaced apart on the lead assembly. In another example, the coverings touch or overlap, and are optionally joined together. In an alternative example, a single covering 260 extends over both the first defibrillation electrode 230 and the second defibrillation electrode 235 , as shown in FIG. 2B .
[0022] In an example, the thickness of the polyethylene covering is between 0.0001 and 0.010 inches, the width of the covering is between 0.1 and 8 inches, and the pore size is between 0.1 micron and 15 microns. In an example, the polyethylene covering shown in FIG. 2A or 2 B has a tensile strength of about 1000 pounds per square inch (psi) and pore size of about 2 microns.
[0023] In an example, a porous polyethylene covering is applied to an electrode in line with other manufacturing processes. Examples polyethylene materials have a processing temperature of around 130-150° C., which allows application of the polyethylene covering in a manufacturing line. In contrast, materials such as PTFE can have processing temperatures in excess of 300° C. To accommodate the high-temperature sintering, a PTFE covering is typically added to a lead assembly in a post process. Forming a cover from polyethylene allows the cover to be applied in-line with other manufacturing steps because of the 130-150° C. processing temperatures associated with polyethylene. For example, polyethylene can be applied by spray coating, dip coating, plasma deposition, laser deposition, or chemical vapor deposition.
[0024] Referring now to FIGS. 3A and 3B , an example method of forming a polyethylene covering on a lead assembly is shown. A piece of porous polyethylene material 305 is wrapped around at least a portion of a lead assembly 315 . The piece includes a first edge 325 and a second edge 330 . The first edge 325 meets or overlaps with the second edge 330 , as shown in FIG. 3B . In an example, the piece of porous polyethylene material 305 is wrapped around an electrode 310 . In an example, the electrode 310 includes a wire 320 wrapped into a coil, and the polyethylene material covers the entire coil. In an example, the piece of porous polyethylene also extends over at least a portion of a lead body 335 . In an example, the cover extends over most or all of the lead assembly.
[0025] The polyethylene cover 305 is secured on the lead assembly, for example, by connecting the cover to itself. In an example, at least a portion of the polyethylene cover 305 is heated to fuse the porous polyethylene material to itself. In an example, the heating also conforms the polyethylene to the outer shape of the electrode or lead body. In an example, the polyethylene material 305 is sintered proximate the first edge 325 to hold the material 305 in a generally tubular shape that extends over the electrode, as shown in FIG. 3B . In an example, the porous polyethylene covering is sintered with a laser, infrared (IR) wand, heat gun, or oven.
[0026] Referring now to FIG. 4 , another method of applying a polyethylene covering is shown. A piece 405 of polyethylene material 406 is wrapped around a lead assembly 415 in a spiral. In an example, the piece 405 is wrapped around an electrode 410 . In an example, a first edge 420 of the piece 405 meets or overlaps with a second edge 425 of the piece from a previous wrap around the lead assembly. The spiral-wrapped piece of polyethylene forms a polyethylene tube 430 that extends over the electrode.
[0027] In an example, spiral-wrapped polyethylene material as shown in FIG. 4 extends past the electrode to cover a portion of the lead assembly, or all of the lead assembly. Covering the lead assembly protects the lead assembly and facilitates extraction, for example by limiting or preventing tissue ingrowth around portions of the lead.
[0028] Referring now to FIG. 5 , a polyethylene covering 505 includes pores 510 . The size of the pores is exaggerated for the purpose of illustration. In an example, the pore size in the porous polyethylene covering is controlled to control tissue ingrowth into the covering. In an example, the pores 515 in a first portion 520 of the polyethylene covering 505 are smaller than the pores 525 in a second portion 530 of the polyethylene covering. For the purpose of illustration, a dotted line is provided FIG. 5 to distinguish the first portion 520 of the covering from the second portion 530 . In an example, the pores 515 in the first portion 520 are large enough to allow at least some tissue ingrowth, and the pores 525 in the second portion 530 are small enough to substantially inhibit tissue ingrowth. In an example, the tissue ingrowth into the pores 515 in the first portion 520 secures the lead to body tissue. In an example, the covering 505 is formed around the lead assembly using the technique illustrated in FIGS. 3A-3B or the technique illustrated in FIG. 4 .
[0029] The size of pores in the polyethylene material can be controlled using one or more of a variety of techniques. In an example, pieces of polyethylene material are manufactured to have differing pore sizes by controlling parameters such as tension or heat during the manufacturing process. In an example, different polyethylene pieces are used at different locations on the lead assembly to allow tissue growth at particular locations on the lead, such as at a distal end portion.
[0030] In another example, pore size is controlled by adjusting tension applied to the polyethylene material as the material is assembled onto the lead assembly. In an example, a polyethylene cover is made using a spiral winding technique, as illustrated in FIG. 4 , and the pore size is controlled by varying the tension on the piece of material 305 . In another example, pore size is varied through application of heat during or after the application of the polyethylene material to the electrode. In an example, two or more of the preceding techniques are used concurrently or sequentially to control the pore size at one or more locations in the polyethylene material. In an example, laser drilling is used to form pores in a specific size and pattern.
[0031] Referring now to FIG. 6A , a lead assembly 605 includes a first porous polyethylene cover 610 proximate a distal end portion 615 of the lead assembly and a second polyethylene cover 620 proximate a middle portion 625 of the lead assembly. In an example, the lead assembly includes a third cover 630 that extends between the first cover 610 and second cover 620 . Other examples include additional polyethylene covers. In an example, covers extend over most or all of the outer surface of the lead assembly. In an example, some or all of the polyethylene covers are fused together using heat. In an example, the ends of adjacent covers are fused together using a laser.
[0032] In an example, a portion of the polyethylene cover 610 proximate the distal end portion of the lead assembly 605 includes pores that are large enough to permit tissue growth. The tissue growth secures the distal end portion of the lead to local tissue. For example, when the lead is implanted in the heart, the tissue growth secures the distal end portion of the lead to the heart.
[0033] In an example, pore size is controlled within one or both of the covers 610 , 620 , which allows for selective tissue ingrowth at locations on the cover. In the example shown in FIG. 6B , a cover 635 includes a first portion 640 that includes pores that are large enough to allow tissue ingrowth, and a second portion 645 that has pores that do not allow tissue ingrowth. In an example, the first portion 640 is formed having larger pores than the second portion 645 by varying parameters such as tension and/or heat during application of the polyethylene to the lead assembly. In another example, the first portion 640 is made from a separate piece of polyethylene material that has been pre-processed to have larger pores than the second portion 645 . In an example, the separate piece is applied to the lead in a separate operation and then sintered to the second portion to form a continuous cover
[0034] In an example, the covering is hydrophilicly treated. In an example, the covering is wetted using a plasma technique. In another example, the covering is wetted using a plasma-assisted chemical vapor deposition technique. In an example, the covering is treated using, glycol, acrylic acid, allyl amine, an alcohol such as isopropyl alcohol (IPA), ethanol, or methanol. In an example, the covering is treated with a laser after the covering is wetted to preserve the hydrophilic state of the covering. In an example, the wavelength, pulse duration, and/or power are adjusted to actuate the polymer surface and promote development of a hydrophilic state. In another example, a chemical hydrophilic treatment is used. In an example, the chemical hydrophilic treatment uses polyvinyl acetate (PVA) or polyethylene glycol (PEG).
[0035] In an example, when the pores are filled with a conductive substance, such as body fluid, the pores in the polyethylene provide a conductive pathway for a defibrillation current. In another example, the polyethylene includes particles of conductive matter to make the covering itself conductive. In another example, a conductive material is deposited on the polyethylene to provide a conductive pathway for a defibrillation current. FIG. 7 is a flow chart that illustrates a method of applying a polyethylene material to a lead assembly. At 705 , a piece of porous polyethylene material is wrapped around a first portion of a lead assembly. In an example, the stock polyethylene material is porous before it is wrapped. In another example, pores are created in the polyethylene when the polyethylene is wrapped. At 710 , the size of the pores in the polyethylene is controlled by adjusting a tension in the polyethylene during wrapping. Applying a higher tension to the polyethylene results in more stretching of the material and larger pores. At 715 , a first portion of the piece of porous polyethylene is fused to a second portion of the piece of polyethylene. In an example, the polyethylene is wrapped spirally onto the lead assembly, and adjacent portions of the material (i.e. adjacent windings) are fused together. In an example, the polyethylene is fused by heating, for example with a laser. In an example, the porous polyethylene is heated to between 80 and 150 degrees C.
[0036] Referring again to FIG. 7 , at 720 , a second piece of porous polyethylene is wrapped around a second portion of the lead assembly. In an example, the second piece of polyethylene has pores that are larger than the pores in the first piece of porous polyethylene. In an example, the second piece of porous polyethylene is wrapped onto the lead assembly before the first piece of porous polyethylene is wrapped onto the lead assembly. At 725 , the second piece of porous polyethylene is joined to the first piece of porous polyethylene. In an example the second piece of porous polyethylene is fused to the first piece of porous polyethylene by heating the polyethylene, for example with a laser.
[0037] At 730 , at least a portion of at least one piece of porous polyethylene is hydrophilically treated. In an example, a hydrophilic agent is deposited on one or both of the pieces of porous polyethylene. In an example, a hydrophilic agent is deposited in a plasma-assisted chemical vapor deposition process. In an example, hydrophilicly treating at least a portion of the piece of porous polyethylene includes treating the first piece of polyethylene with a laser. In an example, laser treating the porous polyethylene preserves hydrophilicity imparted by a hydrophilic agent. In an example, hydrophilicly treating at least a portion of the piece of porous polyethylene includes chemically treating the first piece of polyethylene. In an example, the chemical treatment preserves hydrophilicity imparted by a hydrophilic agent. In an example, the chemical hydrophilic treatment uses polyvinyl acetate (PVA) or polyethylene glycol (PEG).
[0038] Polymer lead coverings having varied material properties are also described in copending application Ser. No. 11/150,021, filed Jun. 10, 2005, now issued as U.S. Pat. No. 7,366,573 to Knapp et al., entitled Polymer Lead Covering with Varied Material Properties (Attorney Docket No. 279.908US1), which is incorporated by reference in its entirety.
[0039] It is to be understood that the above description is intended to be illustrative, and not restrictive. Since many embodiments of the invention can be made without departing from the scope of the invention, the invention resides in the claims hereinafter appended. | This document discusses, among other things, a lead assembly including a porous polyethylene cover. In an example, the cover includes sections that have differing pore sizes. In an example, a section of the cover near a distal end portion of a lead assembly includes pores that are large enough to allow tissue ingrowth. In another example, a lead assembly includes two or more polyethylene covers having different porosities. | 0 |
TECHNICAL FIELD
The present disclosure relates to a radio communication apparatus and a radio communication method.
BACKGROUND ART
Presently, in Third Generation Partnership Project Radio Access Network Long Term Evolution (3GPP RAN LTE), an uplink sounding reference signal (SRS) is studied. Here, “sounding” refers to channel quality estimation and an SRS is mainly subject to time-multiplexing and transmitted in a specific time slot in order to estimate a CQI (Channel Quality Indicator) of an uplink data channel and estimate timing offset between a base station and a mobile station.
Further, possible methods of transmitting an SRS include the method of transmitting an SRS in a specific time slot in wideband and estimating a CQI over wideband at a time, and the method of transmitting a narrowband SRS in a plurality of time slots with shifting frequency bands (frequency hopping) and estimating a CQI over wideband in several times.
Generally, a UE (User Equipment) located near a cell boundary has significant path loss and a limitation of maximum transmission power. Accordingly, if an SRS is transmitted in a wideband, received power for a base station per unit frequency decreases and received SNR (Signal to Noise Ratio) decreases, and, as a result, the accuracy of CQI estimation deteriorates. Therefore, a UE near a cell boundary adopts a narrowband SRS transmission method of narrowing limited power to a predetermined frequency band and performing transmission. In contrast, a UE near the center of a cell has small path loss and received power for a base station per unit frequency can be kept enough, and therefore adopts a wideband SRS transmission method.
Meanwhile, another purpose of transmitting an SRS is to estimate timing offset between a base station and a mobile station. Accordingly, to secure the given accuracy of timing estimation Δt, the SRS bandwidth in one transmission unit (one frequency multiplexing unit) needs to be equal to or more than 1/Δt. That is, the bandwidth of an SRS in one transmission unit needs to fulfill both the accuracy of CQI estimation and the accuracy of timing estimation.
Further, in LTE, a PUCCH (Physical Uplink Control Channel), which is an uplink control channel, is frequency-multiplexed on both ends of the system band. Accordingly, an SRS is transmitted in the band subtracting the PUCCHs from the system bandwidth.
Further, the PUCCH transmission bandwidth (a multiple of the number of channels of one PUCCH bandwidth) varies according to the number of items of control data to be accommodated. That is, when the number of items of control data to be accommodated is small, the PUCCH transmission bandwidth becomes narrow (the number of channels becomes few) and, meanwhile, when the number of items of control data to be accommodated is great, the PUCCH transmission bandwidth becomes wide (the number of channels becomes large). Therefore, as shown in FIG. 1 , when the PUCCH transmission bandwidth varies, the SRS transmission bandwidth also varies. In FIG. 1 , the horizontal axis shows frequency domain, and the vertical axis shows time domain (same as below). In the following, the bandwidth of one channel of a PUCCH is simply referred to as the “PUCCH bandwidth” and the bandwidth by multiplying the PUCCH bandwidth by the number of channels is referred to as the “PUCCH transmission bandwidth.” Likewise, the bandwidth of an SRS in one transmission unit is simply referred to as the “SRS bandwidth” and the bandwidth of an SRS in a plurality of transmission units is referred to as “SRS transmission bandwidth.”
Non-Patent Document 1: 3GPP R1-072229, Samsung, “Uplink channel sounding RS structure,” 7th-11th May 2007
BRIEF SUMMARY
In Non-Patent Document 1, the method shown in FIG. 2 is disclosed as a narrowband SRS transmission method in a case where a PUCCH transmission bandwidth varies. In the SRS transmission method disclosed in Non-Patent Document 1, as shown in FIG. 2 , the SRS transmission bandwidth is fixed to the SRS transmission bandwidth of when the PUCCH transmission bandwidth is the maximum and is not changed even when the PUCCH transmission bandwidth varies. Further, as shown in FIG. 2 , when an SRS is transmitted in a narrowband, the SRS is frequency-hopped and transmitted. According to the method described in Non-Patent Document 1, when the PUCCH transmission bandwidth is less than the maximum value shown in the bottom part of FIG. 2 , bands in which SRSs are not transmitted are produced, and the accuracy of CQI estimation significantly deteriorates in the frequency domain.
Further, as shown in FIG. 3A , if the SRS transmission bandwidth is fixed to the SRS transmission bandwidth of when the PUCCH transmission bandwidth is the minimum, SRSs and PUCCHs interfere with each other when the PUCCH transmission bandwidth increases as shown in FIG. 3B , the PUCCH reception performance deteriorates.
To prevent SRSs and PUCCHs from interfering with each other as shown in FIG. 3B when the PUCCH transmission bandwidth increases, the method of stopping transmission of an SRS interfering with a PUCCH as shown in FIG. 4B is possible. Here, FIG. 4A is the same as FIG. 3A and shown to clarify the explanation in an overlapping manner. According to this method, bands in which SRSs are not transmitted are produced, and the accuracy of CQI estimation deteriorates in the frequency domain.
An embodiment provides a radio communication apparatus and a radio communication method that facilitate reducing the deterioration of the accuracy of CQI estimation due to bands in which SRSs are not transmitted while preventing interference between SRSs and PUCCHs, in cases where the PUCCH transmission bandwidth varies in narrowband SRS transmission.
The radio communication apparatus of an embodiment adopts a configuration including: a generation section that generates a reference signal for measuring uplink data channel quality; a mapping section that frequency-multiplexes and maps the reference signal to a reference signal transmission band in which the reference signal is transmitted; and a control section that controls positions in which the frequency-multiplexing is performed such that the positions in which the frequency multiplexing is performed are placed evenly in a frequency domain without changing the bandwidth of one multiplexing unit of the reference signals according to a variation of a transmission bandwidth of the reference signals.
The radio communication method according to an embodiment includes steps of: generating a reference signal for estimating uplink data channel quality; frequency-multiplexing and mapping the reference signal to a reference signal transmission band in which the reference signal is transmitted; and controlling positions in which the frequency-multiplexing is performed such that the positions in which the frequency-multiplexing is performed are placed evenly in a frequency domain without changing the bandwidth of one multiplexing unit of the reference signals according to a variation of a transmission bandwidth of the reference signals.
According to an embodiment, it is possible to reduce the deterioration of the accuracy of CQI estimation due to bands in which SRSs are not transmitted while preventing interference between SRSs and PUCCHs in cases where the PUCCH transmission bandwidth varies in narrowband SRS transmission.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 shows a conventional case of how the SRS transmission bandwidth varies according to the variations of the PUCCH transmission bandwidth;
FIG. 2 shows a conventional narrowband SRS transmission method used when the PUCCH transmission bandwidth varies;
FIG. 3A shows an example of a conventional narrowband SRS transmission method used when the PUCCH transmission bandwidth varies;
FIG. 3B shows an example of a conventional narrowband SRS transmission method used when the PUCCH transmission bandwidth varies;
FIG. 4A shows an example of a conventional narrowband SRS transmission method used when the PUCCH transmission bandwidth varies;
FIG. 4B shows an example of a conventional narrowband SRS transmission method used when the PUCCH transmission bandwidth varies;
FIG. 5 is a block diagram showing the configuration of the base station according to Embodiment 1;
FIG. 6 is a block diagram showing the configuration of the mobile station according to Embodiment 1;
FIG. 7 is a flow chart showing the processing steps in the SRS allocation determination section according to Embodiment 1;
FIG. 8A shows an allocation example of SRSs determined in the SRS allocation determination section according to Embodiment 1;
FIG. 8B shows an allocation example of SRSs determined in the SRS allocation determination section according to Embodiment 1;
FIG. 9 is a flow chart showing the processing steps in the SRS allocation determination section according to Embodiment 2;
FIG. 10A shows an allocation example of SRSs determined in the SRS allocation determination section according to Embodiment 2;
FIG. 10B shows an allocation example of SRSs determined in the SRS allocation determination section according to Embodiment 2;
FIG. 11A shows an allocation example of SRSs determined in the SRS allocation determination section according to Embodiment 3;
FIG. 11B shows an allocation example of SRSs determined in the SRS allocation determination section according to Embodiment 3;
FIG. 12A shows an allocation example of SRSs determined in the SRS allocation determination section according to Embodiment 4;
FIG. 12B shows an allocation example of SRSs determined in the SRS allocation determination section according to Embodiment 4;
FIG. 13A shows an allocation example of SRSs determined in the SRS allocation determination section according to Embodiment 5;
FIG. 13B shows an allocation example of SRSs determined in the SRS allocation determination section according to Embodiment 5;
FIG. 14A shows an allocation example (example 1) of SRSs determined in an example of the SRS allocation determination section according to an embodiment;
FIG. 14B shows an allocation example (example 1) of SRSs determined in an example of the SRS allocation determination section according to an embodiment;
FIG. 15A shows an allocation example (example 2) of SRSs determined in an example of the SRS allocation determination section according to an embodiment;
FIG. 15B shows an allocation example (example 2) of SRSs determined in an example of the SRS allocation determination section according to an embodiment;
FIG. 16 shows an example of the SRS allocation definition table according to the present embodiment;
FIG. 17A shows an allocation example (example 3) of SRSs determined in an example of the SRS allocation determination section according to an embodiment;
FIG. 17B shows an allocation example (example 3) of SRSs determined in an example of the SRS allocation determination section according to an embodiment;
FIG. 18A shows an allocation example (example 4) of SRSs determined in an example of the SRS allocation determination section according to an embodiment; and
FIG. 18B shows an allocation example (example 4) of SRSs determined in an example of the SRS allocation determination section according to an embodiment.
DETAILED DESCRIPTION
Now, example embodiments will be described in detail with reference to the accompanying drawings.
Embodiment 1
FIG. 5 shows the configuration of base station 100 according to Embodiment 1, and FIG. 6 shows the configuration of mobile station 200 according to Embodiment 1.
To avoid complicated explanation, FIG. 5 shows components involving SRS reception closely relating to the present disclosure, and drawings and explanations of the components involving uplink and downlink data transmission and reception are omitted. Likewise, FIG. 6 shows components involving SRS transmission closely relating to the present disclosure and, drawings and explanations of the components involving uplink and downlink data transmission and reception are omitted.
In base station 100 shown in FIG. 5 , SRS allocation determination section 101 determines allocation of SRSs in the frequency domain and the time domain based on the number of PUCCH channels, and outputs information related to the determined SRS allocation (hereinafter “SRS allocation information”), to control signal generation section 102 and SRS extraction section 108 . The processing in SRS allocation determination section 101 will be described later in detail. Control signal generation section 102 generates a control signal including SRS allocation information, and outputs the generated control signal to modulation section 103 . Modulation section 103 modulates the control signal, and outputs the modulated control signal to radio transmitting section 104 . Radio transmitting section 104 performs transmitting processing including D/A conversion, up-conversion and amplification, on the modulated signal, and transmits the resulting signal from antenna 105 .
Radio receiving section 106 receives SRSs via radio from mobile station 200 via antenna 105 , performs receiving processing including down-conversion and A/D conversion on the SRSs and outputs the SRSs after receiving processing to demodulation section 107 . Demodulation section 107 demodulates the received SRSs and outputs the demodulated SRSs to SRS extraction section 108 . SRS extraction section 108 extracts SRSs allocated in the frequency domain and the time domain based on the SRS allocation information received as input from SRS allocation determination section 101 , and outputs the extracted SRSs to CQI/timing offset estimation section 109 . CQI/timing offset estimation section 109 estimates CQIs and timing offset from the SRSs.
In mobile station 200 shown in FIG. 6 , SRS code generation section 201 generates a code sequence used as an SRS for measuring uplink data channel quality, that is, generates an SRS code, and outputs the SRS code to SRS allocation section 202 . SRS allocation section 202 maps the SRS code to resources in the time domain and frequency domain according to SRS allocation control section 208 , and outputs the mapped SRS code to modulation section 203 . Modulation section 203 modulates the SRS code and outputs the modulated SRS code to radio transmitting section 204 . Radio transmitting section 204 performs transmitting processing including D/A conversion, up-conversion and amplification, on the modulated signal, and transmits the resulting signal from antenna 205 .
Radio receiving section 206 receives a control signal via radio from base station 100 via antenna 205 , performs receiving processing including down-conversion and A/D conversion on the control signal and outputs the control signal after receiving processing to demodulation section 207 . Demodulation section 207 demodulates the received control signal and outputs the demodulated control signal to SRS allocation control section 208 . SRS allocation control signal 208 controls SRS allocation section 202 according to the SRS allocation information included in the demodulated control signal.
Next, the processing in SRS allocation determination section 101 in base station 100 will be explained in detail.
FIG. 7 is a flow chart showing the processing steps in SRS allocation determination section 101 .
First, in step (hereinafter “ST”) 1010 , SRS allocation determination section 101 determines an SRS bandwidth based on the accuracy of CQI estimation and the accuracy of timing offset estimation.
Next, in ST 1020 , SRS allocation determination section 101 calculates the number of SRSs to be multiplexed in the frequency domain based on the system bandwidth, the number of PUCCH channels and the SRS bandwidth. To be more specific, the number of SRSs to be multiplexed in the frequency domain is the maximum number of SRSs which can be multiplexed on the SRS transmission bandwidth obtained by subtracting the PUCCH transmission bandwidth from the system bandwidth, and which each have a bandwidth of one transmission unit determined in ST 1010 . That is, the number of SRSs to be multiplexed in the frequency domain is the integer part of the quotient obtained by dividing the SRS transmission bandwidth by the SRS bandwidth determined in ST 1010 . Here, the PUCCH transmission bandwidth is determined by the number of PUCCH channels, and varies according to the number of items of control data to be accommodated.
Next, in ST 1030 , SRS allocation determination section 101 first determines allocation of SRSs such that the SRSs are frequency-hopped (frequency-multiplexed) in the SRS transmission bandwidth at predetermined time intervals. To be more specific, SRS allocation determination section 101 determines that SRSs are mapped in the frequency domain and time domain such that the SRSs cover the frequency band to be subject to CQI estimation evenly and are mapped at predetermined time intervals in the time domain.
FIGS. 8A and 8B show examples of SRS allocation determined in SRS allocation determination section 101 . FIG. 8A shows a case where the number of PUCCH channels is two, and FIG. 8B shows a case where the number of PUCCH channels is four.
In FIGS. 8A and 8B , the SRS bandwidths are determined so as to fulfill the required accuracy of CQI estimation and the required accuracy of timing offset, and are not changed even when the number of PUCCH channels and SRS transmission bandwidth vary.
Further, the number of PUCCH channels varies between FIGS. 8A and 8B , and therefore, the SRS transmission bandwidth varies and the number of SRSs to be frequency-multiplexed, that is, the number of SRS hopping, obtained by dividing the SRS transmission bandwidth by the SRS bandwidths determined in ST 1010 , varies. When the number of PUCCH channels is two in FIG. 8A , the number of SRSs to be frequency-multiplexed is four, and, when the number of PUCCH channels is four in FIG. 8B , the number of SRSs to be frequency-multiplexed is three.
Then, as shown in FIG. 8 , the positions where SRSs are frequency-multiplexed in the SRS transmission bandwidth are positions to cover the SRS transmission band evenly, that is, the frequency band subject to CQI estimation. This results in dividing the band in which SRSs are not transmitted into a number of bands having smaller bandwidths, that is, this prevents SRSs from being not transmitted over a specific wide range of a band, so that it is possible to reduce the deterioration of the accuracy of CQI estimation due to bands in which SRSs are not transmitted.
In this way, according to the present embodiment, in accordance with an increase and decrease of the number of PUCCH channels, SRS allocation is changed to cover a CQI estimation bandwidth with fixed SRS bandwidths evenly, so that, when the PUCCH transmission bandwidth varies, it is possible to prevent interference between SRSs and PUCCHs while maintaining the accuracy of CQI estimation and the accuracy of timing offset estimation, and reduce the deterioration of the accuracy of CQI estimation due to bands in which SRSs are not transmitted.
Embodiment 2
The base station and the mobile station according to Embodiment 2 adopt the same configurations and basically perform the same operations as the base station and the mobile station according to Embodiment 1. Therefore, block diagrams are not shown here, and the description will be omitted in detail. The base station and the mobile station according to the present embodiment are different from the base station and the mobile station according to Embodiment 1 in the SRS allocation determination section in the base station. The SRS allocation determination section provided in the base station according to the present embodiment is different from SRS allocation determination section 101 provided in the base station according to Embodiment 1 in part of processing.
Now, the processing in the SRS allocation determination section according to the present embodiment will be explained.
FIG. 9 is a flow chart showing the processing steps in the SRS allocation determination section according to the present embodiment. The steps shown in FIG. 9 are basically the same as shown in FIG. 7 and the same reference numerals are assigned to the same steps, and therefore the explanation thereof will be omitted. The steps shown in FIG. 9 are different from the steps shown in FIG. 7 in having ST 2030 instead of ST 1030 .
In ST 2030 , the SRS allocation determination section first calculates the time interval at which SRSs are mapped in the frequency domain and time domain according to the following equation 1. If the SRSs are transmitted using time interval τ(c PUCCH ) calculated according to equation 1, the CQI estimation period in the CQI estimation target band is fixed even if the number of PUCCH channels varies.
[1]
τ( c PUCCH )≈ T/n ( c PUCCH ) (Equation 1)
In equation 1, T represents the CQI estimation period in the CQI estimation target band and c PUCCH represents the number of PUCCH channels. n(c PUCCH ) represents the number of SRSs to be frequency-multiplexed, that is, the number of frequency hopping, when the number of PUCCH channels is c PUCCH . The transmission interval is based on a time slot unit, and therefore τ(c PUCCH ) is a result of the value on the right hand side of equation 1 matched with a time slot.
Further, in ST 2030 , the SRS allocation determination section determines allocation of SRSs such that SRSs are frequency-multiplexed in the SRS transmission bandwidth at the calculated time interval τ. To be more specific, SRS allocation determination section determines to map SRSs so as to cover the frequency band subject to CQI estimation target evenly in the frequency domain and to cover CQI estimation period T evenly in the time domain.
FIGS. 10A and 10B show examples of SRS allocation determined in the SRS allocation determination section according to the present embodiment. FIG. 10 is basically the same as FIG. 8 and the overlapping explanation will be omitted.
In FIGS. 10A and 10B , the SRS bands are not changed in accordance with a variation of SRS transmission bandwidth, and SRSs are frequency-multiplexed so as to cover the SRS transmission bandwidth evenly.
Further, in FIG. 10A , SRSs are mapped using time interval τ(2), and in FIG. 10B , SRSs are mapped using time interval τ(4). That is, in the present embodiment, when the number of PUCCH channels decreases, the SRS transmission interval is made shorter and when the number of PUCCH channels increases, the SRS transmission interval is made longer. By this means, even when the number of PUCCH channels varies, CQI estimation period T does not vary.
In this way, according to the present embodiment, in accordance with an increase and decrease of the number of PUCCH channels, SRS allocation is changed such that a CQI estimation bandwidth is covered with fixing SRS bandwidths evenly. Accordingly, when the PUCCH transmission bandwidth varies, it is possible to prevent SRSs and PUCCHs from interfering each other while maintaining the accuracy of CQI estimation and the accuracy of timing offset, and reduce the deterioration of the accuracy of CQI estimation due to bands in which SRSs are not transmitted.
Further, according to the present embodiment, when the number of PUCCH channels decreases, the SRS transmission interval is made shorter and when the number of PUCCH channels increases, the SRS transmission interval is made longer. By this means, when the PUCCH transmission bandwidth varies, it is possible to maintain a constant CQI estimation period and prevent the accuracy of CQI estimation from deteriorating.
Embodiment 3
The base station and the mobile station according to Embodiment 3 adopt the same configurations and basically perform the same operations as the base station and the mobile station according to Embodiment 1. Therefore, block diagrams are not shown here, and the description will be omitted in detail. The base station and the mobile station according to the present embodiment are different from the base station and the mobile station according to Embodiment 1 in the SRS allocation determination section in the base station. The SRS allocation determination section provided in the base station according to the present embodiment is different from SRS allocation determination section 101 provided in the base station according to Embodiment 1 in part of processing.
Now, the allocation of SRSs determined in the SRS allocation determination section according to the present embodiment will be explained.
FIGS. 11A and 11B show examples of SRS allocation determined in the SRS allocation determination section according to the present embodiment. FIG. 11 is basically the same as FIG. 10 and the overlapping explanation will be omitted.
In FIGS. 11A and 11B , the SRS bands are not changed in accordance with a variation of SRS transmission bandwidth, and SRSs are frequency-multiplexed so as to cover the SRS transmission bandwidth evenly.
Further, as shown in FIGS. 11A and 11B , the number of SRSs to be frequency-multiplexed is the number of when the number of PUCCH channels is the maximum, regardless of whether the number of PUCCHs increases or decreases. Here, the maximum value for the number of PUCCH channels is four and the number of SRSs to be frequency-multiplexed is three.
Further, as shown in FIGS. 11A and 11B , a transmission interval between SRSs is the transmission interval of when the number of PUCCH channels is the maximum, regardless of whether the number of PUCCHs increases or decreases. Here, the maximum value for the number of PUCCH channels is four and the transmission interval is represented by τ(4). According to the method as shown in FIG. 11 , it is not necessary to calculate a transmission interval every time the number of PUCCH channels varies and it is possible to simplify the determination processing of SRS allocation.
In this way, according to the present embodiment, in accordance with an increase and decrease of the number of PUCCH channels, SRS allocation is changed such that a CQI estimation bandwidth is evenly covered with fixing SRS bandwidths. By this means, when the PUCCH transmission bandwidth varies, it is possible to prevent SRSs and PUCCHs from interfering each other while maintaining the accuracy of CQI estimation and the accuracy of timing offset, and reduce the deterioration of the accuracy of CQI estimation due to bands in which SRSs are not transmitted.
Furthermore, according to the present embodiment, in accordance with an increase and decrease of the number of PUCCH channels, SRSs are mapped without changing the number of SRSs to be frequency-multiplexed and the SRS transmission interval, so that it is possible to simplify the SRS allocation process.
Embodiment 4
In Embodiment 4, the method of SRS allocation from a plurality of mobile stations in accordance with a variation of the PUCCH transmission bandwidth, will be explained.
The base station and the mobile station according to Embodiment 4 adopt the same configurations and basically perform the same operations as the base station and the mobile station according to Embodiment 1. Therefore, block diagrams are not shown here, and the description will be omitted in detail. The base station and the mobile station according to the present embodiment are different from the base station and the mobile station according to Embodiment 1 in the SRS allocation determination section in the base station. The SRS allocation determination section provided in the base station according to the present embodiment is different from SRS allocation determination section 101 provided in the base station according to Embodiment 1 in part of processing.
Now, the allocation of SRSs determined in the SRS allocation determination section according to the present embodiment will be explained.
FIGS. 12A and 12B show examples of SRS allocation determined in the SRS allocation determination section according to the present embodiment. FIG. 12 is basically the same as FIG. 8 and the overlapping explanation will be omitted.
In FIGS. 12A and 12B , the SRS bands are not changed in accordance with a variation of SRS transmission bandwidth, and SRSs are frequency-multiplexed so as to cover the SRS transmission bandwidth evenly.
Further, as shown in FIGS. 12A and 12B , in accordance with the variation of the PUCCH transmission bandwidth, the SRS allocation determination section according to the present embodiment maps SRSs without changing the hopping pattern of SRSs in a predetermined frequency band. In other words, SRS allocation to be changed is controlled so as to make different hopping patterns in the same band. To be more specific, by transmitting and not transmitting SRSs mapped to the specific band according to an increase and decrease of the PUCCH transmission bandwidth, it is not necessary to change the hopping pattern in other bands.
In this way, according to the present embodiment, in accordance with an increase and decrease of the number of PUCCH channels, SRS allocation is changed such that a CQI estimation bandwidth is evenly covered with fixing SRS bandwidths. By this means, when the PUCCH transmission bandwidth varies, it is possible to prevent SRSs and PUCCHs from interfering each other while maintaining the accuracy of CQI estimation and the accuracy of timing offset, and reduce the decrease of the accuracy of CQI estimation due to bands in which SRSs are not transmitted.
Further, according to the present embodiment, in accordance with an increase and decrease of the number of PUCCH channels, SRSs are mapped in the frequency domain and time domain without changing the SRS hopping pattern, so that, when the PUCCH transmission bandwidth varies, it is possible to maintain the number of SRSs from mobile stations to be multiplexed and the CQI estimation period in the CQI estimation target band of each mobile station.
Embodiment 5
The base station and the mobile station according to Embodiment 5 adopt the same configurations and basically perform the same operations as the base station and the mobile station according to Embodiment 1. Therefore, block diagrams are not shown here, and the description will be omitted in detail. The base station and the mobile station according to the present embodiment are different from the base station and the mobile station according to Embodiment 1 in the SRS allocation determination section in the base station. The SRS allocation determination section provided in the base station according to the present embodiment is different from SRS allocation determination section 101 provided in the base station according to Embodiment 1 in part of processing.
Now, the allocation of SRSs determined in the SRS allocation determination section according to the present embodiment will be explained.
FIGS. 13A and 13B show examples of SRS allocation determined in the SRS allocation determination section according to the present embodiment.
In FIGS. 13A and 13B , the SRS bands are not changed in accordance with a variation of SRS transmission bandwidth, and SRSs are frequency-multiplexed so as to cover the SRS transmission bandwidth evenly.
Further, in FIGS. 13A and 13B , the number of SRSs to be frequency-multiplexed is the number of when the number of PUCCH channels is the minimum and is fixed regardless of whether the number of PUCCHs increases or decreases. In FIGS. 13A and 13B , the minimum value for the number of PUCCH channels is two and the number of SRSs to be frequency-multiplexed is four.
Further, in FIGS. 13A and 13B , while the SRS transmission bandwidth varies in accordance with an increase and decrease of the number of PUCCH channels, the number of SRSs to be frequency-multiplexed is fixed, and therefore SRSs are mapped in the frequency domain such that a plurality of SRSs partly overlap.
Further, in FIGS. 13A and 13B , the number of SRSs to be frequency-multiplexed does not change in accordance with an increase and decrease of the number of PUCCH channels, and therefore SRS transmission intervals do not change.
In this way, according to the present embodiment, in accordance with an increase and decrease of the number of PUCCH channels, SRS allocation is changed such that a CQI estimation bandwidth is covered with fixing SRS bandwidths evenly. Accordingly, when the PUCCH transmission bandwidth varies, it is possible to prevent interference between an SRS and a PUCCH while maintaining the accuracy of CQI estimation and the accuracy of timing offset, and reduce the deterioration of the accuracy of CQI estimation due to bands in which SRSs are not transmitted.
Further, according to the present embodiment, in accordance with an increase and decrease of the number of PUCCH channels, SRS are mapped such that bands of frequency-multiplexed SRSs partly overlap, without changing the number of SRSs to be frequency-multiplexed, so that it is possible to improve the accuracy of CQI estimation more and prevent the accuracy of CQI estimation from deteriorating due to bands in which SRSs are not transmitted.
The example embodiments have been explained.
Although cases have been explained with the above embodiments where the number of PUCCH channels is two or four, the number is explained with examples only and the present disclosure is not limited to this.
Further, although cases have been explained with the above embodiments where the SRS transmission bandwidth is the band obtained by subtracting the PUCCH transmission bandwidth from the system bandwidth, the present disclosure is not limited to this, and the SRS transmission bandwidth may be a specific band varying according to an increase and decrease of the number of PUCCH channels.
Further, although cases have been explained with the above embodiments as examples where the SRS bands are not changed in accordance with an increase and decrease of the number of PUCCH channels and the positions on which SRSs are frequency-multiplexed in the SRS transmission band change, the present disclosure is not limited to this, and it is possible to change the positions where SRSs are frequency-multiplexed in the SRS transmission band according to an increase and decrease of the number of PUCCH channels, and change the SRS bandwidths. A variation of an SRS bandwidth may be limited within a range in which the deterioration of the accuracy of CQI estimation and the accuracy of timing offset can be ignored, for example within ±1 to 2 RBs, and this facilitates reducing the deterioration of the accuracy of CQI estimation. Here, an RB (Resource Block) refers to a unit representing a specific range of radio resources. FIG. 14A shows an example where the SRS bands extend in a predetermined range and the range of each extended band in FIG. 14A is 1 RB or less. Further, to extend and contract the SRS transmission band here, CAZAC (Constant Amplitude Zero Auto-Correlation) sequence or cyclic extension and truncation of a sequence having the same characteristics as CAZAC may be adopted.
Further, it is possible to allocate uplink data channels for which CQIs cannot be estimated using narrowband SRSs with the above embodiments, to mobile stations transmitting wideband SRSs with priority. FIG. 14B illustrates to explain a case where uplink data channels for which CQIs cannot be estimated using narrowband SRSs are allocated with priority to mobile stations transmitting wideband SRSs. The above packet allocation method makes it possible to prevent the frequency scheduling effect from lowering.
Further, as shown in FIG. 15A , SRSs may be mapped so as to neighbor PUCCHs. Further, as shown in FIG. 15B , allocation of SRSs may vary between hopping cycles.
Further, an SRS may be named as simply a “pilot signal,” “reference signal” and so on.
Further, a known signal used for an SRS may include a CAZAC sequence or a sequence having the same characteristics as a CAZAC.
Further, the SRS allocation information acquired in the base station according to the above embodiments may be reported to mobile stations using a PDCCH (Physical Downlink Control Channel), which is an L1/L2 control channel, or using a PDSCH (Physical Downlink Shared Channel) as an L3 message.
Further, in the above embodiments, DFT-s-OFDM (Discrete Fourier Transform-spread-Orthogonal Frequency Division Multiplexing) employed in LTE may be adopted to the uplink.
Further, in the above embodiments, OFDM employed in LTE may be adopted to downlink.
Further, the SRS allocation information according to the above embodiments may be uniquely associated in advance with a broadcast channel, for example, PUCCH configuration information reported in a BCH (Broadcast Channel). By this means, it is not necessary to transmit SRS allocation information on a per UE basis, so that signaling overhead is reduced. For example, each UE may calculate SRS allocation from the number of PUCCH channels as follows.
Now, an example of equations to calculate SRS allocation from the number of PUCCH channels will be shown below.
If the subcarrier to which an SRS starts to be mapped in the frequency domain is k 0 , k 0 is represented as the following equation 2.
[2]
k 0 =k RB ( n )· N SC RB (Equation 2)
In equation 2, n represents the multiplexing number of an SRS in the frequency domain and N sc RB represents the number of subcarriers per RB. Further, k RB (n) represents the RB number to which the SRS with frequency multiplex number n is mapped and is represented by the following equation 3 or 4.
[
3
]
k
RB
(
n
)
=
N
SRS
BASE
+
⌊
(
n
+
1
)
·
N
RB
UL
-
N
RB
PUCCH
-
N
SRS
BASE
·
N
SRS
N
SRS
+
1
⌋
+
⌊
N
RB
PUCCH
2
⌋
n
=
0
,
1
,
…
N
SRS
-
1
(
Equation
3
)
[
4
]
k
RB
(
n
)
=
n
·
N
SRS
BASE
+
⌊
(
2
n
+
1
)
·
N
RB
UL
-
N
RB
PUCCH
-
N
SRS
BASE
·
N
SRS
2
N
SRS
⌋
+
⌊
N
RB
PUCCH
2
⌋
n
=
0
,
1
,
…
N
SRS
-
1
(
Equation
4
)
In equations 3 and 4, N SRS represents the number of SRSs to be frequency-multiplexed and is represented by the following equation 5.
[
5
]
N
SRS
=
⌊
N
RB
UL
-
N
RB
PUCCH
N
SRS
BASE
⌋
(
Equation
5
)
In equations 3, 4 and 5, N RB PUCCH represents the number of RBs included in the PUCCH transmission band and N RB UL represents the number of RBs included in the system band. N SRS BASE represents the number of RBs included in the SRS transmission bandwidth.
In the above parameters, the parameters other than N RB PUCCH are system parameters, so that the system parameters can be used in a fixed manner once they are signaled or reported. Accordingly, when a mobile station is given N RB PUCCH SRS allocation is able to be derived according to the above equation 2 to equation 5. Here, N RB PUCCH is the parameter determined by the number of PUCCH channels, so that a mobile station is able to derive SRS allocation and transmit SRSs if the mobile station is provided the number of PUCCH channels from the base station.
Further, the mobile station may derive SRS allocation from the number of PUCCH channels with reference to an SRS allocation definition table instead of above equation 2 to equation 5. FIG. 16 shows an example of the SRS allocation definition table. The SRS allocation definition table shown in FIG. 16 defines the RB numbers of RBs to which SRSs are mapped in cases where the number of PUCCH channels is one and four. Further, t represents a transmission timing in hopping cycles. Further, as shown in FIG. 16 , the hopping patterns vary according to varying multiplexing number of SRSs to n. Further, “-” in the table shows that SRSs are not allocated. By holding an SRS allocation definition table, a mobile station is able to derive SRS allocation and transmit SRSs if the mobile station is provided the number of PUCCH channels from the base station.
Further, the information uniquely associated in advance with PUCCH configuration information may include other SRS configuration information including variable information about the above SRS bandwidth and SRS sequence information, in addition to the SRS allocation information.
Further, although examples have been explained with the above embodiments where the narrowband SRS bandwidths evenly cover one SRS transmission bandwidth in the frequency domain, the present disclosure is not limited to this, and, with the present disclosure, one SRS transmission bandwidth may be divided into a plurality of smaller SRS transmission bandwidths (hereinafter “SRS subbands”) and the narrowband SRS bandwidths may be mapped so as to cover each SRS subband bandwidth evenly in the frequency domain.
FIGS. 17A and 17B show an example of a case where two SRS subbands 1 and 2 are provided in one SRS transmission bandwidth and three SRSs are mapped to each subband.
In the example shown in FIG. 17A , the allocation and the intervals of SRSs mapped in SRS subband 1 are changed according to the variation of a bandwidth of SRS subband 1 such that CQI estimation bandwidth is covered evenly in SRS subband 1 . Likewise, the allocation and the intervals of SRSs mapped in SRS subband 2 are changed according to the variation of a bandwidth of SRS subband 2 such that CQI estimation bandwidth is covered evenly in SRS subband 2 .
Further, as in the example shown in FIG. 17B , the bandwidths of SRS subbands may vary. In this case, the allocation and the intervals of SRSs mapped in SRS subbands may be changed on a per SRS subband basis such that CQI estimation bandwidth is evenly covered.
Although a case has been explained as an example where the number of SRS subbands is two in FIGS. 17A and 17B , the number of SRS subbands may be three or more with the present disclosure. Further, although a case has been explained as an example where the number of SRSs in the SRS subband is three in FIGS. 17A and 17B , with the present disclosure, a plurality of SRSs besides three SRSs may be mapped in the SRS subband.
Further, although mapping examples have been explained with the above embodiments where SRSs are neighboring each other evenly in the SRS transmission bandwidth, in practical systems, SRS bandwidths and positions where SRSs are allocated in the frequency domain are discrete values. Therefore, cases may occur where the SRS transmission bandwidth is not divided by one SRS band. In this case, without using frequency allocation units that have fractions left as a remainder of division, it is also possible to map SRSs so as to cover the CQI estimation bandwidth evenly in the frequency domain in a range that is divisible ( FIG. 18A ). Further, it is also possible to allocate frequency allocation units that have fractions left as a remainder of division between SRSs on a per frequency unit basis ( FIG. 18B ).
Here, the RB (Resource Block) in FIGS. 18A and 18B represents an allocation unit in the frequency domain. FIGS. 18A and 18B are examples where the SRS bandwidth is 4 RBs and the SRS transmission bandwidth is 18 RBs.
Further, although cases have been explained with the above embodiments where SRSs are frequency-hopped (frequency-multiplexed) in the SRS transmission bandwidth at predetermined time intervals, the present disclosure is not limited to this, and provides the same advantage as in cases where frequency hopping is not carried out, as explained with the above embodiments.
The SRSs in the above embodiments may be mapped in RB units or subcarrier units, and may not be limited to any unit.
Further, a CQI showing channel quality information may be referred to as “CSI (Channel State Information).”
Further, a base station apparatus may be referred to as “Node B” and a mobile station may be referred to as “UE.”
Further, although cases have been described with the above embodiments as examples where the present disclosure is configured by hardware, the present disclosure can also be realized by software.
Each function block employed in the description of each of the aforementioned embodiments may typically be implemented as an LSI constituted by an integrated circuit. These may be individual chips or partially or totally contained on a single chip. “LSI” is adopted here but this may also be referred to as “IC,” “system LSI,” “super LSI,” or “ultra LSI” depending on differing extents of integration.
Further, the method of circuit integration is not limited to LSIs, and implementation using dedicated circuitry or general purpose processors is also possible. After LSI manufacture, utilization of a programmable FPGA (Field Programmable Gate Array) or a reconfigurable processor where connections and settings of circuit cells within an LSI can be reconfigured is also possible.
Further, if integrated circuit technology comes out to replace LSI's as a result of the advancement of semiconductor technology or a derivative other technology, it is naturally also possible to carry out function block integration using this technology. Application of biotechnology is also possible.
The disclosures of Japanese Patent Application No. 2007-211548, filed on Aug. 14, 2007, and Japanese Patent Application No. 2008-025535, filed on Feb. 5, 2008, including the specifications, drawings and abstracts, are incorporated herein by reference in their entirety.
INDUSTRIAL APPLICABILITY
The present disclosure is applicable to, for example, mobile communication systems. | Provided is a radio communication device which can prevent interference between SRS and PUCCH when the PUCCH transmission bandwidth fluctuates and suppress degradation of CQI estimation accuracy by the band where no SRS is transmitted. The device includes: an SRS code generation unit ( 201 ) which generates an SRS (Sounding Reference Signal) for measuring uplink line data channel quality; an SRS arrangement unit ( 202 ) which frequency-multiplexes the SRS on the SR transmission band and arranges it; and an SRS arrangement control unit ( 208 ) which controls SRS frequency multiplex so as to be uniform in frequency without modifying the bandwidth of one SRS multiplex unit in accordance with the fluctuation of the reference signal transmission bandwidth according to the SRS arrangement information transmitted from the base station and furthermore controls the transmission interval of the frequency-multiplexed SRS. | 7 |
REFERENCE TO PENDING PRIOR PATENT APPLICATION
[0001] This application claims the benefit under 35 U.S.C. 119 (e) of U.S. Provisional Patent Application No. 61/537,568, filed Sep. 21, 2012 by Hany A. Al-Ansary, et al., for “CERAMIC FOAM SOLAR SOLID PARTICLE RECEIVER,” which patent application is hereby incorporated herein by reference.
BACKGROUND
[0002] The general concept of a cavity receiver 5 for a solar central receiver system 10 can be described as follows. Sunlight is reflected from many mirrors (heliostats), such that most of the reflected sunlight is focused on one small area 15 at the top of a tower 20 . At that location, the concentrated sunlight is allowed to pass through the aperture of a cavity. The intense solar radiation entering the cavity is then used to heat a material, usually a fluid. The heat absorbed by the fluid can then be used to generate power in a variety of ways.
[0003] A different design, called the solid particle receiver, was first conceived in the 1980s. In this design, the material being heated within the cavity is solid particles 25 rather than a fluid. In the tests conducted on this concept, the solid particles were released from a long narrow slot located at the top of the cavity and were allowed to fall freely, forming what may be called a “curtain”. The concentrated sunlight passing through the aperture was captured directly by the solid particle curtain. As a result, the temperature of the solid particles rose significantly. See, for example, FIG. 1 .
SUMMARY
[0004] This Summary is provided to introduce a selection of concepts in a simplified form that are further described below in the Detailed Description. This Summary is not intended to identify key aspects or essential aspects of the claimed subject matter. Moreover, this Summary is not intended for use as an aid in determining the scope of the claimed subject matter.
[0005] In an embodiment, there is provided a receiver panel, configured to receive a curtain of particles in a solar central receiver system, the panel comprising a porous structure having a top end and a bottom end, the porous structure disposed between the top end and the bottom end, and the porous structure having a size to impede movement of the particles during downward travel from the top end to the bottom end.
[0006] In another embodiment, there is provided a solar central receiver system, comprising a plurality of receiver panels, an individual receiver panel configured to receive a curtain of particles, the panel comprising a porous structure having a top end and a bottom end, the porous structure disposed between the top end and the bottom end, and the porous structure having a size to impede movement of the particles during downward travel from the top end to the bottom end; a tower having an upper portion and a lower portion, the upper portion supporting the plurality of receiver panels in a configuration to receive solar irradiation; and a hopper positioned at a height above the plurality of receiver panels, the hopper forming a slot configured to dispose the particles at a given location on to the porous structure.
[0007] In yet another embodiment, there is provided a pipe configured to receive particles in a solar central receiver system, the pipe comprising an inlet portion not necessarily circular in cross section having a first cross section area, the inlet portion forming a passageway sized to transmit at least one of a fluid (such as a molten slat or other fluid) and a stream of solid particles; an outlet portion having a second shape and cross section area, the outlet portion forming a passageway sized to transmit the at least one of the fluid and the stream of solid particles; and a porous structure disposed between the inlet portion and the outlet portion, the porous structure having a size to impede movement of the at least one of the fluid and the stream of solid particles during downward travel from the inlet portion to the outlet portion.
[0008] In still another embodiment, there is provided a method of capturing solar energy with a solar central receiver system, the method comprising releasing a curtain of particles into a cavity configured to receive solar irradiation; and increasing a resident time of the curtain of particles falling through the cavity with a porous structure impeding the fall of the particles.
[0009] Other embodiments are also disclosed.
[0010] Additional objects, advantages and novel features of the technology will be set forth in part in the description which follows, and in part will become more apparent to those skilled in the art upon examination of the following, or may be learned from practice of the technology.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] Non-limiting and non-exhaustive embodiments of the present invention, including the preferred embodiment, are described with reference to the following figures, wherein like reference numerals refer to like parts throughout the various views unless otherwise specified. Illustrative embodiments of the invention are illustrated in the drawings, in which:
[0012] FIG. 1 illustrates prior art experiments on the solid particle receiver concept at Sandia National Laboratories;
[0013] FIG. 2 illustrates a general description of the cavity receiver, (a) illustrates a general layout of the receiver inside the tower, and (b) illustrates a composition of a single receiver panel;
[0014] FIG. 3 illustrates side view of the panel, showing one structural exemplary embodiment;
[0015] FIG. 4 illustrates an exemplary embodiment of solid particle flow within the porous structure;
[0016] FIG. 5 illustrates an exemplary embodiment of a staggered series having a staggered block formation;
[0017] FIG. 6 illustrates an exemplary embodiment of staggered series embodiment having a zig-zag pattern;
[0018] FIG. 7 illustrates an exemplary embodiment of a porous foam block with indented holes;
[0019] FIG. 8 illustrates an exemplary embodiment of a finned pipe;
[0020] FIG. 9 illustrates an exemplary embodiment of opaque surface;
[0021] FIG. 10 illustrates an exemplary embodiment of transmissive cover;
[0022] FIG. 11 illustrates an exemplary embodiment of mesh surface; and
[0023] FIG. 12 illustrates an exemplary embodiment of a simple cavity.
DETAILED DESCRIPTION
Overview
[0024] Embodiments are described more fully below in sufficient detail to enable those skilled in the art to practice the system and method. However, embodiments may be implemented in many different forms and should not be construed as being limited to the embodiments set forth herein. The following detailed description is, therefore, not to be taken in a limiting sense.
[0025] The actual conversion efficiency of the system shown in FIG. 1 was relatively low for two main reasons:
[0026] 1) Due to their free-fall from the long narrow slot, the solid particles 25 quickly attain high velocities such that there is not enough residence time for the particles to attain very high temperatures.
[0027] 2) The presence of voids between the falling solid particles allows some of the incoming concentrated sunlight to penetrate the solid particle curtain 25 and hit the back wall of the cavity, instead of being directly utilized to heat the solid particles.
[0028] Embodiments described herein overcome issues with other solid particle receivers, and also add other enhancing features. FIG. 2 shows a general layout of a new receiver design 200 , which constitutes a core embodiment.
[0029] In one embodiment, the receiver consists of multiple panels 205 that are installed inside a cavity 210 having an aperture 215 and arranged in a general curved shape. The backsides 220 of all panels 205 may be fixed to a structure that can be easily assembled or disassembled for maintenance purposes. Cavity 201 is disposed at a top portion of a tower 225 .
[0030] In an embodiment, each panel may include three components: a porous structure (e.g., a foam block); a back plate; and an insulation block. However, the exact composition of the each panel may vary depending on design and operating conditions.
[0031] FIG. 3 is illustrative of an embodiment of a receiver panel 205 having different layers and is a side view. These layers may include a porous block 305 (or other porous structure 305 ). A back plate 310 may be provided together with an insulation block 315 .
[0032] The following is a description for a working procedure of an exemplary embodiment (see FIG. 4 ):
Solid particles 25 are released from one or more hoppers through a long slender slot and allowed to flow by virtue of gravity. The hoppers are made of appropriate size and flow regulation capabilities. Right after the point of release, the solid particles 25 are immediately allowed to go through the porous block 305 . The presence of numerous ligaments 405 within the porous structure 305 causes the solid particles 25 to collide with those ligaments 405 , thereby impeding their movement and reducing their speed. As the solid particles 25 trickle down the porous block 305 , the originally narrow “curtain” of solid particles 25 may spread. This depends on a number of parameters. The “curtain” spreads in the direction transverse to the general downward direction of solid particle movement due to the aforementioned collisions with the ligaments of the porous structure. As the concentrated sunlight irradiates the porous block 305 , the solar radiation may be partially absorbed by the slow-moving solid particles. Furthermore, any radiation that penetrates through the voids between solid particles 25 may mostly be absorbed by the ligaments 405 of the porous material 305 which, in turn, will transfer the heat to the solid particles 25 .
[0037] As FIG. 4 shows, it is preferable to have the point of release of solid particles 25 retarded or recessed from the front face of the porous foam block 25 . This minimizes radiation reflected by the solid particles 25 , which may not have optimal absorption.
[0038] Since solid particles 25 do not flow through a portion of the porous block 405 , referred to as foam buffer 410 , the buffer 410 is expected to be somewhat hotter than the solid particles. However, the particles 25 flow just behind the buffer 410 induce air flow through the buffer 410 to cause cooling.
[0039] The depth of the foam buffer 410 depends on the dispersion of solid particles 25 during trickle down through the porous foam block. This dispersion depends on a number of parameters, including grain size, initial and terminal velocity, particle sheet thickness, and the porosity and density of the porous foam.
[0040] Another feature that could be employed is preheating of solid particles prior to reaching one or more of the hoppers 415 . This can be done by taking advantage of the hot air that is expected to accumulate at the top of the cavity. The ramp that leads to the one or more hoppers can be designed in a way such that it will be in contact with the hot air. On the other side of the ramp, solid particles can slide down at relatively high speed, getting heated in the process, and making use of the expected high heat transfer coefficient.
[0041] This embodiment overcomes the issues encountered in earlier solid particle receiver designs in a number of ways:
[0042] By employing a cavity receiver 205 , radiation losses are minimized.
[0043] Collision of the solid particles 25 with the numerous ligaments 405 inside the porous block causes the flow of solid particles 25 to be impeded and its velocity to be reduced, thereby providing the solid particles 21 with longer residence time to absorb more energy.
[0044] The reduced velocity of solid particles 25 also reduces the voids between the particles 25 . Furthermore, even if some of the sunlight penetrates the voids between the solid particles 25 , it will be absorbed by ligaments 405 within the porous block 305 , which in turn, indirectly contributes to heating the solid particles 25 . Therefore, the solar energy conversion efficiency may be rather high.
[0045] Since most of the flowing solid particles 25 will be contained within the porous block 305 , solid particle drift due to wind is expected to be very small compared to other designs.
[0046] Finally, instead of porous blocks 305 , an embodiment can also be realized by the use of mesh screens, including metallic mesh screens or mesh screens made of other materials.
Staggered Series
[0047] In this embodiment, the velocity of solid particles is reduced intermittently by the use of obstacles of various forms.
[0048] Staggered Blocks or Meshes
[0049] FIG. 5 illustrates an embodiment of a staggered series of porous foam blocks 305 (or meshes 305 ) arranged vertically to temporarily arrest the free fall of particles 25 and form a panel 505 configured to be irradiated by concentrated sunlight 515 . The spacing 510 of the blocks/meshes 305 is set to control the overall residence time of the particles 25 from their point of release to their point of collection. In this variation, solid particles 25 are irradiated directly during their travel between blocks 305 .
[0050] FIG. 6 illustrates an embodiment of slanted porous foam blocks 305 (or meshes 305 or solid plates 305 ) arranged in a zig-zag pattern 605 to temporarily arrest the free fall of particles 25 and form a panel 610 to be irradiated by concentrated sunlight 615 . The spacing and angle of the blocks/meshes/plates 305 are set to control the overall residence time of the particles 25 and heat the particles passing through the irradiated panel 610 .
[0051] Surface with Front Holes
[0052] In this embodiment, and referring to FIG. 7 , a porous foam block 305 (or mesh screens 305 ) similar to those described above have indented holes 705 in the front surface 710 of the block 305 and arranged in a manner so as to influence the flow of particles 25 and form a panel configured to be irradiated by concentrated sunlight 715 . In this embodiment, more solid particles are allowed to absorb direct sunlight. The spacing of the holes 705 is set to control the overall residence time of the particles 25 and heat the particles passing through the irradiated panel.
[0053] Finned Pipe
[0054] In this embodiment, and referring to FIG. 8 , a porous foam block 305 or mesh screens 305 encase a pipe to form a panel 810 to be irradiated by concentrated sunlight 815 . A fluid 25 (or solid particles 25 ) may move through the pipe 805 and become heated as it passes though the irradiated panel 810 . In this embodiment, the porous foam block 305 (or mesh screen) 305 acts as fins that enhance the heat transfer to the pipe 805 due to the large internal surface area. In various embodiments, the pipe may be configured to receive particles in a solar central receiver system. The pipe may include an inlet portion, which may be circular or other shapes (i.e., the pipe is not necessarily circular in cross section.) The pipe may have a first cross section area. The inlet portion may form a passageway sized to transmit at least one of a fluid (such as a molten salt or other fluid), a stream of solid particles, or both the fluid and stream of solid particles. An outlet portion may be provided having a second shape and cross section area. The outlet portion may form a passageway sized to transmit one or both of the fluid or the stream of solid particles. A porous structure may be disposed between the inlet portion and the outlet portion. The porous structure may have a size to impede movement of the fluid, the stream of solid particles, or both, during downward travel from the inlet portion to the outlet portion.
[0055] In addition to the basic embodiments described earlier, there are a number of other considerations regarding materials used in building the receiver, working materials, surface treatment, as well as receiver location and arrangement.
[0056] Receiver Materials
[0057] The receiver panel may be made of any material that possesses high thermal conductivity and high-temperature durability. However materials of particular interest are silicon carbide, zirconia, titanium oxide, tungsten, and high-temperature steel alloys.
[0058] Working Materials
[0059] It is preferable that particulate materials used in conjunction with the embodiments discussed above possess have high absorptivity, small grain size, high melting point, and high cycling durability. Of particular interest are silica sand, fracking sand, and fracking alumina beads. In an embodiment, 32 . a stream of particles may include a combination of a first set of particles and a second set of particles The first set of particles may include natural particles having a given solar absorptivity. The second set of particles may include artificially created particles having a solar absorptivity greater than the first set of particles. In one embodiment, the higher absorptivity particles may be captured and recirculated through the receiver.
[0060] Surface Treatment
[0061] The surface which receives the incoming concentrated sunlight may be treated in many different ways. The following are exemplary surface treatments:
[0062] Natural Open Face
[0063] This is the surface type described in embodiments discussed above. However, the surface may have a coating to increase absorptivity to solar irradiation.
[0064] Opaque Surface
[0065] This is a surface that is sealed to prevent particles from escaping (see, for example, FIG. 9 ). As in the previous case, the surface may be treated with a coating 905 to increase absorptivity to solar irradiation.
[0066] Transmissive Cover
[0067] This is a clear layer 1005 over the front face to prevent particles from escaping and allow direct transmission of solar irradiation (see, for example, FIG. 10 ). A potential material for this layer is quartz.
[0068] Mesh Surface
[0069] This is a mesh layer 1105 over the front face to partially prevent particulates from escaping and partially allow direct transmission of solar irradiation (see, for example, FIG. 11 ). The mesh may be made of a high-temperature material such as tungsten.
[0070] Receiver Location and Arrangement
[0071] The receiver may be located inside a cavity, with a number of panels, and may be arranged in a generally curved shape. However, there are other possibilities for location of the receiver and its arrangement.
[0072] Simple Cavity
[0073] FIG. 12 illustrates a cavity 1205 with a general cubic shape, and the receiver is made of multiple panels 305 lining the sides of the cavity.
[0074] Flat Receiver
[0075] In its simplest form, the receiver can be flat, consisting of one or more panels. In this case, the receiver is not enclosed within a cavity.
[0076] Although the above embodiments have been described in language that is specific to certain structures, elements, compositions, and methodological steps, it is to be understood that the technology defined in the appended claims is not necessarily limited to the specific structures, elements, compositions and/or steps described. Rather, the specific aspects and steps are described as forms of implementing the claimed technology. Since many embodiments of the technology can be practiced without departing from the spirit and scope of the invention, the invention resides in the claims hereinafter appended. | There is disclosed a receiver panel. In an embodiment, the panel is configured to receive a curtain of particles in a solar central receiver system. A porous structure of the panel has a top end and a bottom end. The porous structure is disposed between the top end and the bottom end. The porous structure has a size to impede movement of the particles during downward travel from the top end to the bottom end. There is disclosed a solar central receiver system. In an embodiment, the receiver system includes a plurality of receiver panels, a tower supporting the plurality of receiver panels in a configuration to receive solar irradiation, and a hopper forming a slot configured to dispose the particles at a given location on to the porous structure. Other embodiments are also disclosed. | 5 |
The invention relates to a device with a prosthesis implantable in the body of a patient, especially in a blood vessel or other body cavity, and designed as a hollow body. The prosthesis is compressible against the action of restoring spring forces down to a cross section which is reduced relative to an (expanded) operating position. The prosthesis may be also automatically expanding to a cross section corresponding to the operating position following removal of the restraining forces effecting the compression.
BACKGROUND
Devices of this type are known, and serve for percutaneous implantation of vascular prostheses in particular. Prostheses which are introducible percutaneously and expand in the lumen are either expandable mechanically by means of a known balloon catheter from a small radius to the larger radius to hold a vascular lumen open, or they expand automatically following previous compression prior to implantation by spring force, due to spring pretensioning generated during compression.
Various systems are already known for inserting self-expanding vascular prostheses which are under spring force into the body of a patient, and to implant or anchor them in the vessel by removing the restraining force.
The commonest method, which is described in EP-A-0 183 372, consists in compressing an endoprosthesis, made in the form of a tubular hollow body, to a reduced cross section and then pushing it in the compressed state, using a so-called pusher, through a catheter previously introduced into a vessel until they are in the correct position in the vessel. However, this system suffers from the disadvantage that a considerable expenditure of force is required to push the prosthesis through the catheter because its displacement is counteracted by considerable frictional forces.
Another method (not confirmable by publications) consists in retracting a sheath covering the endoprosthesis and holding the latter together, in the vessel at the implantation site. Here again there is the disadvantage that high frictional forces must be overcome. Moreover, the tube system is quite rigid because of the sheath covering the prosthesis, making introduction into a vessel through curves very difficult.
In another system (U.S. Pat. No. 4,732,152) a woven and spring-tensioned prosthesis is held together in the compressed state by a double sheath, sealed at the distal end. This sheath is retracted from the folded prosthesis like a stocking being pulled off the foot of a wearer. To reduce the friction which then occurs, liquid can be introduced between the two sheath layers. This system, which initially appears elegant because of the reduction of the frictional resistances, is extremely cumbersome to handle however and requires two persons to operate.
On the other hand, the invention is intended to provide an especially simple and readily operable device for implantation of a prosthesis made in the form of a hollow body, with a vascular prosthesis envisioned in particular.
SUMMARY OF THE INVENTION
This goal is achieved by virtue of the fact that in the device according to the preamble of claim 1 the prosthesis is surrounded by a sheath which can be pulled off it, said sheath consisting of at least one through thread, and compressed to a reduced cross section, and by the fact that at least one drawstring is provided, said drawstring being laid so it extends away from the sheath holding the prosthesis in its radially compressed state, the thread forming said sheath being retractable.
In the invention, the prosthesis is therefore held in its radially compressed state by means of this external sheath and reaches its intended expansion position only after removal of this sheath, which is designed to be pulled off, thanks to the pretensioning force generated during compression.
The sheath can be in particular a meshwork produced by crocheting, knotting, tying, or other methods of mesh formation.
Advantageously the prosthesis, held by the sheath which can be pulled off in the radially compressed state, can be received on a probe, or a flexible guide wire, and advanced thereon. In one design of a device of this kind, implantation is accomplished by introducing the guide wire in known fashion into a vessel and then advancing the prosthesis, held in a radially compressed state, along the guide wire, said wire being advanced for example by means of a sleeve likewise advanced over the guide wire and engaging the end of the prosthesis away from the insertion end thereof.
Another improvement, on the other hand, provides that the prosthesis, held in the radially compressed state by the sheath which can be pulled off, is held in an axially fixed position on the insertion end of a probe. Specifically, this probe can be a catheter advanced over a guide wire.
Even with the axially fixed mounting of the prosthesis, held in the compressed state, on the insertion end of a probe or a catheter, implantation takes place in simple fashion with the probe or catheter being advanced together with the prosthesis mounted on the insertion end, for example under the control of x-rays, up to the implantation site, and then by pulling off the sheath, made for example as a covering meshwork, the prosthesis is exposed and implanted in the proper location by its automatic expansion.
In mounting the prostheses on the insertion ends of probes or catheters, it has been found to be advantageous for the prosthesis to be mounted on a non-slip substrate surrounding the probe or catheter, so that undesired slipping and sliding during the release of the thread material forming the meshwork cannot occur.
Advantageously, the self-expanding prosthesis can be a tube made by crocheting, knitting, or other methods of mesh formation, composed of metal and plastic thread material with good tissue compatibility, said tube being compressible radially against the action of pretensioning forces and automatically expanding into its operating position after the restraining forces are removed, and then remaining in the expanded position.
In the case of the prosthesis designed as meshwork, according to a logical improvement, successive rows of mesh can be made alternately of resorbable thread material and non-resorbable thread material. This means that within a predetermined period of time after implantation, the resorbable thread material will be dissolved and the prosthesis parts, then consisting only of non-resorbable thread material, will remain in the patient's body. These remaining components form circumferential rings of successive open loops. This avoids thread intersections which could exert undesirable shearing forces on surrounding and growing tissue coatings.
In the improvement just described, drugs can also be embedded in the resorbable thread material so that the prosthesis constitutes a drug deposit which gradually dispenses drugs during the gradual dissolution of the resorbable thread material.
An especially advantageous improvement on the invention is characterized by making the tubular meshwork holding the prosthesis in the compressed state in such a way that the mesh changes direction after each wrap around the prosthesis and when successive meshes are pulled off, the thread sections forming the latter separate alternately to the right and left from the prosthesis.
The advantage of this improvement consists in the fact that the mesh wrapped successively and alternately left and right around the prosthesis can be pulled off without the thread material becoming wrapped around the probe holding the prosthesis or a catheter serving as such, or undergoing twisting, which would make further retraction of the thread material more difficult because of the resultant friction.
It has also been found to be advantageous in the improvement described above for the loops or knots of the mesh wrapped successively around the prosthesis and capable of being pulled off, to be located sequentially with respect to one another or in a row running essentially axially.
Another important improvement on the invention provides for the drawstring to extend away from the mesh surrounding the insertion end of the prosthesis, and therefore the prosthesis, as the meshwork is pulled off its distal end, gradually reaches its expanded position.
In this improvement, the thread material to be pulled off when the prosthesis is tightened can never enter the area between the already expanded part of the prosthesis and the wall of a vessel for example. The thread material to be pulled off instead extends only along the part of the mesh which has not yet been pulled off and thus in the area of the prosthesis which is still held in the compressed position.
The ends of the thread material forming the meshwork can be held by releasable knots, in the form of so-called slip knots for example, and thereby have their releasability preserved. One especially simple means that has been found for axial mounting of the prosthesis on a probe or on a catheter serving as such is for the beginning of the thread material forming the meshwork and an end mesh to be pinched in holes in the probe or catheter, yet capable of being pulled out of their pinched positions by means of the drawstring. The beginning of the thread material can be pinched between the probe and the cuff mounted held on the latter, however.
The cuff material is held especially securely, but at the same time in such a way that it can be easily pulled off, if from the knot of the mesh of the first mesh on the pull-off side of the meshwork, a loop passed through a hole extends, one end of said loop making a transition in the vicinity of the above knot to the drawstring. As a result, this loop can be pulled off by means of the drawstring through the above-mentioned knot and then all of the mesh forming the meshwork can be pulled off in succession.
According to another logical improvement on the invention, the prosthesis can also be held in its radially compressed position by means of a meshwork applied from the distal end of the probe or catheter and extending over the insertion end of the prosthesis and by means of a meshwork that extends in the direction opposite the proximal end and also extends over the end mesh of the first meshwork. It has been found advantageous in this connection for the two meshworks to be capable of being pulled off in opposite directions from their loop-shaped end meshes by means of drawstrings.
In a design of this kind, following correct placement of the prosthesis mounted on a probe or a catheter in a vessel, the meshwork applied from the distal end is pulled off first, beginning with the end mesh removed from the distal end and then advancing gradually until this meshwork is removed completely and the thread material is retracted. Then the meshwork applied from the proximal end is pulled off, starting with the end mesh toward the distal end and then advancing toward the proximal end. It is obvious that when the meshwork is pulled off in this way, the self-expanding prosthesis is expanded gradually, starting at its distal end, into its intended operating position.
In another important embodiment, the sheath that holds the prosthesis in its radially compressed position consists of loops surrounding the prosthesis and spaced axially apart, said loops being formed by the thread material, pulled through a hole in the prosthesis, of a thread guided along inside the prosthesis, with the ends of the loops each being brought back through a hole, adjacent to the first hole in the circumferential direction, into the interior of the prosthesis, and a warp thread, likewise running along the inside of the prosthesis and guided through the ends of the loops, holds in the loops in their wrapping positions. It is clear that in this design the prosthesis is released by pulling the warp thread out of the end segments of the loops, and that the thread material forming the loops, like the warp thread, can be retracted in simple fashion. In a similar improvement on the invention, the sheath holding the prosthesis in its radially compressed position consists of loops which are axially spaced apart and are wrapped around the prosthesis, said loops being formed by thread material, pulled through a hole in the prosthesis, of a thread guided along inside the prosthesis, with the ends of the loops each being brought back into the interior of the prosthesis through holes spaced axially from the first hole, and held in place by the fact that a loop formed from the thread material running inside the prosthesis is pulled through each loop end brought back into the prosthesis, said loop then being brought out through a hole following in the axial direction, then being wrapped around the prosthesis and brought back in the same manner with its loop end passing through a hole into the prosthesis and being secured in this position. In this design also, the pulling off of the sheath holding the prosthesis in its radially compressed position is accomplished in simple fashion by means of the thread extending from the last loop, from which the loops surrounding the prosthesis are formed.
For especially tight wrapping and the resultant compression of the prosthesis, it has also been found advantageous to use shrinkable thread material to form the meshwork. The meshwork that can be pulled off can also consist of a plurality of threads running parallel to one another.
Another important improvement on the invention provides that between the prosthesis and the sheath holding the latter in the radially compressed state, at least one additional sheath is provided which loosely fits around the prosthesis and allows a partial expansion of the prosthesis when the outer sheath is pulled off, and is itself subsequently capable of being pulled off.
This improvement is also one that involves a sheath, surrounding the prosthesis loosely and with a certain amount of play, being mounted on said prosthesis, which can be a meshwork, with the prosthesis and the inner sheath being surrounded closely by an outer sheath which holds the prosthesis, together with the sheath mounted directly on it, in the radially compressed state. The prosthesis is consequently surrounded by two layers, so to speak, and after the outer sheath is stripped, can expand only within the limits set by the inner sheath. The final implantation is then accomplished by stripping the inner sheath, i.e. in stages.
Of course, several meshworks surrounding one another with a certain amount of play can be provided, which permit expansion of the prosthesis in several successive stages.
Within the scope of the invention, the spaces between the meshes of a meshwork surrounding the prosthesis and holding it in the compressed state can be filled and smoothed with gelatin or a similar substance which dissolves in the body of a patient. This facilitates introduction of such a device.
According to yet another improvement, at least one end of the prosthesis can be surrounded in the compressed state by a cuff, said end, because of the axial shortening of the prosthesis that takes place during expansion, escaping the grip exerted by the cuff. A cuff of this kind can be mounted permanently on the probe and/or a catheter, with the open side facing the prosthesis, for example on the side toward the distal end. This produces a smooth transition that facilitates introduction, at the end of the prosthesis which is at the front in the insertion device.
For improved attachment of the prosthesis to a probe or to a catheter serving as same, the end of the prosthesis facing away from the insertion end can abut at a radially projecting step or shoulder or a cuff mounted on the probe or catheter.
Yet another improvement on the invention provides that when a catheter is used as a probe, the drawstring is introduced through a hole passing through the catheter wall in the vicinity of one end of the prosthesis, enters the lumen of the catheter, extends through the latter, and extends beyond the end of the catheter.
However, a double-lumen catheter can also serve as a probe with one lumen serving to advance the catheter over a guide wire and the other lumen being used to guide the drawstring.
When using a catheter with one or two lumina as a probe, with the drawstring passing through the catheter lumen, assurance is provided that the walls of the vessels or other body cavities in which a prosthesis is to be implanted cannot be damaged by the drawstring and/or, when the meshwork is stripped, by the thread material, which is then pulled back through the catheter lumen.
It has also proven to be advantageous for the drawstring and/or the thread material of the meshwork to be provided with a friction-reducing lubricant.
In addition, at least the drawstring can be made in the form of a metal thread or provided with an admixture of metal, so that good visibility with x-rays is ensured.
Finally, according to yet another improvement, the prosthesis, kept in the radially compressed position by the strippable sheath, can expand to resemble a trumpet at its proximal end in the expanded state following removal of the sheath,. This prosthesis design is important for implants in the vicinity of branches in the vessels, because there is always the danger of the prosthesis slipping into the branching vessel. In view of the trumpet-shaped expansion at the proximal end, however, such slipping during implantation is effectively suppressed when the sheath surrounding the prosthesis is stripped off the proximal end.
DESCRIPTION
One embodiment of the device according to the invention will now be described with reference to the attached drawing. Schematic views show the following:
FIG. 1 shows a catheter with a vascular prosthesis mounted on its distal end held under radial pretensioning in the compressed state by a crocheted material in the form of a strippable tubular meshwork;
FIG. 2 is a view showing the formation of an initial mesh of crocheted material on the prosthesis, with a loop brought around the vascular prosthesis on the right side;
FIG. 3 is a view like that in FIG. 2, showing the formation of a crocheted mesh adjoining the initial mesh, wrapped around the vascular prosthesis on the left side;
FIG. 4 is a view similar to FIG. 1, showing a design for a device in which the vascular prosthesis mounted on the catheter is held in its compressed state with radial pretensioning by means of strippable crocheted material mounted on the distal and proximate ends;
FIG. 5 shows the device according to FIG. 4 but with the crocheted material applied from the distal end;
FIG. 6 shows the device according to FIG. 4 with the crocheted material applied from the proximal end alone, eliminating the crocheted material shown in FIG. 5;
FIG. 7 shows the vascular prosthesis alone, held in a radially compressed position by wrapping loops;
FIG. 8 is a view like that in FIG. 7 of a prosthesis in which the loops holding the latter in a radially compressed position are formed by crocheting, and
FIG. 9 shows a portion of a vascular prosthesis in the form of knitted fabric.
In device 10 shown in FIG. 1, an elongated catheter 11 serves as a probe, with a through lumen by which the catheter can be advanced in known fashion over a guide wire inserted in a vessel. In the vicinity of its distal end 12 , catheter 11 carries a prosthesis 15 held in a compressed position under radial pretensioning by means of a crocheted material 14 , said prosthesis, following elimination of the restraining force provided by the crocheted material, changing to its intended expanded position by expanding automatically. For example, the prosthesis can be a tubular knitted fabric radially compressible against the effect of a restoring spring force into a position in which it fits closely around the catheter in the vicinity of its distal end.
Prosthesis 15 is surrounded by a crocheted material 14 formed by a continuous thread, with successive meshes wrapped around the prosthesis alternately on one side or the other, in other words alternately on the right or left side. The initial section 17 of the thread material, located in front of the first mesh 16 associated with the distal end 12 of catheter 11 , is pulled through a slot 18 in the catheter wall, pinched in said slot, and then extends through the catheter lumen and out through the distal end of the catheter. A strippable loop 22 is pulled through a knot 21 that closes end mesh 20 which is remote from the distal end, said loop being pulled through two cuts 23 , 23 ′ in the catheter wall, and is therefore likewise held axially by pinching.
The free thread end guided through knots 21 of said end mesh 20 forms a drawstring 24 extending along catheter 11 , by means of which drawstring, first loop 22 held on the catheter by pinching and then gradually the mesh formed of crocheted material extending around the prosthesis and holding the latter in its compressed state, can be stripped through said end knot. Since the meshes are wrapped alternately right and left around prosthesis 15 , when the mesh is stripped the threads on the right and left sides of the catheter are released alternately from the corresponding mesh knots, and after the mesh facing the distal end comes loose, initial segment 17 of the thread material can be pulled out of its pinched position in slot 18 at distal end 12 of catheter 11 .
In an enlarged view, FIGS. 2 and 3 show the mesh formation with alternate front and back wrapping of catheter 15 , which in these figures is shown as a rigid tubular structure for the sake of simplicity. After securing initial section 17 of the thread material in the manner shown in FIG. 1 by pinching in slot 18 , the thread is wrapped around the catheter, then a loop 26 is pulled through under the thread, and then from free thread material 27 , a mesh on the back of the catheter is pulled around the latter and passed through loop 26 , whose section pulled through the above loop 26 in turn forms a loop 28 to form the next mesh. FIG. 2 shows free thread material 27 in solid lines before it is pulled through loop 26 , and shows it in dashed lines after it is pulled through this loop and forms loop 28 for the next mesh.
To form the next mesh, as shown in FIG. 3, forming another loop 30 in the manner shown by the dashed lines, the free thread material is pulled out of the position shown at 31 in front of the catheter, through previously formed loop 28 , and then this process of loop and mesh formation is continued, with the thread material pulled alternately behind and in front of the catheter through the respective loops until the prosthesis held in the catheter is crocheted over its entire length.
Loop 22 , pulled through the loop associated therewith or through a knot 21 formed by pulling together these loops to form end mesh 20 , is then pulled in the manner shown schematically in FIG. 1 through the two axially spaced slots 23 , 23 ′ in the wall of the catheter and held in place by pinching. The remaining thread material then forms drawstring 24 which extends from the loop of end mesh 20 and permits the crocheted material to be stripped, with the thread material of the meshes as they are stripped alternately coming loose on one side or the other of prosthesis 15 , thereby releasing the prosthesis to expand under the pretensioning force imposed during crocheting as a result of radial compression.
In embodiment 40 shown in FIG. 4, a prosthesis 45 is mounted and held in its compressed position under radial pretensioning on an elongated catheter 41 in the vicinity of distal catheter end 42 . This purpose is served by crocheted material 46 , 47 shown in FIGS. 5 and 6. Catheter 41 , like catheter 11 of the embodiment shown in FIG. 1, is advanceable by means of a guide wire located in a vessel, in said vessel so that prosthesis 45 mounted on the catheter is implantable positionwise in the vessel prior to its implantation by stripping the crocheted material.
The crocheted material that holds prosthesis 45 in the compressed position shown in FIG. 4 is applied sequentially, with crocheted material 46 starting at the distal end. The other crocheted material 47 is applied from the proximal end and then overlaps the end of the first crocheted material 46 .
FIG. 5 shows that catheter 41 is provided on the distal end with a silicone cuff 43 , which serves to hold the initial segment 48 of the thread required for the formation of the first crocheted material. For this reason, initial segment 48 of this thread is pulled through beneath silicone cuff 43 . Then the first meshes 49 , in the manner explained above in conjunction with FIGS. 1 to 3 , are crocheted on catheter 41 , and provide a firm seat on the catheter for the first crocheted material. Subsequent meshes 50 fit over the end of prosthesis 41 that points toward the distal end of the catheter, and compress the latter under radial pretensioning with simultaneous axial immobilization of the prosthesis on the catheter, as shown in FIG. 5. A final mesh 51 of this crocheted material 46 is then applied externally on prosthesis 45 , with thread 52 extending from this mesh as a drawstring to strip the mesh of the above-mentioned crocheted material.
FIG. 6 shows the application of the second crocheted material 47 from the proximal end. Beginning 55 of the thread material of this crocheted material is again held by means of a silicone cuff 54 pulled onto the proximal end of catheter 41 , while the beginning of the thread is pulled through beneath this cuff. Then several meshes 56 are crocheted onto the catheter in the direction of the distal end, followed by additional meshes 57 , while wrapping prosthesis 41 during its simultaneous radial compression up to and beyond meshes 50 , 51 of the first crocheted material 46 facing away from the distal end, which are held thereby. A last mesh 58 of the crocheted material 47 applied from the proximal end is then pulled through under silicone cuff 43 pushed onto the distal end of the catheter, and held thereby. In addition, thread 60 extends from the end mesh facing the distal end of the crocheted material 47 applied from the proximal end, as a drawstring to strip the mesh of this crocheted material.
The prosthesis 45 in the embodiment shown in FIGS. 4 to 6 , like that in the embodiment shown in FIGS. 1 to 3 , is held under radial pretensioning in the compressed position on catheter 41 and automatically expands to its expanded position after removal of crocheted material 46 , 47 . Following introduction of the prosthesis mounted on the catheter into a vessel and its location in place, implantation occurs in such fashion that crocheted material 46 applied from the distal end is removed first. This is accomplished by stripping the mesh of this crocheted material by means of drawstring 52 , with mesh 51 located beneath the crocheted material applied from the proximal side being stripped first and then gradually meshes 50 and 49 abutting the distal end being stripped until eventually the first mesh adjacent to silicone cuff 43 comes free and the beginning of thread 48 beneath the silicone cuff is pulled out.
Since the end of the prosthesis that points toward the distal catheter end is released by stripping crocheted material 46 applied from the distal end, this end of the prosthesis expands radially as a result of the pretensioning forces of the prosthesis itself, while the remaining part of the prosthesis is still held in the compressed position by crocheted material 47 applied from the proximal end. Partially expanded prosthesis 45 is axially immobilized in this position both by the adhesive effect between the catheter and the prosthesis and by a silicone cuff 62 mounted on the proximal end of prosthesis 45 on catheter 41 , which cuff the prosthesis abuts axially.
After stripping first crocheted material 46 , crocheted material 47 applied from the proximal end is also stripped, specifically by means of drawstring 60 extending from its end mesh 58 on the side pointing toward the distal end. It is clear that when the drawstring is pulled, loop 58 held at the distal end beneath silicone cuff 43 is stripped first and then meshes 57 and 56 are stripped, starting at the side facing the distal end, gradually in the direction of the proximal end, with prosthesis 45 expanding radially and abutting the walls of a vessel to be equipped with a prosthesis. At the end of the stripping process, thread end 55 located beneath silicone cuff 54 at the proximal end is pulled free. Prosthesis 45 is then free of catheter 41 and the latter can be withdrawn in simple fashion out of the vessel.
Prosthesis 70 shown in FIG. 7 is likewise tubular in shape and self-expanding. It can be a meshwork, roughly in the form of a knitted fabric. The prosthesis is provided with holes 71 , 72 associated with one another pairwise and located at approximately equal axial distances from one another. Loops 74 surrounding the prosthesis externally hold the prosthesis together in its radially compressed state. These loops are thread material, each pulled through a hole 71 , of a thread 75 running along the inside of the prosthesis, said thread then surrounding the prosthesis forming a loop with tension, and with loop end 76 , each being introduced through a hole 72 corresponding to matching hole 71 , back into the interior of the prosthesis. The loops are held in the wrapping position shown in FIG. 7 by means of a warp thread 78 guided through loop ends 76 inside the prosthesis.
The advantage of the embodiment shown in FIG. 7 consists in the fact that loops 74 wrapped around the prosthesis at essentially constant axial intervals are used as means for radial compression of prosthesis 70 , said loops having no external knots at all but formed by a thread 75 running along the inside of the prosthesis and held in the tensioned position by means of the warp thread 78 likewise running along the inside of the prosthesis.
The prosthesis according to FIG. 7, in the same way as described above in conjunction with FIGS. 1 to 6 , is mounted in a radially compressed state on a catheter in the vicinity of the distal catheter end, and is implantable by means of the catheter by advancing the latter in a vessel. Following correct positioning in the vessel, implantation is accomplished in simple fashion by pulling warp thread 78 out of ends 76 of loops 74 , whereupon prosthesis 70 expands radially under its own spring pretensioning force to its proper expanded position. Thread 75 which is pulled to form the loop can then likewise be simply pulled back.
The embodiment shown in FIG. 8 differs from the embodiment in FIG. 7 in that loops 74 surrounding prosthesis 70 ′ and spaced axially apart are formed by crocheting. Through a hole 71 ′ in the prosthesis, thread material from thread 75 guided along the interior of the prosthesis is pulled out and wrapped as a loop 74 ′ around the prosthesis, and is also introduced through a hole 72 ′ spaced axially from above-mentioned hole 71 ′, together with loop end 76 ′, back into the interior of the prosthesis. Thread material is then pulled through this loop end 76 ′ located in the interior of the prosthesis, forming another loop and guided externally through a hole 71 ′ following in the axial direction, then is wrapped again around the prosthesis as loop 74 ′ and secures the loop end, brought back into the interior of the prosthesis through another hole 72 ′, in the same manner as the first loop.
Referring to FIG. 9, a knitted intravascular prosthesis 80 (partial view to illustrate component threads) is shown in which a thread 81 of resorbable material and a thread 82 of non-resorbable material are knitted together alternately. The non-resorbable thread material can be tantalum for example.
The advantage of this prosthesis design consists in the fact that the resorbable thread material dissolves following expiration of a predetermined period of time after implantation, and then only the non-degradable components remain in the body of a patient. These remaining components form circular rings of successive open loops. In this manner, thread crossings are avoided, which could exert unnecessary shearing forces on the surrounding and growing tissue coatings.
Prostheses according to FIG. 9 can also be designed in simple fashion as drug deposits with drugs being imbedded in the resorbable thread material and released as this material degrades. | The device comprises a prosthesis designed as a hollow body compressed against the action of restoring spring forces to a cross section reduced relative to an expanded use position, and held in this position by a strippable sheath. After the sheath is stripped, the prosthesis automatically expands to a cross section corresponding to the use position. The sheath, which can be a meshwork in the approximate form of crocheted material, extends over the entire length of the prosthesis and consists of at least one continuous thread and at least one drawstring. The prosthesis, held in the radially compressed position by the sheath, can be mounted displaceably on a feed wire or non-axially-displaceably on the insertion end of a probe or a catheter. | 3 |
This application is a continuation of application Ser. No. 383,427, filed July 27, 1973, now abandoned.
CROSS-REFERENCE TO RELATED APPLICATION
Putman U.S. patent application Ser. No. 383,425, filed July 27, 1973, is a related application in that it discloses and claims the basic invention upon which this invention is considered to be an improvement.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to the art of refrigerant expansion valves.
2. Description of the Prior Art
One commonly used automatic expansion valve for controlling the flow of refrigerant between a condenser and an evaporator is called a constant pressure refrigerant expansion valve and is designed to attempt to keep a constant absolute pressure in the evaporator during operation of the system. This valve is typically operated by a preset spring force and a force derived from the feedback of the pressure from the evaporator. The valve is arranged so that with the valve set and feeding refrigerant at a given pressure, a small increase in the evaporator pressure will act to move the valve toward a closing direction, thereby restricting the refrigerant flow and limiting the evaporator pressure. When the evaporator pressure drops below the valve setting because of a decrease in load, the valve moves in an opening position to increase the refrigerant flow in an effort to raise the evaporator pressure to the particular balanced valve setting. In a number of applications of the valve, including some room air conditioners, the valve is provided with a bypass in the form of a small slot or drilled hole in the valve seat or valve pin to prevent complete valve close-off when the compressor shuts down. This is to permit refrigerant to continue to flow at a reduced rate until high and low side pressures are equalized.
While the bypass type valve provides for the equalization after several minutes, it is believed that the bypass itself contributes to a problem which occurs when an air conditioner is operated without any forced air flow over the evaporator and condenser. In such an arrangement using a constant pressure bypass type valve, and starting with the system pressures equalized, but with the fans not operating, the valve remains closed and gives a bypass feed only. If this occurs in a system using an expansion valve which also includes a relief valve, and with, say, R-22 refrigerant, the relief valve will open at say a 600-700 p.s.i. differential so that refrigerant can then flow to the compressor and load it sufficiently that the current and temperature overload means will be operated to shut the compressor down. However if the expansion valve does not include the relief value, the condenser pressure can build up to a valve of up to 200 p.s.i. over what would be desirable before the current and temperature overload of the compressor operates. It is believed that if the bypass in the expansion valve were omitted, it is likely that the high pressure problem would be avoided. However this would not permit equalization of the system after shutdown.
The valve according to the invention is considered to be preferable in that no bypass arrangement is needed for equalization, and under a fan failure condition the valve functions in a manner which does not create any problems for the air conditioning system itself.
Of the prior art patents of which applicant is aware, U.S. Pat. No. 1,786,110 is considered to be the closest in the field of refrigerant expansion valves, but differs substantially in that it in effect includes two valves, one of which functions as an on-off valve, while the other functions like a capillary tube; neither of which corresponds to the operation of the valve of applicants' invention.
Flow control devices for controlling the flow of lubricant to hydrostatic bearings and similar in structure to the valve arrangements embodying this invention are disclosed in U.S. Pat. No. 3,110,527. However these devices are incorporated in a system where an increase in differential pressure between a source pressure and the load pressure is taught to result in a restriction of the flow which would be directly the opposite of the result of the operation of the refrigerant expansion valve of this invention.
SUMMARY OF THE INVENTION
In accordance with this invention, the refrigerant expansion valve includes a valve body having a disc-shaped deflectable member supported at its periphery from the valve body and separating the interior of the valve body into an upstream space and a downstream space, the disc-shaped deflectable member being provided with a generally centered aperture, the valve body also having structure therein spaced relatively closely to that part of the deflectable members defining the aperture so that the structure defines, with the aperture defining part, an annular refrigerant expansion orifice therebetween, the upstream space in the valve body confining the liquid refrigerant in its passage through the valve and thereby subjecting the upstream face of the member to the pressure of the liquid refrigerant, and with the downstream space in the valve confining the expanded vaporous refrigerant in its passage and thereby subjecting the downstream face to the pressure of the expanded vaporous refrigerant, so that the deflection of the deflectable member and correspondingly the change in the effective opening of the orifice is in accordance with changes in the differential pressure of the liquid and expanded vaporous refrigerant.
As is noted in the companion Putman patent application, it is emphasized that the differential pressure across the expansion valve is used to control the refrigerant flow area of the valve so that the quantity of flow is a function of the difference between the supply (condenser) and outlet (evaporator) pressures, rather than simply being a function of the pressure in the evaporator as is the case with the constant pressure refrigerant expansion valves.
DRAWING DESCRIPTION
FIG. 1 is a schematic representation of an air conditioning system in which the invention may be incorporated;
FIG. 2 is a sectional view of the expansion valve according to the invention and corresponds to a view taken along the line II--II of FIG. 3;
FIG. 3 is a plan view of one form of the valve;
FIG. 4 is a sectional view corresponding to one taken along the line IV--IV of FIG. 2;
FIG. 5 is an enlarged fragmentary view illustrating the general relationship between the part of the disc including the aperture and the facing nozzle-shaped structure;
FIG. 6 is a schematic representation of a refrigerant expansion valve of the type having an apertured disc-shaped deflectable member for reference in connection with selecting specific values in accordance with a design example;
FIG. 7 is a graphical representation illustrating the general relationship between pressure drop and valve openings for a typical air conditioner for purposes of explaining the design example; and
FIG. 8 is a graphical representation of pressure drop versus valve opening for the design example for a specific room air conditioner.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The same general principles in the design of the valve forms disclosed in the companion noted patent application, and the form of valve of this invention are applicable, and accordingly reference should be had to the noted patent application for the fullest understanding of these general principles.
In FIG. 1, the schematically illustrated refrigerant system includes a compressor 10, condenser 12, evaporator 14, the connecting refrigerant lines between these components, an expansion device 16 in the line between the condenser and evaporator, and a fan-motor assembly 18 for supplying separate flows of air over the condenser and evaporator as is conventional in air conditioning systems.
An example of a currently preferred form that the valve according to the present invention may take is shown in FIGS. 2-5. The hollow valve body 36 is provided with an inlet 22 adapted to be connected to a refrigerant system condenser, and one or more outlets 24 and 24a adapted to be connected to a refrigerant system evaporator. The hollow interior of the valve body contains a flexible disc-shaped member 38 supported at its periphery by the valve body 36 and having a generally centered aperture 40. The structure 42 which is supported from the valve body base and which with the member 38 defines the expansion orifice 44 has an upper chamfered end 43 which is similar in shape to a nozzle structure and accordingly is so termed the nozzle structure 42. The annular expansion orifice 44 is defined between the upper rim of the nozzle structure 42 and the bottom rim of the aperture 40. With this arrangement the space 46 on the upper side of the disc 38 is subject to the liquid refrigerant supply pressure from the condenser, while the lower space 48 below the disc is subject to the expanded vaporous refrigerant pressure. As will be apparent hereinafter, the aperture 40 is large enough relative to the annular expansion orifice 44 that the expansion takes place in the passage of the refrigerant through the orifice 44.
As noted in the companion patent application, it is believed that the arrangement of the valve as shown in FIG. 2, in which the entire opposite faces of the disc 38 are subject to the different pressures, is advantageous in that this is believed to reduce the likelihood of flow induced vibrations requiring dampening of the flexible member. The theory is that a pumping type action would arise from vibration of the disc and this would be self-dampening. Also, since the differential pressure ie effective over virtually the total disc area, it is believed that the valve can likely be operated at higher force levels with less uncertainty (on a percentage basis) about the area the pressure differential acts upon. Additionally, any potential problem from deformation of the lower part of the valve body is reduced since it is acted upon by the outlet pressure, which is substantially lower than the supply pressure. Finally, it will be appreciated that since the entire lower space 48 contains expanded refrigerant, multiple outlets from the space can be accommodated more easily than where the upper end of the nozzle structure 42 constitutes the inlet to the outlet passage from the valve. The use of multiple outlets from the lower space 48 can be advantageous where the valve is to be used for multiple evaporator circuit applications.
In the arrangement described, the upper face of the disc is subject to the liquid refrigerant supply pressure, while the lower face of the disc is subject to the pressure of the expanded vaporous refrigerant. Based upon the total area of the faces of the disc subject to the pressure producing the forces causing deflection, slight differences in the diameter of the aperture 40, and the diameter of the upper end of the nozzle structure 42 are of little significance with respect to the forces applied to cause deflection of the disc. With the arrangement described, the change in differential pressure across the expansion orifice (which corresponds substantially with the changes in the differential pressure between the condenser and evaporator) results in changes in the deflection of the disc and accordingly results in changes in the effective opening of the expansion orifice 44.
In the operation of the valve described, under a high load condition for an air conditioning system the pressure differential between the condenser and evaporator is greater than when the system is operating under rated conditions, or under a low load condition. Under the high load condition, the greater differential pressure causes greater deflection of the disc, and accordingly results in an effective expansion orifice which is smaller than at the other conditions. The converse is of course also true in that the effective opening of the orifice is greater when the load is less, due to the lesser differential pressure.
In designing a valve to carry out the invention, the designer starts with knowledge of the desired pressure drop across the valve for, say, two of three conditions such as high load, rated load, and low load, and then can determine the required valve openings for two of the three conditions. That is, the valve is designed so that its characteristic is such that it passes through two selected points on a plot of differential pressures versus valve openings. The way in which a valve such as that illustrated in FIG. 2 is designed and calculated is described in the following.
The basic parts of the described expansion valve are the deflectable disc 38 and the expansion orifice 44 as are shown schematically in FIG. 6. The concept of using this valve as a refrigerant control device is based on the pressure and flow rate characteristics of a selected air conditioner system. The notations below are defined for the purpose of the calculations which follow, and which are intended to explain an example of the underlying theory and design procedure for a particular valve.
P 1 = psi, inlet pressure
P 2 = psi, outlet pressure
ΔP = P 1 - P 2 = psi, pressure drop across the valve
x = in., orifice opening
x o = in., value of x when ΔP = 0
d = in., disc diameter of faces of disc subject to pressure (selected as 1.0")
A = in. 2 , effective orifice area
K = lb/in., disc stiffness
t = in., disc thickness
n = in., nozzle diameter (selected as 0.110")
r = in., disc aperture radius (selected as 0.0475")
Q = f 3 /sec, discharge flow rate
C d = discharge coefficient
ρ = slug/ft 3 , fluid density
f = lb, force on the disc
W = lb, total applied load
y = x o - x = in., vertical deflection
E = psi, modulus of elasticity
Subscripts h and l denote the high and low load conditions, respectively.
The force acting on the disc body can be expressed by f = (π/4) d 2 Δ P. Also, the force can be expressed in terms of disc stiffness and deflection, i.e., f = Ky = K(x o - x). Hence, (π/4) d 2 Δ P = K(x o - x)
or
ΔP = (4/π) (K/d.sup.2) (x.sub.o - x) = m(x.sub.o - x) (1)
where
m = (4/π) (K/d.sup.2)
From Equation (1) it may be seen that the valve opening is related to the pressure drop across the valve. This relationship is also graphically illustrated by the straight line valve characteristic line 66 in FIG. 7.
Line 68 of FIG. 7 illustrates a typical shape of a curve of values of pressure drop versus valve opening that can be obtained by adjusting the valve opening of a manually adjustable expansion valve of an air conditioner operated under a high load condition while measuring the corresponding pressure drop. Line 70 of FIG. 7 illustrates a typical shape of a curve for operation under a low load condition.
The valve designer has control over the slope and the x intercept of the valve characteristic. Therefore, as illustrated in FIG. 7, it is theoretically possible to design the valve to satisfy any high load and low load pressure drop requirements (i.e., by operation at points H and L) so long as these requirements are consistent with other constraints of the valve design.
Although the above discussion has been based upon meeting specified high load and low load operating points, by design the valve can as well meet specified high load and rated load, or low load and rated load points. Since there are only two independent design parameters, the slope and the intercept, the design cannot generally meet independently specified high load, rated load, and low load operating pressure drops. However, from a practical point of view it is not necessary to meet three independent conditions.
The following paragraphs give a numerical example of how to design a valve to meet high and low load conditions for a specific room air conditioner charged with R-22 refrigerant and having a nominal 15,000 BTU per hour rating. The values set forth in the table below are those measured and calculated from the operation of such an air conditioner provided with a conventional automatic expansion valve.
______________________________________ Low Load Rating High Load Conditions Conditions Conditions______________________________________Pressure Drop P (psi) 142 253 322Flow Rate (lb/hr) 203 209 244Density before Valve(Slug/ft.sup.3) 2.225 2.190 2.145Flow Rate (cfs) 7.90 × 10.sup.-.sup.4 8.24 × 10.sup.-.sup.4 9.05 × 10.sup.-.sup.4______________________________________
From the standard orifice equation, the effective expansion orifice area A is found for high and low load conditions, as follows: ##EQU1## where C d = 0.611 is obtained from FIG. 85 of the reference book of H. Rouse entitled "Elementary Mechanics of Fluids," published by John Wiley and Sons, 1960.
The nozzle diameter is selected to be 0.110 in. to get reasonable values of x for high and low load conditions.
x.sub.h = (A.sub.h /π .sub.n), x = (A/90 .sub.n)
Then, x h = 0.00298 in., and x 1 = 0.00397 in.
The ratio of the area of disc aperture πr 2 and the area of effective orifice (πnx l ) at low load conditions is 5.16. This area ratio is large enough so that the annular opening is the principal restriction and controls the expansion.
By plotting the high and low load operating points in a ΔP versus x plane as shown in FIG. 8, a calculated or a graphical determination can be made of the x o intercept and -m the slope, these determinations being x o = 0.0048 in. and -m = - 1.82 × 10 5 lb./in 3 , from line 72.
Then the required beam stiffness is calculated based on a disc diameter of d = 1.00 in.
K = (πd.sup.2 /4) (m) = (π/4)(1.0).sup.2 × 1.82 × 10.sup.5 = 1.423 × 10.sup.5 lb/in
Next, it is required to determine the disc thickness which will realize this stiffness. The relationship between the deflection and load for such a disc is given in the text by R. J. Roark. Formulas for Stress and Strain and takes the form:
Y = (W/ Et.sup.3) C (4)
where
E = 30 × 10 6
W is the total load uniformly distributed.
C in in. 2 is a constant which depends upon the outside diameter, the hole diameter and Poisson's ratio which is taken to be 0.270. For an outside diameter of 1.0 in. and a hole diameter of 0.095 in., the value of C is 0.245.
The stiffness is w/y so that the disc thickness can be expressed as follows: ##EQU2##
Experimental operation of the disc type valve of this invention shows that it, along with the beam-type valves of the companion patent application, compares favorably with the conventional automatic expansion valve in performing the throttling function at low, rated and high load conditions. Since it does not respond to evaporator pressure increases alone, and is open during off periods of compressor operation, it does not impose a limitation of waiting to restart the compressor until equalization of pressures occurs through a bleed port. Fan motor failures are avoided as a problem with this type of valve without any requirement of a pressure relief device. Finally, the simplicity of the construction, and the limited number of parts, should be apparent from the foregoing description. | An automatic expansion valve for controlling refrigerant flow from a condenser to an evaporator in which the valve includes an apertured deflectable disc which defines the refrigerant expanson orifice with other structure within the valve, and with the flow passage arrangement in the valve body being such as to subject the upstream face of the disc to the pressure of the liquid refrigerant, and the downstream face of the disc to the pressure of the expanded vaporous refrigerant so that the disc deflects in accordance with the differential pressure on the opposite faces and accordingly effects changes in the effective opening of the expansion orifice. | 5 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a §371 national stage entry of International Application No. PCT/AU2013/000906, filed Aug. 16, 2013, entitled “MODULATED CLAMPING FORCE GENERATOR FOR TOROIDAL CVT,” which claims priority to Australian Application No. AU 2012903525, filed Aug. 16, 2012, which are incorporated herein by reference in their entireties.
TECHNICAL FIELD
The present invention relates to continuously variable transmissions (CVT).
BACKGROUND OF THE INVENTION
Most CVT mechanisms rely on pressure to create a frictional force between one surface and another to transfer torque from one rotating member to another.
In the case of a Toroidal CVT, traction rollers are clamped between an input and output disc; while in the case of belt or chain CVTs belt segments are clamped between similar discs. In both cases tangential force is transferred from the clamped component (roller or belt segment) to and from the discs through a special Traction Fluid.
The Traction Fluid has the unique property of increasing its viscosity when under pressure. When under high pressure of 0.5 GPa this increase is of the order of 10,000 times while when under very high pressures of 2 GPa the increase is of the order of 1,000,000,000 times. The graph in FIG. 1 illustrates this pressure dependant relationship and also its corresponding relationship with temperature.
This high viscosity allows the fluids to transmit high shearing forces between two surfaces with only small differences in speed (creep) between the two surfaces when the contact pressure between the two surfaces is high. The limitation on how large these forces can be is related to the properties of the materials used in the rolling or translating elements, and the design life of the device.
The power density of a CVT using these fluids is directly related to the relationship of the allowed tangential force to the applied clamping force. This is most often referred to as the Traction Coefficient. The maximum Traction Coefficient is the highest ratio between the tangential force and the contact force and is typically less than 0.1. When the tangential force is greater than that defined by this upper limit the contact will start to slip excessively. The heat generated by this slip reduces the viscosity and the slip increases at an exponential rate. By using a higher Traction Coefficient more torque can be transferred; but above a certain level too much creep or slip will occur and the efficiency of the CVT will suffer. Most toroidal traction drives use a traction coefficient of around 0.06-0.07.
The clamping force must be high enough to transfer the tangential forces without excessive slipping, and the tangential force must never become great enough to cause a gross breakdown of the fluid film caused by excessive slip and accompanying excessive heating.
It is not generally accepted that the clamping force remain constant and large enough to manage the highest tangential forces that could be generated in the CVT. Normally some form of Ball Ramp device is placed in the input drive that is designed to generate a clamping force that is directly proportional to the input torque. This ensures that high contact forces are only present when high torque is passing through the CVT. This significantly extends the fatigue life of the components stressed by the clamping force and the life of the Traction Fluid.
These ball ramps are designed to convert the input torque (typically from an engine) to an axial or clamping force and are for this reason placed on the input side to the CVT.
However the quantum of the tangential forces generated within the toroidal CVT mechanism is both a function of the torque and the ratio position of the rollers. Typically, with the Ball Ramp mounted on the input side, the system is adequately clamped when in low gear (when tangential forces are high) but “over clamped” when the system is in high gear.
The detailed geometry of the rollers and discs also affect the degree of over- or under-clamping. The particular geometry of the half toroidal CVT (SHTV) is suited to an input mounted ball ramp as it becomes only slightly over clamped when in high and low gear.
Elimination of over-clamping will extend the life of a CVT and improve its efficiency.
Typical Ball Ramp
A typical Ball Ramp arrangement consists of two plates that are each machined with slots that face each other and trap a ball or roller. One plate is connected to the inputted rotating energy and the other to the system being rotated. The slots consist of two ramps so that when torque is applied to the “Input Ramp Disc” the ramps force the roller against the opposing ramp machined in the “Output Ramp Disc” and create a clamping force.
The quantum of the clamping force is defined by this equation:
CF =( T× 1 /r )/TAN θ
Where:
1. CF is the clamping force in Newtons 2. T is the input torque in Nm 3. r is the radial distance from the centreline of rotation to the centre of the roller or ball in meters 4. θ is the ramp angle in degrees
In a typical CVT the amount of normal force required to transmit forces is given by this equation:
NF=TF/μ
Where
1. NF is the normal force in N 2. TF is the tangential force at the point of contact in N that must be generated between the input disc and the roller belt or chain. 3. μ is the traction coefficient
The use of a Ball Ramp with a Toroidal CVT is relatively simple and shown in FIG. 2 . FIG. 3 depicts a similar arrangement using a roller supported on an axle that bears up against a single ramp. Because the toroidal discs do not move the clamping can be executed using only mechanical interactions, provided deflections are allowed for.
The angle of the ramp is arranged to provide the right clamping force to ensure no slip occurs at the contact of the Discs and Rollers.
As noted earlier, the correct angle is derived from the formula NF=TF/μ, with TF being the maximum tangential force, which in this arrangement occurs at low gear.
As the CVT changes ratio towards a higher gear the clamping force becomes more than is needed and the discs are effectively over clamped. Only in low gear is the Traction Coefficient operating at its preferred value. This behaviour is peculiar to toroidal traction drives, other traction drives such as those that use balls or discs like a kopp variator, are most suitable for application of an input clamping ball ramp.
It is possible to design a system that uses an additional piston that can be engaged or disengaged as the ratio changes giving a stepped reduction in clamping force.
With this two stage system it is important that any reversed torque (such as that occurring during engine braking) is very low; as when the torque reverses the relative tangential forces become greater in over drive (high gear) than in under-drive. This arrangement is fundamentally unsuitable for use in a flywheel based KERS as the reversing torques are very high. It is also unsuitable when used in a multi stage IVT when the variator is swept more than once through a full ratio change.
It is an object of the present invention to create a clamping system based on simple mechanical components to create as close to ideal normal clamping forces on the roller contact points in a traction based variator.
The invention can be applied to toroidal variators, both single and half, and to other forms of variator requiring control of clamping forces.
SUMMARY OF THE INVENTION
According to the present invention there is provided a toroidal variable speed traction drive comprising: a driving toroidal disc assembly and a driven toroidal disc assembly, the toroidal disc assemblies having a common axis of rotation; a plurality of roller assemblies interposed between the toroidal discs, each roller assembly comprising at least one roller; wherein the toroidal discs are urged together against the interposed roller assemblies by an axially directed clamping force, wherein each roller of each roller assembly contacts each toroidal disc at contact points; the driving toroidal disc assembly is driven by an input drive shaft which provides an input torque; the driven toroidal disc drives an output structure, that rotates around the common axis of rotation, the output structure driving an output shaft; wherein an interposed clamping arrangement is provided between the driven toroidal disc and the output structure, the interposed clamping arrangement provides the axially directed clamping force which is proportional to an output torque experienced by the output shaft.
In exemplary embodiments, the driving toroidal disc assembly is driven by an input structure, that rotates around the common axis of rotation, the input structure is driven by the input drive shaft; wherein a second interposed clamping arrangement is provided between the driving toroidal disc and the input structure, the second interposed clamping arrangement provides an axially directed clamping force which is proportional to the input torque; wherein the axially directed clamping force provided by the second clamping arrangement is opposite in direction to the axially directed clamping force provided by the first clamping arrangement.
The input and output structures can be connected to allow the displacement of one structure to cause displacement of the other structure, wherein the mutual displacement of the input and output structures ends when the clamping forces provided by the first and second clamping arrangements reach equilibrium.
The invention proposed here encompasses a system of a clamping Ball Ramp or ramps that use an output based ball ramp either in isolation or use both ramps, one on the input side and one on the output side. When the output ramp is employed the clamping in high gear can be arranged to be very close to the required clamping when in the overdrive (speed up) ratios but over clamped when in the underdrive (speed down) ratios. This is advantageous in particular applications where low torque states are experienced only in low gear such as a Variable Volume Super Charger where no resistance torque is possible until the turbine is spinning at high speed. When both ramps are used it is possible to arrange so that, the lowest clamping forces generated on either side becomes the actual clamping force so that excessive over-clamping is avoided across the entire ratio spread.
BRIEF DESCRIPTION OF THE DRAWINGS
Preferred embodiments of the present invention will now be described with reference to the accompanying drawings, in which:
FIG. 1 is a graph showing the typical pressure and viscosity relationship of a traction fluid;
FIG. 2 illustrates a schematic of a prior art configuration of a full toroidal CVT with an input ball clamping arrangement;
FIG. 3 illustrates a schematic of a prior art configuration of a full toroidal CVT with an input roller clamping arrangement;
FIG. 4 shows a graph illustrating the force relationships for input and output based clamping arrangements with a schematic of such arrangements;
FIG. 5 shows a graph illustrating the force for input and output based clamping arrangements for a VVS mechanism operating at a speed of 2,000 rpm;
FIG. 6 shows a graph of the same arrangement as FIG. 5 operating at a speed of 4,000 rpm;
FIG. 7 shows a graph of the same arrangement as FIG. 5 operating at a speed of 6,000 rpm;
FIG. 8 is a cross-sectional view of an embodiment of the present invention applied to a single cavity double roller full toroidal variator coupled to a variable volume supercharger;
FIG. 9 is a cross-sectional view of another embodiment of the present invention applied to a double roller full toroidal variator when in a high ratio position;
FIG. 10 represents a longitudinal section along the input and output clamping arrangements for the embodiment illustrated in FIG. 9 when in various ratio and load conditions;
FIG. 11 represents an axial view of the input and output clamping arrangements of FIG. 9 ;
FIG. 12 illustrates the embodiment shown in FIG. 9 when in a low gear position;
FIG. 13 shows cross-sectional views of another embodiment of the present invention applied to a double cavity, double roller full toroidal variator in high and low gear.
DETAILED DESCRIPTION OF THE INVENTION
As a precursor to the present invention it is proposed to arrange a Ball Ramp on the output side of the CVT and design the ramp angle so that it provides the correct clamping for High Gear operation. In practice, it was found that this will cause over-clamping as the CVT moves to lower gears. This over clamping necessitates that the CVT is designed much heavier than a CVT with an input ramp. The over clamping in high gear caused by an input ramp affects the efficiency and life but does not necessitate a heavier design and for this reason can used in Toroidal devices.
A particular type of engine enhancement system called Variable Volume Supercharger (VVS) is being applied to internal combustion engines as a way of downsizing their swept volume but retaining a large engine performance. In this application, a Toroidal CVT is coupled to a turbine so that when the engine is running at low RPM and the driver calls for acceleration the CVT moves from a low gear to a high gear and speeds up the turbine creating boost pressure at low RPM allowing for rapid acceleration response. The CVT then backs away from high gear as the engine speed increases to avoid over revving the turbine. Known designs to date all use an input based clamping force generating ramp.
This mechanism can benefit from the use of an output based ramp system because although the output ramp “over clamps” in low gear the torque in low gear is typically very low and the over clamping never necessitates the deliberate over engineering that would be necessary in a typical CVT transmission.
However, if the CVT is used in a Turbo Compounder where exhaust gas energy is returned to the engine crankshaft (once the engine is running at a high speed) the torque is high enough to make this state the critical state when determining the component sizes. The result being a situation where the CVT in low gear is both over clamped and over stressed.
FIG. 8 depicts a section through a Variable Volume Supercharger in which a pulley 38 drives a shaft 14 that is splined to a driving toroidal disc 4 that is clamped over rollers 16 onto a driven disc 3 . The pulley diameter is typically arranged to run at around double the engine speed. A ball ramp with a captured ball 1 is built into the driven disc 3 and a ramp structure 5 that drives an output disc 12 connected to an output shaft 13 . The output shaft 13 drives the planet carrier of a traction drive epicyclic step-up gear set 42 that increases the speed of the shaft 43 that is connected to the turbine 40 located inside a turbine housing 39 by a typical ratio of between 10:1 and 13:1. A thrust bearing 11 is held against the back of the driven disc 3 and the shaft 14 that acts as the clamping force restraint mechanism. In this arrangement the turbine is designed to deliver compressed air to the intake manifold of an Internal Combustion engine. The sump 41 is designed to collect the traction fluid in which these devices operate.
The rollers 16 and associated carriages can be rotated by the circular rack gear 45 driven by the worm 46 so as to change the relative speeds of the Driven and Driving discs 3 , 4 . The worm gear is in turn driven via a pinion gear connected to a shaft driven by an electric motor 44 . The section is drawn in the ratio where the driving disc 4 is speeding up the driven disc 3 and in turn the turbine 40 by a combined speed increase of around 30:1. When the rollers 16 are rotated back to low gear position the speed increase is typically 6:1.
The pressure of the air is dependent on the speed of the turbine and generally is very low at speeds below 60,000 RPM rising to 1-2 bar at speeds of 120,000 RPM. This means that when in low gear there is very little torque passing through the system and the clamping force generated by the ball ramp arrangement 1 is well below what it develops when in high gear. When in High gear the ramp arrangement 1 develops the clamping force required to ensure that no slip occurs between the discs 3 , 4 and rollers 16 .
A similar situation exists when applied to a kinetic energy recovery system (KERS) where energy is stored in a high speed flywheel and torque flows in both directions in and out of the flywheel. Any simple mechanical clamping system either placed on the input or output side will result in both over clamping and over stressing in some ratios.
It is also important to understand that because the clamping force created by either an input or output ramp is parallel to the discs' axis of rotation the actual “normal” force needed at the contact point to resist this is always greater in any position other than the central position. There is a “wedging” affect because of the curvature in the toroidal disc so that the actual normal force is equal to the axial force (created by the ramp) times the inverse of the COS of the angle by which the roller has been rotated.
FIG. 4 shows the relationships of the required normal forces (at constant torque) to produce a constant relationship between the normal force and the traction force (Constant traction coefficient or “perfect clamping”) and the force created by an input or output based ramp. It can be seen that the input based ramp creates over-clamping in High gear (between B and C) while the output based ramp over-clamps in low gear (between A and B).
FIG. 5 shows a similar relationship for a VVS mechanism operating at an engine speed of 2,000 RPM. It can be seen that when the CVT is in low gear the turbine is running at such a low speed that very little torque is required to be inputted to the CVT. As the ratio is changed and the turbine is sped up a greater and greater amount of torque is required to be inputted with the greatest torque level reached when the CVT is in high gear. If an input based ramp is being used to control the clamping force it will create a normal force on the rollers that is much more than is necessary and in designing with this type of arrangement the rollers will need to be made larger than necessary to carry this force. The physical size of the CVT will become bigger than necessary. It can be seen that although the output based ramp creates a normal force that is greater than necessary when the CVT is in a low gear that this force is always much less than the maximum required normal force and has no effect on the design of the CVT in terms of component sizing.
FIG. 6 shows the same VVS mechanism with the engine operating at 4,000 RPM. It is now necessary to restrict the upper level ratio of the CVT to around 1.5:1 so that the turbine does not over speed. It can be seen that the use of an output based ramp continues to keep the normal forces higher than necessary but the output based ramp remains at or below the maximum required normal force.
FIG. 7 shows it at an engine speed of 6,000 RPM where the CVT ratio must be restricted to below 1:1 to prevent the turbine over speeding. Again the output based ramp delivers close to the correct normal force at the 1:1 ratio and is in fact identical to it in this design. The output based ramp does over clamp the CVT more than the input ramp at this speed but again never clamps more than the maximum (ever) required normal force.
Another embodiment is shown in FIG. 9 .
The cross section illustrated is of a Double Roller Full Toroidal Variator or DFTV using a single cavity. A driven disc 104 is rotated by a clamping roller that is trapped inside the input ramps 102 . One of these ramps is formed in the driven disc 104 and one is formed in the ramp support structure 106 . The ramp support structure 106 is driven by torque fingers 108 connected to a finger support plate 113 which is driven by an input shaft 109 . Preload springs 115 are loaded between the input ramp support structure 106 and the finger support plate 113 . The fingers 108 can move axially inside apertures in the input ramp support structure 106 running on low friction rollers.
A clamping shaft 114 bears up on the back of the preload springs 115 and passes through the discs 103 , 104 to the other side of the variator to be held onto a thrust bearing 111 by a nut 118 . The thrust bearing 111 on the output side bears up against an output ramp support structure 105 which has a ramp 101 formed in its face matching a similar ramp in the driving disc 103 inside which is another trapped clamping roller. The trapped clamping rollers are ideally ball bearings, as shown. The driven disc 104 and the driving disc 103 clamp over rollers 116 providing the necessary axial force in operation to create the normal forces that are large enough but not excessively large to carry the tangential rolling contact forces.
The roller trapped within ramp 101 is driven by the driving disc 103 which drives the output ramp support structure 105 which drives torque fingers 107 which are connected to an output drive plate 112 which drives an output shaft 110 .
It can be seen that when the variator is in a high gear position the torque generated at the input side is greater than that generated at the output side. The input ramp 102 is capable then of overcoming the force generated at the output and it rolls the trapped rollers along the input ramps 102 until the output ramp 101 is closed.
This action can be seen in FIG. 10 . Position A corresponds with the section shown in FIG. 9 (High Gear but carrying low torque). The force generated in the output ramp 101 is overcome by the force being generated by the input ramp 102 and the output ramp 101 is “closed” with the roller on the input side reaching a stop where it can no longer exert any greater force. The clamping force is now being generated by the output ramp 101 . This particular state is one in which the input torque is great enough to overcome the preload springs 115 but not enough to cause large axial deflections in the variator itself. Consequently, the roller trapped within output ramp 101 is located towards the centre of the output ramps 101 . If the input torque is increased, deflections allow the trapped roller to roll a considerable distance along the output ramp 101 and so the ramps must be long enough to accommodate this axial deflection. In this case, the design is for a typical road car transmission where the forward torques are much larger than the reverse (engine braking torque) so the input ramp 102 on the reversed torque side can be much smaller.
Position B corresponds with the variator being in low gear (see FIG. 12 ) where the output ramp 101 generates a higher clamping force than the input side ramp 102 and the trapped rollers shuttle to the other side with the ramp structures themselves moving a small distance X (see FIG. 12 ) and moving the Clamping Shaft 114 axially to the left. In diagram B of FIG. 10 the system is carrying low torque so the input ramp roller remains near the centre of the input ramp 102 .
In Diagram C, the system is operating under high torque that will create deflections that allow the trapped input roller to move along the input ramp 102 . The trapped roller on the output ramp 101 has moved all the way to the end-stop where it can no longer clamp to any greater degree than the input ramp roller 102 .
It can be seen by now looking at the graphs in FIGS. 4 to 7 that the object of maintaining a degree of clamping that is sufficient to avoid slip, but not a great deal too much, is achieved.
The “clamping shaft” 114 with thrust bearing 111 attached can move axially a small distance if the force being generated at one of the ramps 101 , 102 is greater than the other. The ramps 101 , 102 themselves are built into the back of the input and output toroidal discs 103 , 104 and the input ramp structure 106 and the output ramp structure 105 plates. They are formed in the shape of a flat “V” which terminates in a stop that prevents the trapped rollers from rolling any further along the slot when it reaches the end of the ramp.
FIG. 10 shows typical sections through these ramps with the trapped clamping rollers in the positions they adopt for various configurations.
FIG. 11 shows a plan view and section of these ramps as they relate to the input and output ramps. The ramp angle for these ramps is set up to deliver the required clamping for either ramp that will be sufficient to ensure that the traction coefficient is always kept low enough to guarantee no gross slip. In this design the ramp angle of the Output ramp A is 2.28° and the Input ramp B 5.2°. The section through the output ramp A shows the Driving disc 103 and the output ramp structure 105 with the Input ramp made up of Driven disc 104 and Input Ramp structure 106 . Each ramp has a forward torque section 119 and a reverse torque section 120 . The relative size of 19 and 20 being related to the relative intensity of the maximum forward and reverse torques.
In this case the ramps are designed for a conventional transmission application where the forward torques (acceleration) are always much greater than the reverse torques (engine braking) and so one side of the ramp is longer to accommodate the greater overall deflections that occur in the forward torque state. In a mechanism, such as a Kinetic Energy Recovery System where forward and reverse torques would be more or less the same, the ramps would need to be equal lengths.
It can be seen that when one ramp is generating the greatest force the trapped ball roller will roll up the ramp to the end stop and the actual clamping force will become the lower of the two forces. In this way a very good compromise normal force is applied to the rollers 116 with little over clamping regardless of what ratio the CVT is in. This can be seen in the earlier described FIG. 4 .
FIG. 12 shows the same CVT as in FIG. 9 after it has moved to Low gear with the clamping force being generated by the input ramp 102 . The Clamping Shaft 114 has moved to the left under the influence of the higher clamping force being generated on the output ramp 101 . The trapped roller ball on the output ramp 101 is now hard up against the respective ramp end stop with the other trapped roller ball on the input ramp 102 being free to move and generate the input ramp clamping force.
Diagram D in FIG. 10 represents the roller ramp positions when operating under zero torque. Both trapped rollers have moved to the bottom of the ramps under the influence of the preload springs 115 . The rollers roll through this position during a torque reversal when, for an instant, there is no torque. As soon as torque is generated the rollers will roll up both ramps 101 , 102 and establish equilibrium when the clamping force from both ramps 101 , 102 is equal.
The ramps 101 , 102 can also be designed with a curved slope so that the clamping balance is established when each trapped roller is resting on a section of the ramp that allows the torque to establish equal clamping forces. A curved ramp can be used to create exactly the correct clamping force with a small degree of excessive clamping that exists with the ramp using a constant slope and a stop eliminated. It is also possible to create a hybrid of curve and stop that makes the arrangement less sensitive to deflection induced hysteresis in a way that can reduce over clamping to an even greater extent.
FIG. 13 shows the double ramp system applied to a double cavity DFTV. It can be seen that in this case the clamping shaft 214 also carries torque to a second cavity and it is necessary for the shaft 214 and the entire second cavity arrangement to move axially during a ramp “change over”. The change over occurs at or near the 1:1 ratio point. Because there is no torque reaction in the torque reaction plates when at the 1:1 position, very little torque is passing the torque tube as the transition occurs.
FIG. 13A represents the section of the variator when in high gear positions with the output ramp 201 providing the clamping force and the input ramp trapped roller 202 on the stops. FIG. 13B shows the same variator in Low gear with the output ramp 201 on the ramp stop and the Input Ramp 202 providing the clamping force.
There are two driving or input discs 204 and 204 A and two driving or output discs 203 and 203 A that form two toroidal cavities, enclosing the rollers 216 . In this double roller design the rollers 216 are supported on Yokes 231 which are connected by a swivel joint (not shown) to a trunnion 230 . The Trunnions 230 are fitted with circular rack gears 228 in the second cavity and 229 in the first cavity which are driven by a worm gear 237 located in the first cavity and another 226 located in the second cavity.
The worm gear 226 , 237 is driven by a pinion gear 236 connected to a shaft (not shown) driven by an electro mechanical actuator.
The trunnions 230 in the first cavity C are supported on a pair of Torque Reaction Plates 227 and the trunnions 230 in the second cavity D are supported on a similar pair of plates 233 . These plates 227 , 233 carry the torque reactions from the trunnions 230 which, in the 1:1 ratio, are zero in a double roller design. One of these Torque Reaction Plates in both cavities is provided with a Torque reaction Tube 224 and 225 that transfer torque from the second cavity to the first cavity through Torque Fingers 222 , which include rollers on the First cavity tube that roll in an aperture built into the second cavity tube. An oil gallery sliding tube flows oil to flow from one Torque Reaction Plate to the other which provides lubrication to the rollers.
The entire assembly of second cavity D discs, reaction plates, trunnions, yokes, gears and rollers can slide axially along the Clamping Shaft 214 . The worm gears are provided with a castellated sliding connection 223 that allows them to slide axially while maintaining the same rotational position relative to the Circular rack gears.
When input torque is provided to the input shaft 209 all of this torque is transferred via the input torque fingers 208 via the input torque disc 213 to apertures in the Input Ramp Structure 206 . Approximately 50% of this torque is transferred to the second cavity D via a splined connection 235 between the shaft 214 and the ramp structure 206 . The other 50% is transferred to the First cavity input (driven) disc 204 by the interaction of the rollers and ramps 202 such interaction also producing a clamping force that acts through the rollers 216 to the first cavity output (driving) disc 203 .
The first cavity output disc 203 drives the trapped roller 201 located in the Output ramp structure 205 while providing a clamping force that reacts on the second cavity output disc 203 A which clamps on the rollers 216 in the second cavity which bear up against the second cavity input disc 204 A. The clamping force is transferred along the shaft 214 to counteract the force being generated in the first cavity by the trapped rollers on the input ramp 202 . The output ramp structure 205 outputs torque via the torque fingers 207 to the Output Bell housing 234 which is connected to the output shaft 210 . The output ramp support structure 205 is connected or even part of the second cavity output disc 203 A and the 50% torque that arrives from the second cavity passes to it for collection by the output torque fingers 207 .
It is important to understand that the first and second cavity will share the torque equally between themselves because small slips occur at all of the rolling contacts. The size of these slips is related to the amount of torque being passed and if one cavity is carrying more than 50% of the torque it will slip more and in consequence lose the ability to carry more than 50% of the torque.
The system can now respond to different input torques and different ratio positions as before with the clamping forces being created by half the input torque and generally being half the size of the clamping forces in a single cavity variator using this method of clamping. As the variator passes through the 1:1 position where the clamping force created at the input ramp 202 and output ramps 201 are equal the mechanism inside the second cavity will move the distance X in FIG. 13B which swaps the ramps creating the clamping maintaining optimized clamping.
It can be seen that the shaft 214 could be arranged to extend through the output shaft 210 allowing for collection of the two shaft speeds and torques for incorporation in an IVT mechanism that uses an epicyclic gear to achieve additional benefits.
The illustrated embodiments are of a Double Roller Full Toroidal Variator however it is clear that the method described in this invention could be used in other forms of Toroidal Variator including the Single Roller Full Toroidal Variator, the Single Roller Half Toroidal Variator and variators using other forms of control method including Torque Control.
It can also be seen that the double ramp arrangement could be used as a servo system using lower forces and much smaller ramps and ball rollers or sliding ramps to create a hydraulic pressure designed to provide the full clamping force. In such a system the ramps could be physically remote from each other using only the hydraulic fluid to connect them.
It will be understood by someone skilled in the art of traction based CVTs, including but not limited to toroidal, planetary, belt and chain types, that the use of a double ramp could be used in many ways to control clamping forces so as to improve efficiency, power density or life of the mechanism. | A toroidal variable speed traction drive is provided. The drive comprises a driving toroidal disc assembly ( 4 ) and a driven toroidal disc assembly ( 3 ). The toroidal disc assemblies ( 3, 4 ) have a common axis of rotation. A plurality of roller assemblies are interposed between the toroidal discs ( 3, 4 ). Each roller assembly comprises at least one roller ( 16 ). The toroidal discs ( 3, 4 ) are urged together against the interposed roller assemblies by an axially directed clamping force. Each roller ( 16 ) of each roller assembly contacts each toroidal disc ( 3, 4 ) at contact points. The driving toroidal disc assembly ( 4 ) is driven by an input drive shaft ( 14 ) which provides an input torque. The driven toroidal disc ( 3 ) drives an output structure ( 5 ), that rotates around the common axis of rotation, the output structure ( 5, 12 ) driving an output shaft ( 13 ). An interposed clamping arrangement ( 1, 5 ) is provided between the driven toroidal disc ( 3 ) and the output structure ( 5, 12 ), the interposed clamping arrangement ( 1, 5 ) provides the axially directed clamping force which is proportional to an output torque experienced by the output shaft ( 13 ). | 5 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. application Ser. No. 10/628,781 filed on Jul. 28, 2003, which is hereby incorporated by reference. Applicant therefore, claims priority based on the filing date of U.S. application Ser. No. 10/628,781.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] Not Applicable.
BACKGROUND OF THE INVENTION
[0003] 1. Field of the Invention
[0004] The present invention relates to a visualization technique for co-rendering multiple attributes in real time, thus forming a combined image of the attributes. The combined image is visually intuitive in that it distinguishes certain features of an object that are substantially indistinguishable in their natural environment.
[0005] 2. Related Art
[0006] In the applied sciences, various fields of study require the analysis of two-dimensional (2-D) or three-dimensional (3-D) volume data sets wherein each data set may have multiple attributes representing different physical properties. An attribute, sometimes referred to as a data value, represents a particular physical property of an object within a defined 2-D or 3-D space. A data value may, for instance, be an 8-byte data word which includes 256 possible values. The location of an attribute is represented by (x, y, data value) or (x, y, z, data value). If the attribute represents pressure at a particular location, then the attribute location may be expressed as (x, y, z, pressure).
[0007] In the medical field, a computerized axial topography (CAT) scanner or magnetic resonance imaging (MRI) device is used to produce a picture or diagnostic image of some specific area of a person's body, typically representing the coordinate and a determined attribute. Normally, each attribute within a predetermined location must be imaged separate and apart from another attribute. For example, one attribute representing temperature at a predetermined location is typically imaged separate from another attribute representing pressure at the same location. Thus, the diagnosis of a particular condition based upon these attributes is limited by the ability to display a single attribute at a predetermined location.
[0008] In the field of earth sciences, seismic sounding is used for exploring the subterranean geology of an earth formation. An underground explosion excites seismic waves, similar to low-frequency sound waves that travel below the surface of the earth and are detected by seismographs. The seismographs record the time or arrival of seismic waves, both direct and reflected waves. Knowing the time and place of the explosion, the time of travel of the waves through the interior can be calculated and used to measure the velocity of the waves in the interior. A similar technique can be used for offshore oil and gas exploration. In offshore exploration, a ship tows a sound source and underwater hydrophones. Low frequency (e.g., 50 Hz) sound waves are generated by, for example, a pneumatic device that works like a balloon burst. The sounds bounce off rock layers below the sea floor and are picked up by the hydrophones. In either application, subsurface sedimentary structures that trap oil, such as faults and domes are mapped by the reflective waves.
[0009] The data is collected and processed to produce 3-D volume data sets. A 3-D volume set is made up of “voxels” or volume elements having x, y, z coordinates. Each voxel represents a numeric data value (attribute) associated with some measured or calculated physical property at a particular location. Examples of geological data values include amplitude, phase, frequency, and semblance. Different data values are stored in different 3-D volume data sets, wherein each 3-D volume data set represents a different data value. In order to analyze certain geological structures referred to as “events” information from different 3-D volume data sets must be separately imaged in order to analyze the event.
[0010] Certain techniques have been developed in this field for imaging multiple 3-D volume data sets in a single display, however, not without considerable limitations. One example includes the technique published n The Leading Edge called “Constructing Faults from Seed Picks by Voxel Tracking” by Jack Lees. This technique combines two 3-D volume data sets in a single display, thereby restricting each original 256-value attribute to 128 values of the full 256-value range. The resolution of the display is, therefore, significantly reduced, thereby limiting the ability to distinguish certain events or features from the rest of the data. Another conventional method combines the display of two 3-D volume data sets, containing two different attributes, by making some data values more transparent than others. This technique becomes untenable when more than two attributes are combined.
[0011] Another technique used to combine two different 3-D volume data sets in the same image is illustrated in U.S. patent application Ser. No. 09/936,780, assigned to Magic Earth, inc. and incorporated herein by reference. This application describes a technique for combining a first 3-D volume data set representing a first attribute and a second 3-D volume data set representing a second attribute in a single enhanced 3-D volume data set by comparing each of the first and second attribute data values with a preselected data value range or criteria. For each data vale where the criteria are met, a first selected data value is inserted at a position corresponding with the respective data value in the enhanced 3-D volume data set. For each data value where the criteria are not met, a second selected data value is inserted at a position corresponding with the respective data value in the enhanced 3-D volume data set. The first selected data value may be related to the first attribute and the second selected data value may be related to the second attribute. The resulting image is an enhanced 3-D volume data set comprising a combination or hybrid of the original first 3-D volume data set and the second 3-D volume data set. As a result, the extra processing step needed to generate the enhanced 3-D volume data set causes interpretation delays and performance slow downs. Furthermore, this pre-processing technique is compromised by a “lossy” effect which compromises data from one seismic attribute in order to image another seismic attribute. Consequently, there is a significant loss of data visualization.
[0012] In non-scientific applications, techniques have been developed to define surface details (texture) on inanimate objects through lighting and/or shading techniques. For example, in the video or computer graphics field, one technique commonly used is texture mapping. Texture typically refers to bumps, wrinkles, grooves or other irregularities on surfaces. Textured surfaces are recognized by the way light interacts with the surface irregularities. In effect, these irregularities are part of the complete geometric form of the object although they are relatively small compared to the size and form of the object. Conventional texture mapping techniques have been known to lack the necessary surface detail to accomplish what is conventionally meant by texture. In other words, conventional texture mapping techniques provide objects with a colorful yet flat appearance. To this end, texture mapping was expanded to overcome this problem with what is now commonly referred to as a bump mapping.
[0013] Bump mapping is explained in an article written by Mark Kilgard called “A Practical and Robust Bump Mapping Technique for Today's GPU's” (hereinafter Kilgard) which is incorporated herein by reference. In this article, bump mapping is described as “a texture-based rendering approach for simulating lighting effects caused by pattern irregularities on otherwise smooth surfaces.” Kilgard, p. 1. According to Kilgard, “bump mapping simulates a surface's irregular lighting appearance without the complexity and expense of modeling the patterns as true geometric perturbations to the surface.” Kilgard, p. 1. Nevertheless, the computations required for original bump mapping techniques proposed by James Blinn in 1978 are considerably more expensive than those required for conventional hardware texture mapping. Kilgard at p. 2.
[0014] In view of the many attempts that have been made over the last two decades to reformulate bump mapping into a form suitable for hardware implementation, Kilgard proposes a new bump mapping technique. In short, Kilgard divides bump mapping into two steps. First, a perturbed surface normal is computed. Then, a lighting computation is performed using the perturbed surface normal. These two steps must be performed at each and every visible fragment of a bump-mapped surface. Kilgard.
[0015] Although Kilgard's new technique may be suitable for simulating surface irregularities (texture) representative of true geometric perturbations, it does not address the use of similar lighting effect to distinguish certain features of an object that are substantially indistinguishable in their natural environment.
SUMMARY OF THE INVENTION
[0016] The present invention meets the above needs and overcomes one or more deficiencies in the prior art by providing systems and methods for co-rendering multiple attributes in a three-dimensional data volume.
[0017] In one embodiment, the present invention includes a method for co-rendering multiple attributes in a three-dimensional data volume that comprises i) selecting a first attribute volume defined by a first attribute and a second attribute volume defined by a second attribute; ii) creating a three-dimensional sampling probe, wherein the sampling probe is a subvolume of the first attribute volume, the second attribute volume and the data volume; iii) drawing at least a portion of an image of the sampling probe on a display device using a graphics card, the image comprising an intersection of the sampling probe, the first attribute volume, the second attribute volume and the data volume; and iv) repeating the drawing step in response to movement of the sampling probe within the data volume so that as the sampling probe moves through the data volume, the image of the sampling probe is redrawn at a rate sufficiently fast to be perceived as moving in real-time.
[0018] In another embodiment, the present invention includes a computer readable medium having computer executable instructions for co-rendering multiple attributes in a three-dimensional data volume. The instructions are executable to implement i) selecting a first attribute volume defined by a first attribute and a second attribute volume defined by a second attribute; ii) creating a three-dimensional sampling probe, wherein the sampling probe is a subvolume of the first attribute volume, the second attribute volume and the data volume; iii) drawing at least a portion of an image of the sampling probe on a display device using a graphics card, the image comprising an intersection of the sampling probe, the first attribute volume, the second attribute volume and the data volume; and iv) repeating the drawing step in response to movement of the sampling probe within the data volume so that as the sampling probe moves through the data volume, the image of the sampling probe is redrawn at a rate sufficiently fast to be perceived as moving in real-time.
[0019] In another embodiment, the present invention includes a method for co-rendering multiple attributes in a three-dimensional data volume that comprises i) selecting a first attribute and a second attribute from multiple attributes, the first attribute the second attribute each having its own vertices; ii) creating a normal map using at least one of the first and second attributes, the normal map having its own vertices; iii) converting the normal map vertices and the vertices of the at least one of the first and second attributes used to create the normal map into a tangent space normal map; iv) calculating a diffused lighting component from the tangent space normal map and the at least one of the first and second attributes used to create the normal map; and v) combining an ambient lighting component with the diffused lighting component and the first and second attributes to form an enhanced image comprising at least part of the first attribute and part of the second attribute.
[0020] In yet another embodiment, the present invention includes a computer readable medium having computer executable instructions for co-rendering multiple attributes in a three-dimensional data volume. The instructions are executable to implement i) selecting a first attribute and a second attribute from multiple attributes, the first attribute the second attribute each having its own vertices; ii) creating a normal map using at least one of the first and second attributes, the normal map having its own vertices; iii) converting the normal map vertices and the vertices of the at least one of the first and second attributes used to create the normal map into a tangent space normal map; iv) calculating a diffused lighting component from the tangent space normal map and the at least one of the first and second attributes used to create the normal map; and v) combining an ambient lighting component with the diffused lighting component and the first and second attributes to form an enhanced image comprising at least part of the first attribute and part of the second attribute.
[0021] Additional aspects, advantages and embodiments of the invention will become apparent to those skilled in the art from the following description of the various embodiments and related drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0022] The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the U.S. Patent and Trademark Office upon request and payment of the necessary fee.
[0023] The present invention will be described with reference to the accompanying drawings, in which like elements are referenced with like reference numerals, and in which:
[0024] FIG. 1 is a block diagram illustrating one embodiment of a software program for implementing the present invention;
[0025] FIG. 2 is a flow diagram illustrating one embodiment of a method for implementing the present invention;
[0026] FIG. 3 is a color drawing illustrating semblance as a seismic data attribute;
[0027] FIG. 4 is a color drawing illustrating amplitude as a seismic data attribute;
[0028] FIG. 5 is a color drawing illustrating the combined image of both attributes illustrated in FIGS. 3 and 4 ;
[0029] FIG. 6 is a color drawing illustrating the combined image of FIG. 5 with the light source positioned to the left of the image.
[0030] FIG. 7 is a color drawing illustrating the combined image of FIG. 5 with the light source positioned perpendicular to the image.
[0031] FIG. 8 is a color drawing illustrating the combined image of FIG. 5 with the light source positioned to the right of the image.
[0032] While the present invention will be described in connection with presently preferred embodiments, it will be understood that it is not intended to limit the invention to those embodiments. On the contrary, it is intended to cover all alternatives, modifications, and equivalents included within the spirit of the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0033] The present invention may be implemented using hardware, software or a combination thereof, and may be implemented in a computer system or other processing system. The following description applies the present invention to various seismic data attributes which are contained within a specified space or volume referred to as a probe. Each probe comprises voxel data represented by x, y, z, data value. Each data value is associated with a particular seismic data attribute at a specified location (x, y, z). The present invention, therefore, may employ one or more of the hardware and software system components required to display and manipulate the probe as described in U.S. patent application Ser. No. 6,765,570 (“'570 Patent”) assigned to Landmark Graphics Corporation and incorporated herein by reference. For a more complete description of the probe requirements, reference is made to the '570 Patent.
[0034] In addition to the probe requirements, the present invention may be implemented using current high performance graphics and personal computer commodity hardware in order to insure real time performance. Examples of available hardware for the personal computer include graphics cards like GeForce® marketed by NVIDIA® and 2.4 Ghz x86 instruction set computer processors manufactured by Intel® or AMD®.
[0035] One embodiment of a software or program structure for implementing the present invention is shown in FIG. 1 . At the base of program structure 100 is an operating system 102 . Suitable operating systems may include, for example, UNIX® or Linux® operating systems, Windows NT®, and other operating systems generally known in the art.
[0036] Menu and interface software 104 overlays operating system 102 . Menu and interface software 104 are used to provide various menus and windows to facilitate interaction with the user, and to obtain user input and instructions. Menu and interface software 104 may include, for example, Microsoft Windows®, X Free 86®, MOTIF®, and other menu and interface software generally known in the art.
[0037] A basic graphics library 106 overlays menu and interface software 104 . Basic graphics library 106 is an application programming interface (API) for 3-D computer graphics. The functions performed by basic graphics library 106 include, for example, geometric and raster primitives, RGBA or color index mode, display list or immediate mode, viewing and modeling transformations, lighting and shading, hidden surface removal, alpha blending (translucency), anti-aliasing, texture mapping, atmospheric effects (fog, smoke, haze), feedback and selection, stencil planes, and accumulation buffer.
[0038] A particularly useful basic graphics library 106 is OpenGL®, marketed by Silicon Graphics, Inc. (“SGI®”). The OpenGL® API is a multi-platform industry standard that is hardware, window, and operating system independent. OpenGL® is designed to be callable from C, C++, FORTRAN, Ada and Java programming languages. OpenGL® performs each of the functions listed above for basic graphics library 106 . Some commands in OpenGL® specify geometric objects to be drawn, and others control how the objects are handled. All elements of the OpenGL® state, even the contents of the texture memory and the frame buffer, can be obtained by a client application using OpenGL®. OpenGL® and the client application may operate on the same or different machines because OpenGL® is network transparent. OpenGL® is described in more detail in the OpenGL® Programming Guide (ISBN: 0-201-63274-8) and the OpenGL® Reference Manual (ISBN: 0-201-63276-4), both of which are incorporated herein by reference.
[0039] Visual simulation graphics library 108 overlays the basic graphics library 106 .
[0040] Visual simulation graphics library 108 is an API for creating real-time, multi-processed 3-D visual simulation graphics applications. Visual simulation graphics library 108 provides functions that bundle together graphics library state control functions such as lighting, materials, texture, and transparency. These functions track state and the creation of display lists that can be rendered later.
[0041] A particularly useful visual simulation graphics library 108 is OpenGL Performer®, which is available from SGI®. OpenGL Performer® supports the OpenGL® graphics library discussed above. OpenGL Performer® includes two main libraries (libpf and libpr) and four associated libraries (libpfdu, libpfdb, libpfui, and libpfutil).
[0042] The basics of OpenGL Performer® is the performance rendering library libpr, a low-level library providing high speed rendering functions based on GeoSets and graphics state control using GeoStates. GeoSets are collections of drawable geometry that group same-type graphics primitives (e.g., triangles or quads) into one data object. The GeoSet contains no geometry itself, only pointers to data arrays and index arrays. Because all the primitives in a GeoSet are of the same type and have the same attributes, rendering of most databases is performed at a maximum hardware speed. GeoStates provide graphics state definitions (e.g., texture or material) for GeoSets.
[0043] Layered above libpr is libpf, a real-time visual simulation environment providing a high-performance multi-process database rendering system that optimizes use of multiprocessing hardware. The database utility library, libpfdu, provides functions for defining both geometric and appearance attributes of 3-D objects, shares states and materials, and generates triangle strips from independent polygonal input. The database library libpfdb uses the facilities of libpfdu, libpf and libpr to import database files in a number of industry standard database formats. The libpfui is a user interface library that provides building blocks for writing manipulation components for user interfaces (C and C++ programming languages). Finally, the libpfutil is the utility library that provides routines for implementing tasks and graphical user interface (GUI) tools.
[0044] An application program which uses OpenGL Performer® and OpenGL® API typically performs the following steps in preparing for real-time 3-D visual simulation:
1. Initialize OpenGL Performer®; 2. Specify number of graphics pipelines, choose the multiprocessing configuration, and specify hardware mode as needed; 3. Initialize chosen multiprocessing mode; 4. Initialize frame rate and set frame-extend policy; 5. Create, configure, and open windows as required; and 6. Create and configure display channels as required.
[0051] Once the application program has created a graphical rendering environment by carrying out steps 1 through 6 above, then the application program typically iterates through the following main simulation loop once per frame:
1. Compute dynamics, update model matrices, etc.; 2. Delay until the next frame time; 3. Perform latency critical viewpoint updates; and 4. Draw a frame.
[0056] Alternatively, Open Scene Graph® can be used as the visual simulation graphics library 108 . Open Scene Graph® operates in the same manner as OpenGL Performer®, providing programming tools written in C/C++ for a large variety of computer platforms. Open Scene Graph® is based on OpenGL® and is publicly available.
[0057] A multi-attribute co-rendering program 110 of the present invention overlays visual simulation graphs library 108 . In a manner generally well known in the art, program 110 interfaces with, and utilizes the functions carried out by, the visual simulation graphics library 108 , basic graphics library 106 , menu and interface software 104 operating system 102 and the probe described in the '634 application. Program 110 is preferably written in an object oriented programming language to allow the creation and use of objects and object functionality. One preferred object oriented programming language is C++.
[0058] In this particular embodiment, program 110 stores the 3-D volume data set in a manner generally well known in the art. For example, the format for a particular data volume may include two parts: a volume header followed by the body of data that is as long as the size of the data set. The volume header typically includes information in a prescribed sequence, such as the file path (location) of the data set, size, dimensions in the x, y, and z directions, annotations for the x, y and z axes, annotations for the data value, etc. The body of data is a binary sequence of bytes and may include one or more bytes per data value. For example, the first byte is the data value at volume location (0,0,0); the second byte is the data value at volume location (1,0,0); and the third byte is the data value at volume location (2,0,0). When the x dimension is exhausted, then the y dimension and the z dimension are incremented, respectively. This embodiment is not limited in any way to a particular data format.
[0059] The program 110 facilitates input from a user to identify one or more 3-D volume data sets to use for imaging and analysis. When a plurality of data volumes is used, the data value for each of the plurality of data volumes represents a different physical parameter or attribute for the same geographic space. By way of example, a plurality of data volumes could include a geology volume, a temperature volume, and a water-saturation volume. The voxels in the geology volume can be expressed in the form (x, y, z, seismic amplitude). The voxels in the temperature volume can be expressed in the form (x, y, z, ° C.). The voxels in the water-saturation volume can be expressed in the form (x, y, z, % saturation). The physical or geographic space defined by the voxels in each of these volumes is the same. However, for any specific spatial location (x 0 , y 0 , z 0 ), the seismic amplitude would be contained in the geology volume, the temperature in the temperature volume, and the water-saturation in the water-saturation volume. The operation of program 110 is described in reference to FIGS. 2 through 8 .
[0060] Referring now to FIG. 2 , a method 200 is illustrated for co-rendering multiple attributes in a combined image. The following description refers to certain bump mapping algorithms and techniques discussed in Kilgard.
[0061] In step 202 , a first attribute and a second attribute are selected from the available attributes using the GUI tools (menu/interface software 104 ) described in reference to FIG. 1 . Although other available stored attributes may be used, such as frequency and phase, semblance is used as the first attribute illustrated in the probe 300 of FIG. 3 , and amplitude is used as the second attribute illustrated in the probe 400 of FIG. 4 . The seismic data is displayed on the visible planar surfaces of the probe using conventional shading/opacity (texture mapping) techniques, however, may be displayed within the planar surfaces defining the probe using volume rendering techniques generally well known in the art. In order to display seismic data in the manner thus described, voxel data is read from memory and converted into a specified color representing a specific texture. Textures are tiled into 256 pixel by 256 pixel images. For large volumes, many tiles exist on a single planar surface of the probe. This process is commonly referred to by those skilled in the art as sampling, and is coordinated among multiple CPU's on a per-tile basis. These techniques, and others employed herein, are further described and illustrated in the '570 Patent.
[0062] In step 204 , a normal map is calculated in order to convert the texture based semblance attribute illustrated in FIG. 3 , sometimes referred to as a height field, into a normal map that encodes lighting information that will be used later by the register combiners. This technique enables the application of per-pixel lighting to volumetric data in the same way the probe displays volumetric data. In other words, it is a 2-D object which is actually displayed, however, because it is comprised of voxel data and the speed at which it is displayed, appears as a 3-D object. In short, this step converts the data values representing the semblance attribute into perturbed normalized vectors that are used by the graphics card to calculate lighting effects which give the illusion of depth and geometry when, in fact, a planar surface is displayed.
[0063] The normal map comprises multiple perturbed normal vectors which, collectively, are used to construct an illusion of height, depth and geometry on a planar surface. Each perturbed normal vector is derived from the cross product of the vertical and horizontal components for each data value on a given surface (e.g., 310 ) in FIG. 3 . Each perturbed normal vector is stored in the hardware as a texture unit (normal map) wherein each spatial coordinate (x, y, z) for each perturbed normal vector is assigned a specified color red, green or blue (RGB) value. The coordinate space in which these coordinates are assigned RGB values is generally known as texture coordinate space. Thus, the blue component of the perturbed normal vector represents the spatial coordinate (z). A pixel in the texture that is all blue would therefore, represent a typical tangent vector in planar objects such as the surface 310 in FIG. 3 . As the data values vary, the normal map appearance becomes less blue and appears almost chalky. The techniques necessary to derive a normal map from a height field are generally described in Section 5.3 of Kilgard. By applying the equations referred to in Section 2.6 of Kilgard to the data values shown in the probe 300 of FIG. 3 , a normal map may be constructed. One set of instructions to perform this method and technique is illustrated in Appendix E of Kilgard.
[0064] In order to obtain a more accurate lighting effect, a vertex program is applied in step 206 to the vertices that constrain the planar surface 310 of the underlying attribute illustrated in FIG. 3 and the vertices that constrain the corresponding planar surface of the normal map (not shown). A new coordinate space, tangent space, is contained in a transformation matrix used by the vertex program. The programmable hardware on the graphics card is used for rendering coordinate space transforms that drive the vertex program. The tangent space is constructed on a per-vertex basis, and typically requires the CPU to supply per-vertex light-angle vectors and half-angle vectors as 3-D texture coordinates. The light angle vectors and half angle vectors are likewise converted to tangent space when multiplied by the tangent space matrix. This step employs the techniques generally described in Section 5.1 of Kilgard.
[0065] For example, normal and tangent vectors are calculated on a per-vertex basis for a given geometric model—like the probe 300 in FIG. 3 . A bi-normal vector is calculated by taking the cross product of the tangent and normal vector components for each vertex. The tangent, normal and bi-normal vectors thus, form an ortho-normal basis at each vertex. The ortho-normal basis represents a matrix used to transform objects, space, light and eye position into tangent space. One set of instructions for performing this technique is illustrated in Appendix C of Kilgard.
[0066] Register combiners or texture shaders (not shown) are applied by the graphics card in step 208 to calculate the lighting equations described in Sections 2.5 through 2.5.1 of Kilgard. The GeForce® and Quadro® register combiners, available through NVIDIA®, provide a configurable, but not programmable, means to determine per-pixel fragment coloring/shading, and replace the standard OpenGL® fixed function texture environment, color sum, and fog operations with an enhanced mechanism for coloring/shading fragments. With multi-textured OpenGL®, filtered texels from each texture unit representing the normal map and the second attribute (amplitude) illustrated in the probe 400 of FIG. 4 are combined with the fragments' current color in sequential order. The register combiners are generally described in Section 4.2 of Kilgard as a sequential application of general combiner stages that culminate in a final combiner stage that outputs an RGBA color for the fragment. One set of instructions for programming OpenGL® register combiners is illustrated in Appendix B of Kilgard.
[0067] As further explained in Section 5.4 of Kilgard, the register combiners are configured to compute the ambient and diffuse illumination for the co-rendered image that is displayed in step 210 by means generally well-known in the art. In short, the register combiners are used to calculate ambient and diffuse lighting effects (illumination) for the normal map, after the vertex program is applied, and the second attribute which are combined to form an enhanced image representing the first and second attributes. The resulting data values for the combined image represent a blended texture or combined texture of both the first and second attributes. One set of instructions for programming the register combiners to compute the ambient and diffuse illumination is illustrated in Appendix G of Kilgard.
[0068] Alternatively, fragment routines, generally well known in the art, may be used with the register combiners to provide a more refined per-pixel lighting effect for the normal map.
[0069] As illustrated in FIG. 3 , certain geological features, such as faults represented by the black color values 312 , are distinguished from the blue color values 314 due to discontinuity between the adjacent data values measured along the z-axis. In FIG. 4 , the same geological features 412 are barely distinguishable because they are illustrated by a different attribute (amplitude) that is assigned multiple color values and contains more consistent adjacent data values along the z-axis. The same geological features 512 are even more readily distinguished in FIG. 5 due to the enhanced surface texture which appears to give the planar surface 510 on the probe 500 depth and height.
[0070] In FIG. 5 , the first attribute (semblance) is distinguished by shading from the second attribute (amplitude) which is shown by various color values. This illusion is uncharacteristic of the actual geological feature which is substantially indistinguishable in its natural environment. Although both attributes are not visible at the same time over the planar surface 510 of the probe 500 , they are imaged in the same space and capable of being simultaneously viewed depending on the angle of the probe 500 relative to the light source. Thus, as the probe 500 is rotated, certain voxels representing the first attribute become masked while others representing the second attribute become visible, and vice-versa. This technique is useful for enhancing images of certain features of an object which are substantially indistinguishable in their natural environment. The present invention may also be applied, using the same techniques, to image volume-rendered seismic-data attributes.
[0071] As the image is displayed in step 210 , several options described in reference to steps 212 through 220 may be interactively controlled through the menu/interface software 104 to compare and analyze any differences between the various images.
[0072] In step 212 , the specular or diffuse lighting coefficients may be interactively controlled to alter the shading/lighting effects applied to the combined image. Accordingly, the register combiners are reapplied in step 208 to enhance the image displayed in step 210 .
[0073] In step 214 , the imaginary light source may be interactively repositioned or the probe may be interactively rotated to image other geological features revealed by the attributes. The movement of the probe is accomplished by means generally described in the '634 application. In FIGS. 6-8 , the planar surface 510 of the probe 500 illustrated in FIG. 5 is fixed at a position perpendicular to the line of sight as the light source is interactively repositioned. As the light source moves, different voxels become illuminated according to the position of the light source. The effect is similar to that achieved when the probe is rotated. Accordingly, steps 206 and 208 are reapplied to provide different perspectives of the image displayed in step 210 .
[0074] In FIG. 6 , for example, the light source is positioned to the left of the probe face 610 so that voxels 612 , which are perceived as indentions, appear darker while voxels 614 , which are perceived as bumps, appear lighter or more illuminated. When the light source is repositioned to the right of the probe face 810 , as in FIG. 8 , different voxels 812 , 814 appear darker and lighter than those illustrated in FIG. 6 . As illustrated in FIG. 7 , the light source is positioned perpendicular to the probe face 710 and the entire image appears brighter. This effect is attributed to the specular component of the lighting equation, and enhances the illusion of depth and height in the image as the light source is repositioned or the probe is rotated. One set of instructions explaining how to configure the register combiners to compute the specular component is illustrated in Appendix H of Kilgard. In this manner, the combined image can be interactively manipulated to simultaneously reveal multiple attributes with nominal loss in the clarity of each attribute.
[0075] In step 216 , the per-pixel lighting height is interactively controlled to alter the normal depth of the indentions and/or height of the bumps which are shaded and illuminated as described in reference to step 208 . The per-pixel lighting height is interactively controlled by scaling each perturbed normal vector from zero which cancels any indentations or bumps. If the per-pixel lighting is scaled in positive increments, then each perturbed normal vector height (bump) or depth (indentation) is increased. Conversely, if the per-pixel lighting is scaled in negative increments, then each perturbed normal vector height or depth is decreased. The net effect produces an image that appears to alter the position of the light source so that different features of the object are enhanced. Accordingly, steps 204 , 206 , and 208 are reapplied to provide different perspectives of the image displayed in step 210 .
[0076] In step 218 , different attributes are interactively selected in the manner described in reference to step 202 . Accordingly, steps 204 , 206 , and 208 are reapplied to provide an entirely new image, illustrating different data values in step 210 . Furthermore, the image displayed in step 210 may illustrate more than two attributes which are selected in step 218 . For example, if the available attributes include amplitude, phase and semblance, then a normal map is created for any two of these attributes in the manner described in reference to step 204 . In other words, a normal map is calculated or each of the two selected attributes and the resulting value for each perturbed normal vector in one normal map is then added to the value of each perturbed normal vector in the other normal map, at the same location, to create a single normal map that is used in the manner described in reference to steps 206 and 208 . Alternatively, the voxels for one of the selected attributes can be added to the voxels of the other selected attribute at the same location and a normal map is calculated for the combined voxel values in the manner described in reference to step 204 . The normal map is then used in the manner described in reference to steps 206 and 208 . In either application where there are more than two attributes, one attribute will serve as the static attribute until step 208 , while the others will be used in the manner thus described.
[0077] In step 220 , the probe is interactively controlled so that it can be resized or moved in a manner more particularly described in the '570 Patent. This step necessarily alters the voxels displayed on the planar surfaces of the probe for the combined image displayed in step 210 . As a result, the first and second attributes must be re-sampled in step 222 and steps 204 , 206 , and 208 must be reapplied to display a new image in step 210 illustrating the same attributes at a different location.
[0078] The techniques described by the foregoing invention remove the extra processing step normally encountered in conventional bump mapping techniques by interactively processing the attributes using hardware graphics routines provided by commodity PC graphics cards. These techniques are therefore, particularly useful to the discovery and development of energy resources.
[0079] The foregoing disclosure and description of the invention is illustrative and explanatory thereof, and it will be appreciated by those skilled in the art, that various changes in the size, shape and materials, the use of mechanical equivalents, as well as in the details of the illustrated construction or combinations of features of the various elements may be made without departing from the spirit of the invention. | Systems and methods for enhancing the combined image of multiple attributes without comprising the image of either attribute. The combined image of the multiple attributes is enhanced for analyzing a predetermined property revealed by the attributes. The combined image can be interactively manipulated to display each attribute relative to an imaginary light source or highlighted using a specular component. The systems and methods are best described as particularly useful for analytical, diagnostic and interpretive purposes. | 6 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an inverter circuit that is suitably applicable to, for example, a display device using an organic EL (Electro Luminescence) element. The present invention also relates to a display device provided with the above-mentioned inverter circuit.
2. Description of the Related Art
In recent years, in the field of display devices that display images, a display device that uses, as a light emitting element for a pixel, an optical element of current-driven type whose light emission luminance changes according to the value of a flowing current, e.g. an organic EL element, has been developed, and its commercialization is proceeding. In contrast to a liquid crystal device and the like, the organic EL element is a self-luminous element. Therefore, in the display device using the organic EL element (organic EL display device), gradation of coloring is achieved by controlling the value of a current flowing in the organic EL element.
As a drive system in the organic EL display device, like a liquid crystal display, there are a simple (passive) matrix system and an active matrix system. The former is simple in structure, but has, for example, such a disadvantage that it is difficult to realize a large and high-resolution display device. Therefore, currently, development of the active matrix system is brisk. In this system, the current flowing in a light emitting element arranged for each pixel is controlled by a drive transistor.
In the above-mentioned drive transistor, there is a case in which a threshold voltage V th or a mobility μ changes over time, or varies from pixel to pixel due to variations in production process. When the threshold voltage V th or the mobility μ varies from pixel to pixel, the value of the current flowing in the drive transistor varies from pixel to pixel and therefore, even when the same voltage is applied to the gate of the drive transistor, the light emission luminance of the organic EL element varies and uniformity of a screen is impaired. Thus, there has been developed a display device in which a correction function to address a change in the threshold voltage V th or the mobility μ is incorporated (see, for example, Japanese Unexamined Patent Application Publication No. 2008-083272).
A correction to address the change in the threshold voltage V th or the mobility μ is performed by a pixel circuit provided for each pixel. As illustrated in, for example, FIG. 16 , this pixel circuit includes: a drive transistor Tr 100 that controls a current flowing in an organic EL element 111 , a write transistor Tr 200 that writes a voltage of a signal line DTL into the drive transistor Tr 100 , and a retention capacitor C s , and therefore, the pixel circuit has a 2Tr1C circuit configuration. The drive transistor Tr 100 and the write transistor Tr 200 are each formed by, for example, an n-channel MOS Thin Film Transistor (TFT).
FIG. 15 illustrates an example of the waveform of a voltage applied to the pixel circuit and an example of a change in each of the gate voltage V g and the source voltage V s of the drive transistor Tr 100 . In Part (A) of FIG. 15 , there is illustrated a state in which a signal voltage V sig and an offset voltage V ofs are applied to the signal line DTL. In Part (B) of FIG. 15 , there is illustrated a state in which a voltage V dd for turning on the write transistor Tr 200 and a voltage V ss for turning off the write transistor Tr 200 are applied to a write line WSL. In Part (C) of FIG. 15 , there is illustrated a state in which a high voltage V ccH and a low voltage V ccL are applied to a power-source line PSL. Further, in Part (D) and (E) of FIG. 15 , there is illustrated a state in which the gate voltage V g and the source voltage V s of the drive transistor Tr 100 change over time in response to the application of the voltages to the power-source line PSL, the signal line DTL and the write line WSL.
From FIG. 15 , it is found that a WS pulse P is applied to the write line WSL twice within 1 H, a threshold correction is performed by the first WS pulse P, and a mobility correction and signal writing are performed by the second WS pulse P. In other words, in FIG. 15 , the WS pulse P is used for not only the signal writing but also the threshold correction and the mobility correction of the drive transistor Tr 100 .
SUMMARY OF THE INVENTION
Incidentally, in the display device employing the active matrix system, each of a horizontal drive circuit (not illustrated) that drives the signal line DTL and a write scan circuit (not illustrated) that selects each pixel 113 sequentially is configured to basically include a shift resister (not illustrated), and has a buffer circuit (not illustrated) for each stage, corresponding to each column or each row of pixels 113 . For example, the buffer circuit within the write scan circuit is typically configured such that two inverter circuits are connected in series. Here the inverter circuit has, as illustrated in FIG. 17 , for example, a single channel type of circuit configuration in which two n-channel MOS transistors Tr 1 and Tr 2 are connected in series. An inverter circuit 200 illustrated in FIG. 17 is inserted between high voltage wiring L H to which a high-level voltage is applied and low voltage wiring L L to which a low-level voltage is applied. The gate of the transistor Tr 2 on the high voltage wiring L H side is connected to the high voltage wiring L H , and the gate of the transistor Tr 1 on the low voltage wiring L L side is connected to an input terminal IN. Further, a connection point C between the transistor Tr 1 and the transistor Tr 2 is connected to an output terminal OUT.
In the inverter circuit 200 , as illustrated in FIG. 18 , for example, when a voltage V in of the input terminal IN is V ss , a voltage V out of the output terminal OUT is not V dd , and instead is V dd -V th . In other words, the threshold voltage V th of the transistor Tr 2 is included in the voltage V out of the output terminal OUT, and the voltage V out of the output terminal OUT is largely affected by variations in the threshold voltage V th of the transistor Tr 2 .
Thus, for example, as illustrated by an inverter circuit 300 in FIG. 19 , it is conceivable that the gate and the drain of the transistor Tr 2 may be electrically separated from each other, and the gate may be connected to high voltage wiring L H2 to which a voltage V dd2 (≧V dd V th ) that is higher than the voltage V dd of the drain is applied. In addition, for example, a bootstrap type of circuit configuration as illustrated by an inverter circuit 400 in FIG. 20 is conceivable. Specifically, it is conceivable to provide a circuit configuration in which a transistor Tr 12 is inserted between the gate of the transistor Tr 2 and the high voltage wiring L H , the gate of the transistor Tr 12 is connected to the high voltage wiring L H , and a capacitive element C 10 is inserted between: a connection point D between the gate of the transistor Tr 2 and the source of the transistor Tr 12 ; and the connection point C.
However, in the circuit in any of FIG. 17 , FIG. 19 and FIG. 20 , until the time when the input voltage V in becomes high, namely when the output voltage V out becomes low, a current (through current) flows from the high voltage wiring L H side to the low voltage wiring L L side via the transistors Tr 1 and Tr 2 . As a result, power consumption in the inverter circuit also becomes large. In addition, in the circuits of FIG. 17 , FIG. 19 and FIG. 20 , when, for example, the input voltage V in is V dd as indicated with a point surrounded by a broken line in Part (B) of FIG. 18 , the output voltage V out is not V ss , and the peak value of the output voltage V out varies. As a result, there has been such a shortcoming that the threshold corrections and the mobility corrections of the drive transistors Tr 100 in pixel circuits 112 vary among the pixel circuits 112 , and such variations result in variations in luminance.
Incidentally, the above-described shortcoming not only occurs in the scan circuit of the display device, but may take place similarly in any other devices.
In view of the foregoing, it is desirable to provide an inverter circuit capable of setting the peak value of an output voltage at a desired value while suppressing power consumption, and a display device having this inverter circuit.
According to an embodiment of the present invention, there is provided a first inverter circuit including: a first transistor, a second transistor, a third transistor, a fourth transistor, a fifth transistor, a sixth transistor and a seventh transistor each having channels of same conduction type; a first capacitive element; and an input terminal and an output terminal. The first transistor makes or breaks electric connection between the output terminal and a first voltage line, in response to a potential difference between a voltage of the input terminal and a voltage of the first voltage line or a potential difference corresponding thereto. The second transistor makes or breaks electric connection between a second voltage line and the output terminal, in response to a potential difference between a voltage of a first terminal that is a source or a drain of the seventh transistor and a voltage of the output terminal or a potential difference corresponding thereto. The third transistor makes or breaks electric connection between a gate of the seventh transistor and the third voltage line, in response to a potential difference between the voltage of the input terminal and a voltage of a third voltage line or a potential difference corresponding thereto. The fourth transistor makes or breaks electric connection between the first capacitive element and the gate of the seventh transistor, in response to a first control signal inputted into a gate of the fourth transistor. The fifth transistor makes or breaks electric connection between the first capacitive element and a fourth voltage line, in response to a second control signal inputted into a gate of the fifth transistor. The sixth transistor makes or breaks electric connection between the first terminal and the fifth voltage line, in response to a potential difference between the voltage of the input terminal and a voltage of a fifth voltage line or a potential difference corresponding thereto. The seventh transistor makes or breaks electric connection between the first terminal and a sixth voltage line, in response to a potential difference between a gate voltage of the seventh transistor and a gate voltage of the second transistor or a potential difference corresponding thereto. The first capacitive element is inserted between a drain or a source of the fifth transistor and a seventh voltage line.
According to an embodiment of the present invention, there is provided a first display device having a display section and a drive section, the display section including a plurality of scanning lines arranged in rows, a plurality of signal lines arranged in columns and a plurality of pixels arranged in rows and columns, and the drive section including a plurality of inverter circuits each provided for each of the scanning lines to drive each of the pixels. Each of the inverter circuits in the drive section includes the same elements as those of the above-described first inverter circuit.
In the first inverter circuit and the first display device according to the above embodiments of the present invention, between the gate of the seventh transistor and the first voltage line, between the gate of the second transistor and the first voltage line, between the source of the second transistor and the first voltage line, there are provided the first transistor, the third transistor and the sixth transistor, respectively, which perform on-off operation according to a potential difference between the input voltage and the voltage of the first voltage line. As a result, for example, when the input voltage falls, on-resistance of each of the first transistor, the third transistor and the sixth transistor gradually becomes large, and the time necessary to charge the gates and the sources of the second transistor and the seventh transistor to the voltage of the first voltage line becomes longer. Further, for example, when the input voltage rises, the on-resistance of each of the first transistor, the third transistor and the sixth transistor gradually becomes small, and the time necessary to charge the gate and the source of the second transistor to the voltage of the first voltage line becomes short. In addition, in the above embodiments of the present invention, when the input voltage falls, the gate of the seventh transistor is charged to a voltage equal to or higher than an on-voltage of the seventh transistor. As a result, for example, when a falling voltage is input into the input terminal, the first transistor, the third transistor and the sixth transistor are turned off, and immediately after that, the seventh transistor is turned on and further, the second transistor is turned on and therefore, the output voltage becomes the voltage on the second voltage line side. Moreover, for example, when the input voltage rises, the first transistor, the third transistor and the sixth transistor are turned on and immediately after that, the second transistor is turned off. As a result, the output voltage becomes the voltage on the first voltage line side.
According to an embodiment of the present invention, there is provided a second inverter circuit including: a first transistor, a second transistor, a third transistor, a fourth transistor, a fifth transistor, a sixth transistor and a seventh transistor each having channels of same conduction type; a first capacitive element; and an input terminal and an output terminal. A gate of the first transistor is electrically connected to the input terminal, one terminal of a drain and a source of the first transistor is electrically connected to a first voltage line, and the other terminal of the first transistor is electrically connected to the output terminal. One terminal of a drain and a source of the second transistor is electrically connected to a second voltage line, and the other terminal of the second transistor is electrically connected to the output terminal. A gate of the third transistor is electrically connected to the input terminal, one terminal of a drain and a source of the third transistor is electrically connected to a third voltage line, and the other terminal of the third transistor is electrically connected to a gate of the second transistor. A gate of the fourth transistor is supplied with a first control signal, and one terminal of a drain and a source of the fourth transistor is electrically connected to a gate of the seventh transistor. A gate of the fifth transistor is supplied with a second control signal, one terminal of a drain and a source of the fifth transistor is electrically connected to a fourth voltage line, and the other terminal of the fifth transistor is electrically connected to the other terminal of the fourth transistor. A gate of the sixth transistor is electrically connected to the input terminal, one terminal of a drain and a source of the sixth transistor is electrically connected to a fifth voltage line, and the other terminal of the sixth transistor is electrically connected to the gate of the second transistor. One terminal of a drain and a source of the seventh transistor is electrically connected to a sixth voltage line, and the other terminal of the seventh transistor is electrically connected to the gate of the second transistor. The first capacitive element is inserted between the other terminal of the fifth transistor and a seventh voltage line.
According to an embodiment of the present invention, there is provided a second display device having a display section and a drive section, the display section including a plurality of scanning lines arranged in rows, a plurality of signal lines arranged in columns and a plurality of pixels arranged in rows and columns, and the drive section including a plurality of inverter circuits each provided for each of the scanning lines to drive each of the pixels. Each of the inverter circuits in the drive section includes the same elements as those of the above-described second inverter circuit.
In the second inverter circuit and the second display device according to the above embodiments of the present invention, between the gate of the seventh transistor and the first voltage line, between the gate of the second transistor and the first voltage line, between the source of the second transistor and the first voltage line, there are provided the first transistor, the third transistor and the sixth transistor, respectively, whose gates are connected to the input terminal. As a result, for example, when the input voltage falls, on-resistance of each of the first transistor, the third transistor and the sixth transistor gradually becomes large, and the time necessary to charge the gates and the sources of the second transistor and the seventh transistor to the voltage of the first voltage line becomes longer. Further, for example, when the input voltage rises, the on-resistance of each of the first transistor, the third transistor and the sixth transistor gradually becomes small, and the time necessary to charge the gate and the source of the second transistor to the voltage of the first voltage line becomes short. In addition, in the above embodiments of the present invention, when the input voltage falls, the gate of the seventh transistor is charged to a voltage equal to or higher than an on-voltage of the seventh transistor. As a result, for example, when a falling voltage is input into the input terminal, the first transistor, the third transistor and the sixth transistor are turned off, and immediately after that, the seventh transistor is turned on and further, the second transistor is turned on and therefore, the output voltage becomes the voltage on the second voltage line side. Moreover, for example, when the input voltage rises, the first transistor, the third transistor and the sixth transistor are turned on and immediately after that, the second transistor is turned off. As a result, the output voltage becomes the voltage on the first voltage line side.
In the first and second inverter circuits and the first and second display devices according to the above-described embodiments of the present invention, a second capacitive element may be inserted between the gate and the source of the second transistor. In this case, a capacity of the second capacitive element is desired to be smaller than a capacity of the first capacitive element.
According to the first and second inverter circuits and the first and second display devices in the above-described embodiments of the present invention, there is no time period over which the first transistor and the second transistor are turned on at the same time, and the fourth transistor and the seventh transistor are turned on at the same time, and the third transistor, the fourth transistor and the fifth transistor are turned on at the same time. This makes it possible to suppress power consumption, because almost no current (through current) flows between the voltage lines, via these transistors. In addition, when the gate of the first transistor changes from high to low, the output voltage becomes a voltage on the second voltage line side or a voltage on the first voltage line side, and when the gate of the first transistor changes from low to high, the output voltage becomes a voltage on the reverse side of the above-mentioned side. This makes it possible to reduce a shift of the peak value of the output voltage from a desired value. As a result, for example, it is possible to reduce variations in the threshold correction and the mobility correction of the drive transistor in the pixel circuit, among the pixel circuits, and further, variations in the luminance among the pixels may be reduced.
Moreover, in the above-described embodiments of the present invention, on either of the low voltage side and the high voltage side, voltage lines may be provided as a single common voltage line. Therefore, in this case, there is no need to increase the withstand voltage of the inverter circuit.
Other and further objects, features and advantages of the invention will appear more fully from the following description.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a circuit diagram illustrating an example of an inverter circuit according to an embodiment of the present invention;
FIG. 2 is a waveform diagram illustrating an example of input-output signal waveforms of the inverter circuit in FIG. 1 ;
FIG. 3 is a waveform diagram illustrating an example of the operation of the inverter circuit in FIG. 1 ;
FIG. 4 is a circuit diagram for explaining an example of the operation of the inverter circuit in FIG. 1 ;
FIG. 5 is a circuit diagram for explaining an example of the operation following FIG. 4 ;
FIG. 6 is a circuit diagram for explaining an example of the operation following FIG. 5 ;
FIG. 7 is a circuit diagram for explaining an example of the operation following FIG. 6 ;
FIG. 8 is a circuit diagram for explaining an example of the operation following FIG. 7 ;
FIG. 9 is a circuit diagram for explaining an example of the operation following FIG. 8 ;
FIG. 10 is a circuit diagram for explaining an example of the operation following FIG. 9 ;
FIG. 11 is a waveform diagram illustrating another example of the input-output signal waveforms of the inverter circuit in FIG. 1 ;
FIG. 12 is a waveform diagram illustrating another example of the operation of the inverter circuit in FIG. 1 ;
FIG. 13 is a schematic configuration diagram of a display device that is one of application examples of the inverter circuit in the present embodiment and its modification;
FIG. 14 is a circuit diagram illustrating an example of a write-line driving circuit and an example of a pixel circuit in FIG. 13 ;
FIG. 15 is a waveform diagram illustrating an example of the operation of the display device in FIG. 13 ;
FIG. 16 is a circuit diagram illustrating an example of a pixel circuit in a display device in related art;
FIG. 17 is a circuit diagram illustrating an example of an inverter circuit in related art;
FIG. 18 is a waveform diagram illustrating an example of input-output signal waveforms of the inverter circuit in FIG. 17 ;
FIG. 19 is a circuit diagram illustrating another example of the inverter circuit in related art;
FIG. 20 is a circuit diagram illustrating another example of the inverter circuit in related art;
FIG. 21 is a circuit diagram illustrating an example of an inverter circuit according to a reference example; and
FIG. 22 is a waveform diagram illustrating an example of input-output signal waveforms of the inverter circuit in FIG. 21 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
An embodiment of the present invention will be described below in detail with reference to the drawings. The description will be provided in the following order.
1. Embodiment ( FIG. 1 through FIG. 10 )
2. Modification ( FIG. 11 and FIG. 12 )
3. Application example ( FIG. 13 through FIG. 15 )
4. Description of related art ( FIG. 16 through FIG. 20 )
5. Description of reference technique ( FIG. 21 and FIG. 22 )
Embodiment
Configuration
FIG. 1 illustrates an example of the entire configuration of an inverter circuit 1 according to an embodiment of the present invention. The inverter circuit 1 outputs, from an output terminal OUT, a pulse signal (e.g., Part (B) of FIG. 2 ) whose waveform is approximately the inverse of the signal waveform of a pulse signal (e.g., Part (A) of FIG. 2 ) input into an input terminal IN. The inverter circuit 1 is suitably formed on an amorphous silicon or amorphous oxide semiconductor and has, for example, seven transistors Tr 1 to Tr 7 of the same channel type. In addition to the seven transistors Tr 1 to Tr 7 , the inverter circuit 1 includes two capacitive elements C 1 and C 2 , the input terminal IN and the output terminal OUT, and has a 7Tr2C circuit configuration.
The transistor Tr 1 is equivalent to a specific example of “the first transistor” according to the embodiment of the present invention, and the transistor Tr 2 is equivalent to a specific example of “the second transistor” according to the embodiment of the present invention, and the transistor Tr 1 is equivalent to a specific example of “the third transistor” according to the embodiment of the present invention. Further, the transistor Tr 4 is equivalent to a specific example of “the fourth transistor” according to the embodiment of the present invention, and the transistor Tr 5 is equivalent to a specific example of “the fifth transistor” according to the embodiment of the present invention. Furthermore, the transistor Tr 6 is equivalent to a specific example of “the sixth transistor” according to the embodiment of the present invention, and the transistor Tr 7 is equivalent to a specific example of “the seventh transistor” according to the embodiment of the present invention. Moreover, the capacitive element C 1 is equivalent to a specific example of “the first capacitive element” according to the embodiment of the present invention, and the capacitive element C 2 is equivalent to a specific example of “the second capacitive element” according to the embodiment of the present invention.
The transistors Tr 1 to Tr 7 are thin-film transistors (TFTs) of the same channel type and are, for example, n-channel MOS (Metal Oxide Film Semiconductor) type of thin-film transistors (TFTs). The transistor Tr 1 is, for example, configured to establish and cut off electric connection between the output terminal OUT and the low voltage line L L , according to a potential difference V gs1 (or a potential difference corresponding thereto) between a voltage (input voltage V in ) of the input terminal IN and a voltage V L of a low voltage line L L . The gate of the transistor Tr 1 is electrically connected to the input terminal IN, and the source or the drain of the transistor Tr 1 is electrically connected to the low voltage line L L . Of the source and the drain of the transistor Tr 1 , one that is a terminal unconnected with the low voltage line L L is electrically connected to the output terminal OUT. The transistor Tr 2 is configured to establish and cut off electric connection between a high voltage line L H and the output terminal OUT, according to a potential difference V gs2 (or a potential difference corresponding to thereto) between a voltage V s7 of a terminal (terminal A) unconnected with the high voltage line L H and the voltage (output voltage V out ) of the output terminal OUT. The terminal A is one of the source and the drain of the transistor Tr 7 . The gate of the transistor Tr 2 is electrically connected to the terminal A of the transistor Tr 7 . The source or the drain of the transistor Tr 2 is electrically connected to the output terminal OUT, and of the source and the drain of the transistor Tr 2 , one that is a terminal unconnected with the output terminal OUT is electrically connected to the high voltage line L H .
The transistor Tr 3 is configured to establish and cut off electric connection between the gate of the transistor Tr 7 and the low voltage line L L , according to a potential difference V gs3 (or a potential difference corresponding thereto) between the input voltage V in and the voltage V L of the low voltage line L L . The gate of the transistor Tr 3 is electrically connected to the input terminal IN. The source or the drain of the transistor Tr 3 is electrically connected to the low voltage line L L , and of the source and the drain of the transistor Tr 3 , one that is a terminal unconnected with the low voltage line L L is electrically connected to the gate of the transistor Tr 7 . The transistor Tr 4 is configured to establish and cut off electric connection between the capacitive element C 1 and the gate of the transistor Tr 7 , according to a control signal input into a control terminal AZ 1 . The gate of the transistor Tr 4 is electrically connected to the control terminal AZ 1 . The source or the drain of the transistor Tr 4 is electrically connected to the capacitive element C 1 , and of the source and the drain of the transistor Tr 4 , one that is a terminal unconnected with the capacitive element C 1 is electrically connected to the gate of the transistor Tr 7 . The transistor Tr 5 is configured to establish and cut off electric connection between the high voltage line L H and the capacitive element C 1 , according to a control signal input into a control terminal AZ 2 . The gate of the transistor Tr 5 is electrically connected to the control terminal AZ 2 . The source or the drain of the transistor Tr 5 is electrically connected to the high voltage line L H . Of the source and the drain of the transistor Tr 5 , one that is a terminal unconnected with the high voltage line L H is electrically connected to the capacitive element C 1 .
The transistor Tr 6 is configured to establish and cut off electric connection between the terminal A of the transistor Tr 7 and the low voltage line L L , according to a potential difference V gs6 (or a potential difference corresponding thereto) between the input voltage V in , and the voltage V L of the low voltage line L L . The gate of the transistor Tr 6 is electrically connected to the input terminal IN. The source or the drain of the transistor Tr 6 is electrically connected to the low voltage line L L , and of the source and the drain of the transistor Tr 6 , one that is a terminal unconnected with the low voltage line L L is electrically connected to the terminal A of the transistor Tr 7 . In other words, the transistors Tr 1 , Tr 3 and Tr 6 are connected to the same voltage line (the low voltage line L L ). Therefore, the terminal on the low voltage line L L side of the transistor Tr 1 , the terminal on the low voltage line L L side of the transistor Tr 3 and the terminal on the low voltage line L L side of the transistor Tr 6 are at the same potential. The transistor Tr 7 is configured to establish and cut off electric connection between the high voltage line L H and one, which is a terminal unconnected with the low voltage line L L , of the source and the drain of the transistor Tr 6 , according to a potential difference V gs7 (or a potential difference corresponding thereto) between the voltage V s7 of the terminal unconnected with the capacitive element C 1 of the source and the drain of the transistor Tr 4 and a gate voltage V g2 (the voltage V s7 of the terminal A) of the transistor Tr 2 . The gate of the transistor Tr 7 is electrically connected to the terminal unconnected with the capacitive element C 1 , which terminal is one of the source and the drain of the transistor Tr 4 . The source or the drain of the transistor Tr 7 is electrically connected to the high voltage line L H , and of the source and the drain of the transistor Tr 7 , one that is the terminal (the terminal A) unconnected with the high voltage line L H is electrically connected to the terminal unconnected with the low voltage line L L , which terminal is one of the source and the drain of the transistor Tr 6 . In other words, the transistors Tr 2 , Tr 5 and Tr 7 are connected to the same voltage line (high voltage line L H ). Therefore, the terminal on the high voltage line L H side of the transistor Tr 2 , the terminal on the high voltage line L H side of the transistor Tr 5 and the terminal on the high voltage line L H side of the transistor Tr 7 are at the same potential.
The low voltage line L L is equivalent to a specific example of “the first voltage line” according to the embodiment of the present invention. The high voltage line L H is equivalent to a specific example of “the second voltage line” according to the embodiment of the present invention.
The high voltage line L H is connected to a power source (not illustrated) that outputs a voltage (constant voltage) higher than the voltage V L of the low voltage line L L . The voltage of the high voltage line L H is V dd at the time of driving the inverter circuit 1 . On the other hand, the low voltage line L L is connected to a power source (not illustrated) that outputs a voltage (constant voltage) lower than a voltage V H of the high voltage line L H , and the voltage V L of the low voltage line L L is a voltage V ss (<V dd ) at the time of driving the inverter circuit 1 .
The control terminal AZ 1 is connected to a power source S 1 (not illustrated) that outputs a predetermined pulse signal. The control terminal AZ 2 is connected to a power source S 2 (not illustrated) that outputs a predetermined pulse signal. The power source S 1 is, for example, configured to output a high while a low is applied to the control terminal AZ 2 , as illustrated in Part (C) of FIG. 2 . On the other hand, the power source S 2 is, for example, configured to output a high while a low is applied to the control terminal AZ 1 , as illustrated in Part (B) of FIG. 2 . In other words, the power source S 1 and the power source S 2 are configured to alternately output highs so that the transistors Tr 4 and Tr 5 are not in an ON state at the same time (namely, the transistors Tr 4 and Tr 5 are turned on and off alternately). The power source S 1 is configured such that the output voltage of the power source S 1 changes from low to high (in other words, the transistor Tr 4 is turned on), in timing different from the timing in which the input voltage V in rises. The power source S 1 is, for example, configured such that the output voltage of the power source S 1 changes from low to high immediately before the input voltage V in drops.
The capacitive element C 1 is inserted between the terminal unconnected with the high voltage line L H , which is one of the source and the drain of the transistor Tr 5 , and the low voltage line L L . The capacitive element C 2 is inserted between the gate of the transistor Tr 2 and the source of the transistor Tr 2 . The value of each of the capacitive element C 1 and the capacitive element C 2 is sufficiently larger than parasitic capacitances of the transistors Tr 1 to Tr 7 . The value of the capacity of the capacitive element C 1 is larger than the capacity of the capacitive element C 2 . When a falling voltage is input into the input terminal IN, and the transistor Tr 3 is turned off, the value of the capacity of the capacitive element C 1 becomes a value that makes it possible to charge the gate of the transistor Tr 7 to a voltage of V ss +V th7 or more. In addition, the V th7 is a threshold voltage of the transistor Tr 7 .
Incidentally, in a relation with an inverter circuit in related art (the inverter circuit 200 in FIG. 17 ), the inverter circuit 1 is equivalent to a circuit in which a control element 10 and the capacitive element C 2 are inserted between the transistors Tr 1 and Tr 2 in an output stage and the input terminal IN. Here, for example, as illustrated in FIG. 1 , the control element 10 includes a terminal P 1 electrically connected to the input terminal IN, a terminal P 2 electrically connected to the low voltage line L L , a terminal P 3 electrically connected to the gate of the transistor Tr 2 and a terminal P 4 electrically connected to a high voltage line L H2 . The control element 10 further includes, for example, as illustrated in FIG. 1 , the transistors Tr 3 to Tr 7 and the capacitive element C 1 .
The control element 10 is, for example, configured to charge the gate of the transistor Tr 2 electrically connected to the terminal P 3 to a voltage of V ss +V th2 or more when a falling voltage is input into the terminal P 1 . Further, for example, the control element 10 is configured to cause the gate voltage V g2 of the transistor Tr 2 electrically connected to the terminal P 3 to be a voltage of less than V ss +V th2 when a rising voltage is input into the terminal P 1 . Incidentally, the description of the operation of the control element 10 will be provided with the following description of the operation of the inverter circuit 1 .
[Operation]
Next, there will be described an example of the operation of the inverter circuit 1 with reference to FIG. 3 to FIG. 10 . FIG. 3 is a waveform diagram illustrating an example of the operation of the inverter circuit 1 . FIG. 4 through FIG. 10 are circuit diagrams illustrating an example of a series of operation of the inverter circuit 1 .
First, as illustrated in FIG. 4 , it is assumed that the input voltage V in is low (V ss ), the transistor Tr 5 is on, and the transistor Tr 4 is off. At the time, the transistors Tr 1 and Tr 3 are off, the capacitive element C 1 is charged with V dd , and a source voltage V s5 of the transistor Tr 5 is V dd . Further, the gate voltage V g2 of the transistor Tr 2 is V dd +ΔV. Here, ΔV is a value equal to or higher than the threshold voltage V th2 of the transistor Tr 2 , and the transistor Tr 2 is on. Therefore, at the time, in the output terminal OUT, V dd is output as the output voltage V out .
Subsequently, as illustrated in FIG. 5 , in a state in which the input voltage V in is low (V ss ), the transistor Tr 4 is turned on after the transistor Tr 5 is turned off. In other words, the transistor Tr 4 is turned on before the input voltage V in changes from low (V ss ) to high (V dd ). The gate voltage V g2 of the transistor Tr 2 is V dd +ΔV before the transistor Tr 4 is turned on. Therefore, even when the transistor Tr 4 changes from OFF to ON, the transistor Tr 2 maintains the ON state, and V dd is maintained for the output voltage V out as well.
Next, in a state in which the input voltage V in is low (V ss ), the transistor Tr 5 is turned on after the transistor Tr 4 is turned off. Similarly, when the transistor Tr 4 is turned on (when the transistor Tr 5 is turned off) after the transistors Tr 4 and Tr 5 repeat ON and OFF, the input voltage V in changes from low (V ss ) to high (V dd ) ( FIG. 6 ). Then, the transistors Tr 1 , Tr 3 and Tr 6 are turned on, and the gates and the sources of the transistors Tr 2 and Tr 7 are charged to the voltage V L (=V ss ) of the low voltage line L L . As a result, the transistor Tr 2 is turned off, and in the output terminal OUT, V ss is output as the output voltage V out . Further, when the transistor Tr 4 is turned on, the capacitive element C 1 charged with V dd is connected to the low voltage line L L via the transistor Tr 4 . As a result, the voltage of the terminal (terminal B) on the transistor Tr 5 side of the capacitive element C 1 gradually decreases from V dd and eventually becomes V ss .
Subsequently, in a state in which the input voltage V in is high (V dd ), the transistor Tr 5 is turned on after the transistor Tr 4 is turned off. Similarly, when the transistor Tr 4 is turned on (when the transistor Tr 5 is off) after the transistors Tr 4 and Tr 5 repeat ON and OFF, the input voltage V in changes from high (V dd ) to low (V ss ). Then, the transistors Tr 1 , Tr 3 and Tr 6 are turned off.
Here, when the transistor Tr 4 is turned on, the voltage (the voltage of the terminal B) of the capacitive element C 1 gradually decreases from V dd2 as described above ( FIG. 7 ). Incidentally, V X in FIG. 7 is the voltage (the voltage of the terminal B) of the capacitive element C 1 in a state immediately before the input voltage V in changes from high (V dd ) to low (V ss ). However, after the transistor Tr 4 is turned on, the input voltage V in changes from high (V dd ) to low (V ss ), and the transistor Tr 3 is turned off ( FIG. 8 ). Therefore, the capacitive element C 1 is connected to the gate of the transistor Tr 7 via the transistor Tr 4 and thus, the capacitive element C 1 charges the gate of the transistor Tr 7 . As a result, each of the voltage of the capacitive element C 1 and the gate voltage V g2 of the transistor Tr 2 becomes a voltage V y .
At the time, in a case in which V y is a value equal to or larger than the sum of the voltage (=V ss ) of the low voltage line L L and the threshold voltage V th7 of the transistor Tr 7 (that is, V ss +V th7 ), the transistor Tr 7 is turned on, and a current flows in the transistor Tr 7 .
Here, the voltage V y will be considered. It is assumed that parasitic capacitances of the transistors Tr 1 through Tr 7 are small enough to be ignored as compared with the capacitive element C 1 . At the time, V y is expressed by an equation (1) using V.
V y =V X (1)
It is apparent from the equation (1) that V y is determined without relying on the capacity of the capacitive element C 1 , and V y always becomes V X .
The source of the transistor Tr 7 and the gate of the transistor Tr 2 are electrically connected to each other. Therefore, when a current flows in the transistor Tr 7 , the gate voltage V g2 of the transistor Tr 2 starts rising. After a lapse of a predetermined period of time, when the gate voltage V g2 of the transistor Tr 2 becomes V s , +V th2 or more, the transistor Tr 2 is turned on and the output voltage V out begins increasing gradually.
Between the gate and the source of the transistor Tr 2 , the capacitive element C 2 is connected. Therefore, due to bootstrap operation by the capacitive element C 2 , the gate voltage V g2 of the transistor Tr 2 also changes as a source voltage V s2 of the transistor Tr 2 changes. Here, when attention is paid to the gate and the source of the transistor Tr 2 , it is found that the gate voltage V g2 of the transistor Tr 2 rises due to the current of the transistor Tr 7 and the rise in the source of the transistor Tr 2 . Therefore, because its transient is faster than that in a case of a rise only due to the current of the transistor Tr 2 , the voltage V gs2 between the gate and the source of the transistor Tr 2 gradually rises.
Here, a gate voltage V g7 of the transistor Tr 7 is V y , and the transistor Tr 4 between the gate of the transistor Tr 7 and the low voltage line L L is on. Therefore, the capacitive element C 1 is connected to the gate of the transistor Tr 7 and thus, the gate voltage V g7 of the transistor Tr 7 hardly follows the change of the source voltage V s7 , and is approximately a value of V y . As a result, the current from the transistor Tr 7 becomes small as the gate voltage V g2 of the transistor Tr 2 rises. Eventually, when the voltage V gs7 between the gate and the source of the transistor Tr 7 becomes the threshold voltage V th7 of the transistor Tr 7 , the current from the transistor Tr 7 becomes considerably small, and due to the current from the transistor Tr 7 , the gate voltage V g2 of the transistor Tr 2 hardly increases. However, at the time, the transistor Tr 2 is on, and the source voltage V s2 (the output voltage V out ) of the transistor Tr 2 continues rising and thus, the gate voltage V g2 of the transistor Tr 2 also keeps rising due to the bootstrap operation, and the transistor Tr 7 is turned off completely.
At the time, when the voltage V gs2 between the gate and the source of the transistor Tr 2 is ΔV, and if ΔV is larger than the threshold voltage V th2 of the transistor Tr 2 , V dd is output to the outside as the output voltage V out ( FIG. 9 ).
Subsequently, the transistor Tr 4 is turned off. Even if the transistor Tr 4 is turned off, the transistor Tr 7 also is turned off and thus, the gate voltage V g2 of the transistor Tr 2 is not affected. Therefore, the output of V dd to the outside as the output voltage V out continues. Further, after the transistor Tr 4 is turned off, the transistor Tr 5 is turned on again, and the source voltage V s5 of the transistor Tr 5 becomes an electric potential of V dd .
When the transistor Tr 4 is turned on after the transistor Tr 5 is turned off, capacitive coupling occurs again, and the gate voltage V g7 of the transistor Tr 7 and the source voltage V s5 of and the transistor Tr 5 come to be at the same potential. When the voltage V gs7 of the transistor Tr 7 at the time is assumed to be V a , as illustrated in FIG. 10 , the gate voltage V g7 between the gate and the source of the transistor Tr 7 is V a −V dd −ΔV, and the transistor Tr 7 still remains off. In addition, the voltage V gs2 between the gate and the source of the transistor Tr 2 continues to be ΔV and thus, V dd is output to the outside as the output voltage V out . By repeating these operations, the gate voltage V g7 of the transistor Tr 7 eventually becomes V dd .
As described above, in the inverter circuit 1 of the present embodiment, the pulse signal (e.g., Part (B) of FIG. 2 ) whose signal waveform is approximately the inverse of the signal waveform (e.g., Part (A) of FIG. 2 ) of the pulse signal input into the input terminal IN is output from the output terminal OUT.
[Effect]
Incidentally, for example, the inverter circuit 200 as illustrated in FIG. 17 in related art has the single channel type of circuit configuration in which the two n-channel MOS transistors Tr 1 and Tr 2 are connected in series. In the inverter circuit 200 , for example, as illustrated in FIG. 18 , when the input voltage V in is V ss , the output voltage V out is V dd −V th2 without being V dd . In other words, the threshold voltage V th2 of the transistor Tr 2 is included in the output voltage V out , and the output voltage V out is greatly affected by the variations of the threshold voltage V th2 of the transistor Tr 2 .
Thus, for example, as illustrated in the inverter circuit 300 of FIG. 19 , it is conceivable that the gate and the drain of the transistor. Tr 2 may be electrically isolated from each other, and the gate may be connected to the high voltage wiring L H2 to which the voltage V dd2 (≧V dd +V th2 ) higher than the voltage V dd of the drain is applied. In addition, for example, it is conceivable to provide the bootstrap type of circuit configuration as indicated by the inverter circuit 400 in FIG. 20 .
However, in the circuit in any of FIG. 17 , FIG. 19 and FIG. 20 , until the time when the input voltage V in becomes high, namely when the output voltage V out becomes low, a current (through current) flows from the high voltage wiring L H side to the low voltage wiring L L side via the transistors Tr 1 and Tr 2 . As a result, the power consumption in the inverter circuit also becomes large. In addition, in the circuits of FIG. 17 , FIG. 19 and FIG. 20 , when, for example, the input voltage V in is V dd as indicated with the point surrounded by the broken line in Part (B) of FIG. 18 , the output voltage V out is not V ss , and the peak value of the output voltage V out varies. Therefore, for example, when any of these inverter circuits is applied to a scanner in an organic electroluminescence display device employing an active matrix system, the threshold corrections and the mobility corrections of the drive transistors in the pixel circuits vary among the pixel circuits, and such variations result in variations in luminance.
Thus, for example, as indicated by an inverter circuit 500 in FIG. 21 , it is conceivable that between the transistors Tr 1 and Tr 2 in the output stage and the input terminal IN, the capacitive elements C 1 and C 2 and the transistors Tr 3 through Tr 5 may be provided, and a control signal as illustrated in FIG. 22 may be input into the transistors Tr 4 and Tr 5 . In the inverter circuit 500 , there is almost no time period over which the transistor Tr 1 and the transistor Tr 2 are turned on at the same time. Therefore, almost no through current flows, and power consumption may be suppressed to a low level. In addition, in response to a fall in the input voltage V in , the output voltage V out becomes a voltage on a high voltage line V H1 side, and in response to a rise in the input voltage V in , the output voltage V out becomes a voltage on the low voltage line L L side. Therefore, there are no variations in the output voltage V out , and variations in luminance from pixel to pixel may be reduced.
Incidentally, in the inverter circuit 500 of FIG. 21 , the newly inserted transistor Tr 5 is connected to a high voltage line L H2 to which a voltage higher than the high voltage line L H1 connected to the transistor Tr 2 is applied. This is to enable turning on of the transistor Tr 2 when the gate of the transistor Tr 2 is charged by the capacitive element C 1 charged with the voltage V dd2 . However, the voltage applied to the high voltage line L H2 is the voltage higher than the input voltage V in . Therefore, when the withstand voltage of the inverter circuit 500 is made equal to the withstand voltage of the inverter circuit 200 , yields may be reduced. Moreover, when the withstand voltage of the inverter circuit 500 is made higher than the withstand voltage of the inverter circuit 200 , manufacturing cost may increase.
On the other hand, in the inverter circuit 1 of the present embodiment, between the gate of the transistor Tr 7 and the low voltage line L L , between the gate of the transistor Tr 2 and the low voltage line L L , and between the source of the transistor Tr 2 and the low voltage line L L , the transistors Tr 1 , Tr 3 and Tr 6 that perform on-off operation according to a potential difference between the input voltage V in and the voltage V L of the low voltage line L L are provided, respectively. As a result, when the gate voltage of each of the transistors Tr 1 , Tr 3 and Tr 6 changes (falls) from high (V dd ) to low (V ss ), on-resistance of each of the transistors Tr 1 , Tr 3 and Tr 6 gradually becomes large, and the time necessary to charge the gates and the sources of the transistors Tr 2 and Tr 7 to the voltage V L of the low voltage line L L becomes long. Further, when the gate voltage of each of the transistors Tr 1 , Tr 3 and Tr 6 changes (rises) from low (V ss ) to high (V dd ), the on-resistance of each of the transistors Tr 1 , Tr 3 and Tr 6 gradually becomes small, and the time necessary to charge the gates and the sources of the transistors Tr 2 and Tr 7 to the voltage V L of the low voltage line L L becomes short. Furthermore, in the inverter circuit 1 of the present embodiment, when the input voltage V in falls, the gate of the transistor Tr 7 is charged to a voltage equal to or higher than the on-voltage of the transistor Tr 7 . As a result, when the falling voltage is input into the input terminal IN, the transistors Tr 1 , Tr 3 and Tr 6 are turned off, and immediately after that, the transistor Tr 7 is turned on and further, the transistor Tr 2 is turned on and thus, the output voltage V out becomes the voltage on the high voltage line L H side. Moreover, when the input voltage V in rises, the transistors Tr 1 , Tr 3 and Tr 6 are turned on, and immediately after that, the transistors Tr 2 and Tr 7 are turned off. As a result, the output voltage V out becomes the voltage on the low voltage line L L side.
In this way, the inverter circuit 1 of the present embodiment is configured such that there are no time period over which the transistor Tr 1 and the transistor Tr 2 are turned on at the same time, time period over which the transistor Tr 6 and the transistor Tr 7 are turned on at the same time, and time period over which the transistors Tr 3 to Tr 5 are turned on at the same time. Therefore, there is almost no current (through current) that flows between the high voltage line V H and the low voltage line L L via the transistors Tr 1 to Tr 7 . As a result, power consumption is allowed to be suppressed. In addition, in the inverter circuit 1 , only a single voltage line is provided on each of the low voltage side and the high voltage side and thus, there is no need to increase the withstand voltage of the inverter circuit 1 . Based upon the foregoing, in the present embodiment, it is possible to reduce the power consumption without increasing the withstand voltage.
<Modification>
In the embodiment described above, for example, as illustrated in FIG. 11 and FIG. 12 , the transistor Tr 4 may be turned off when the falling voltage is input into the input terminal IN, and the transistor Tr 4 may be turned on after the falling voltage is input into the input terminal IN. In this case, it is possible to prevent the voltage (the source voltage of the transistor Tr 5 ) of the capacitive element C 1 from decreasing from V dd2 by the transistor Tr 3 . As a result, it is possible to cause the inverter circuit 1 to operate at a high speed.
In addition, in the embodiment and the modification described above, for example, although not illustrated, it is possible to delete the capacitive element C 2 in the inverter circuit 1 . Even in this case, it is possible to cause the inverter circuit 1 to operate at a higher speed.
Further, in the embodiment and the modification described above, the transistors Tr 1 to Tr 7 are formed by the n-channel MOS TFTs, but may be formed by p-channel MOS TFTs, for example. In this case however, the high voltage line V H is replaced with the low voltage line L L , and the high voltage line V H is replaced with the low voltage line L L . Furthermore, a transient response when the transistors Tr 1 to Tr 7 change (rise) from low to high and a transient response when the transistors Tr 1 to Tr 7 change (drop) from high to low are reversed.
<Application Example>
FIG. 13 illustrates an example of the entire configuration of a display device 100 that is one of application examples of the inverter circuit 1 according to each of the above-described embodiment and the modifications. This display device 100 includes, for example, a display panel 110 (display section) and a driving circuit 120 (drive section).
(Display Panel 110 )
The display panel 110 includes a display area 110 A in which three kinds of organic EL elements 111 R, 111 G and 111 B emitting mutually different colors are arranged two-dimensionally. The display area 110 A is an area that displays an image by using light emitted from the organic EL elements 111 R, 111 G and 111 B. The organic EL element 111 R is an organic EL element that emits red light, the organic EL element 111 G is an organic EL element that emits green light, and the organic EL element 111 B is an organic EL element that emits blue light. Incidentally, in the following, the organic EL elements 111 R, 111 G and 111 B will be collectively referred to as an organic EL element 111 as appropriate.
(Display Area 110 A)
FIG. 14 illustrates an example of a circuit configuration within the display area 110 A, together with an example of a write-line driving circuit 124 to be described later. Within the display area 110 A, plural pixel circuits 112 respectively paired with the individual organic EL elements 111 are arranged two-dimensionally. In the present application example, a pair of the organic EL element 111 and the pixel circuit 112 configure one pixel 113 . To be more specific, as illustrated in FIG. 12 , a pair of the organic EL element 111 R and the pixel circuit 112 configure one pixel 113 R for red, a pair of the organic EL element 111 G and the pixel circuit 112 configure one pixel 113 G for green, and a pair of the organic EL element 111 B and the pixel circuit 112 configure one pixel 113 B for blue. Further, the adjacent three pixels 113 R, 113 G and 113 B configure one display pixel 114 .
Each of the pixel circuits 112 includes, for example, a drive transistor Tr 100 that controls a current flowing in the organic EL element 111 , a write transistor Tr 200 that writes a voltage of a signal line DTL into the drive transistor Tr 100 , and a retention capacitor C s , and thus each of the pixel circuits 112 has a 2Tr1C circuit configuration. The drive transistor Tr 100 and the write transistor Tr 200 are each formed by, for example, an n-channel MOS Thin Film Transistor (TFT). The drive transistor Tr 100 or the write transistor Tr 200 may be, for example, a p-channel MOS TFT.
In the display area 110 A, plural write lines WSL (scanning line) are arranged in rows and plural signal lines DTL are arranged in columns. In the display area 110 A, further, plural power-source lines PSL (member to which the source voltage is supplied) are arranged in rows along the write lines WSL. Near a cross-point between each signal line DTL and each write line WSL, one organic EL element 111 is provided. Each of the signal lines DTL is connected to an output end (not illustrated) of a signal-line driving circuit 123 to be described later, and to either of the drain electrode and the source electrode (not illustrated) of the write transistor Tr 200 . Each of the write lines WSL is connected to an output end (not illustrated) of the write-line driving circuit 124 to be described later and to the gate electrode (not illustrated) of the write transistor Tr 200 . Each of the power-source lines PSL is connected to an output end (not illustrated) of a power-source-line driving circuit 125 to be described later, and to either of the drain electrode and the source electrode (not illustrated) of the drive transistor Tr 100 . Of the drain electrode and the source electrode of the write transistor Tr 200 , one (not illustrated) that is not connected to the signal line DTL is connected to the gate electrode (not illustrated) of the drive transistor Tr 100 and one end of the retention capacitor C s . Of the drain electrode and the source electrode of the drive transistor Tr 100 , one (not illustrated) that is not connected to the power-source line PSL and the other end of the retention capacitor C s are connected to an anode electrode (not illustrated) of the organic EL element 111 . A cathode electrode (not illustrated) of the organic EL element 111 is connected to, for example, a ground line GND.
(Drive Circuit 120 )
Next, each circuit within the drive circuit 120 will be described with reference to FIG. 13 and FIG. 14 . The drive circuit 120 includes a timing generation circuit 121 , a video signal processing circuit 122 , the signal-line driving circuit 123 , the write-line driving circuit 124 and the power-source-line driving circuit 125 .
The timing generation circuit 121 performs control so that the video signal processing circuit 122 , the signal-line driving circuit 123 , the write-line driving circuit 124 and the power-source-line driving circuit 125 operate in an interlocking manner. For example, the timing generation circuit 121 is configured to output a control signal 121 A to each of the above-described circuits, according to (in synchronization with) a synchronization signal 120 B input externally.
The video signal processing circuit 122 makes a predetermined correction to a video signal 120 A input externally, and outputs to the signal-line driving circuit 123 a video signal 122 A after the correction. As the predetermined correction, there are, for example, a gamma correction and an overdrive correction.
The signal-line driving circuit 123 applies, according to (in synchronization with) the input of the control signal 121 A, the video signal 122 A (signal voltage V sig ) input from the video signal processing circuit 122 , to each of the signal lines DTL, thereby performing writing into the pixel 113 targeted for selection. Incidentally, the writing refers to the application of a predetermined voltage to the gate of the drive transistor Tr 100 .
The signal-line driving circuit 123 is configured to include, for example, a shift resistor (not illustrated), and includes a buffer circuit (not illustrated) for each stage, corresponding to each column of the pixels 113 . This signal-line driving circuit 123 is able to output two kinds of voltages (V ofs , V sig ) to each of the signal lines DTL, according to (in synchronization with) the input of the control signal 121 A. Specifically, the signal-line driving circuit 123 supplies, via the signal line DTL connected to each of the pixels 113 , the two kinds of voltages (V ofs , V sig ) sequentially to the pixel 113 selected by the write-line driving circuit 124 .
Here, the offset voltage V ofs is a constant value without relying on the signal voltage V sig . Further, the signal voltage V sig is a value corresponding to the video signal 122 A. A minimum voltage of the signal voltage V sig is a value lower than the offset voltage V ofs , and a maximum voltage of the signal voltage V sig is a value higher than the offset voltage V ofs .
The write-line driving circuit 124 is configured to include, for example, a shift resistor (not illustrated), and includes a buffer circuit 5 for each stage, corresponding to each row of the pixels 113 . The buffer circuit 5 is configured to include plural inverter circuits 1 described above, and outputs, from an output end, a pulse signal approximately in the same phase as a pulse signal input into an input end. The write-line driving circuit 124 outputs two kinds of voltages (V dd , V ss ) to each of the write lines WSL, according to (in synchronization with) the input of the control signal 121 A. Specifically, the write-line driving circuit 124 supplies, via the write line WSL connected to each of the pixels 113 , the two kinds of voltages (V dd , V ss ) to the pixel 113 targeted for driving, and thereby controls the write transistor Tr 200 .
Here, the voltage V dd is a value equal to or higher than an on-voltage of the write transistor Tr 200 . V dd is the value of a voltage output from the write-line driving circuit 124 at the time of extinction or at the time of a threshold correction to be described later. V ss is a value lower than the on-voltage of the write transistor Tr 200 , and also lower than V dd .
The power-source-line driving circuit 125 is configured to include, for example, a shift resistor (not illustrated), and includes, for example, a buffer circuit (not illustrated) for each stage, corresponding to each row of the pixels 113 . This power-source-line driving circuit 125 outputs two kinds of voltages (V ccH , V ccL ) according to (in synchronization with) the input of the control signal 121 A. Specifically, the power-source-line driving circuit 125 supplies, via the power-source line PSL connected to each of the pixels 113 , the two kinds of voltages (V ccH , V ccL ) to the pixel 113 targeted for driving, and thereby controls the light emission and extinction of the organic EL element 111 .
Here, the voltage V ccL is a value lower than a voltage (V c1 +V ca ) that is the sum of a threshold voltage V c1 of the organic EL element 111 and a voltage V ca of the cathode of the organic EL element 111 . Further, the voltage V ccH is a value equal to or higher than the voltage (V c1 +V ca ).
Next, an example of the operation (operation from extinction to light emission) of the display device 100 according to the present application example will be described. In the present application example, in order that even when the threshold voltage V th and the mobility μ of the drive transistor Tr 100 change over time, light emission luminance of the organic EL element 111 remains constant without being affected by these changes, correction operation for the change of the threshold voltage V th and the mobility μ is incorporated.
FIG. 15 illustrates an example of the waveform of a voltage applied to the pixel circuit 112 and an example of the change in each of the gate voltage V g and the source voltage V s of the drive transistor Tr 100 . In Part (A) of FIG. 15 , there is illustrated a state in which the signal voltage V sig and the offset voltage V ofs are applied to the signal line DTL. In Part (B) of FIG. 15 , there is illustrated a state in which the voltage V dd for turning on the write transistor Tr 200 and the voltage V ss for turning off the write transistor Tr 200 are applied to the write line WSL. In Part (C) of FIG. 15 , there is illustrated a state in which the voltage V ccH and the voltage V ccL are applied to the power-source line PSL. Further, in Part (D) and Part (E) of FIG. 15 , there is illustrated a state in which the gate voltage V g and the source voltage V s of the drive transistor Tr 100 change over time in response to the application of the voltages to the power-source line PSL, the signal line DTL and the write line WSL.
(V th Correction Preparation Period)
First, a Preparation for the V th Correction is Made. Specifically, when the voltage of the write line WSL is V off , and the voltage of the power-source line PSL is V ccH (in other words, when the organic EL element 111 is emitting light), the power-source-line driving circuit 125 reduces the voltage of the power-source line PSL from V ccH to V ccL (T 1 ). Then, the source voltage V s becomes V ccL , and the organic EL element 111 stops emitting the light. Subsequently, when the voltage of the signal line DTL is V ofs , the write-line driving circuit 124 increases the voltage of the write line WSL from V off to V on , so that the gate of the drive transistor Tr 100 becomes V ofs .
(First V th Correction Period)
Next, the correction of V th is performed. Specifically, while the write transistor Tr 200 is on, and the voltage of the signal line DTL is V ofs , the power-source-line driving circuit 125 increases the voltage of the power-source line PSL from V ccL to V ccH (T 2 ). Then, a current I ds flows between the drain and the source of the drive transistor Tr 100 , and the source voltage V s rises. Subsequently, before the signal-line driving circuit 123 switches the voltage of the signal line DTL from V ofs to V sig , the write-line driving circuit 124 reduces the voltage of the write line WSL from V on to V off (T 3 ). Then, the gate of the drive transistor Tr 100 enters a floating state, and the correction of V th stops.
(First V th Correction Stop Period)
In a period during which the V th correction is stopped, in, for example, other row (pixel) different from the row (pixel) to which the previous correction is made, the voltage of the signal line DTL is sampled. At the time, in the row (pixel) to which the previous correction is made, the source voltage V s is lower than V ofs −V th . Therefore, during the V th correction stop period, in the row (pixel) to which the previous correction is made, the current I ds flows between the drain and the source of the drive transistor Tr 100 , the source voltage V s rises, and the gate voltage V g also rises due to coupling via the retention capacitor C s , as well.
(Second V th Correction Period)
Next, the V th correction is made again. Specifically, when the voltage of the signal line DTL is V ofs and the V th correction is possible, the write-line driving circuit 124 increases the voltage of the write line WSL from V off to V on , thereby causing the gate of the drive transistor Tr 100 to be V ofs (T 4 ). At the time, when the source voltage V s is lower than V ofs −V th (when the V th correction is not completed yet), the current I ds flows between the drain and the source of the drive transistor Tr 100 , until the drive transistor Tr 100 is cut off (until a between-gate-and-source voltage V gs becomes V th ). Subsequently, before the signal-line driving circuit 123 switches the voltage of the signal line DTL from V ofs to V sig , the write-line driving circuit 124 reduces the voltage of the write line WSL from V on to V off (T 5 ). Then, the gate of the drive transistor Tr 100 enters a floating state and thus, it is possible to keep the between-gate-and-source voltage V gs constant, regardless of the magnitude of the voltage of the signal line DTL.
Incidentally, during this V th correction period, when the retention capacitor C s is charged to V th , and the between-gate-and-source voltage V gs becomes V th , the drive circuit 120 finishes the V th correction. However, when the between-gate-and-source voltage V gs does not reach V th , the drive circuit 120 repeats the V th correction and the V th correction stop, until the between-gate-and-source voltage V gs reaches V th .
(Writing and μ Correction Period)
After the V th correction stop period ends, the writing and the μ correction are performed. Specifically, while the voltage of the signal line DTL is V sig , the write-line driving circuit 124 increases the voltage of the write line WSL from V off to V on (T 6 ), and connects the gate of the drive transistor Tr 100 to the signal line DTL. Then, the gate voltage V g of the drive transistor Tr 100 becomes the voltage V sig of the signal line DTL. At the time, an anode voltage of the organic EL element 111 is still smaller than the threshold voltage V e1 of the organic EL element 111 at this stage, and the organic EL element 111 is cut off. Therefore, the current I ds flows in an element capacitance (not illustrated) of the organic EL element 111 and thereby the element capacitance is charged and thus, the source voltage V s rises by ΔV y , and the between-gate-and-source voltage V g , soon becomes V sig +V th −ΔV y . In this way, the μ correction is performed concurrently with the writing. Here, the larger the mobility μ of the drive transistor Tr 100 is, the larger ΔV y is. Therefore, by reducing the between-gate-and-source voltage V g , by ΔV y before light emission, variations in the mobility μ among the pixels 113 are removed.
(Light Emission Period)
Lastly, the write-line driving circuit 124 reduces the voltage of the write line WSL from V on to V off (T 7 ). Then, the gate of the drive transistor Tr 100 enters a floating state, the current I ds flows between the drain and the source of the drive transistor Tr 100 , and the source voltage V s rises. As a result, a voltage equal to or higher than the threshold voltage V e1 is applied to the organic EL element 111 , and the organic EL element 111 emits light of desired luminance.
In the display device 100 of the present application example, as described above, the pixel circuit 112 is subjected to on-off control in each pixel 113 , and the driving current is fed into the organic EL element 111 of each pixel 113 , so that holes and electrons recombine and thereby emission of light occurs, and this light is extracted to the outside. As a result, an image is displayed in the display area 110 A of the display panel 110 .
Incidentally, in the present application example, for example, the buffer circuit 5 in the write-line driving circuit 124 is configured to include the plural inverter circuits 1 . Therefore, there is almost no through current that flows in the buffer circuit 5 and thus, the power consumption of the buffer circuit 5 may be suppressed. In addition, since there are few variations in the output voltages of the buffer circuits 5 , it is possible to reduce the variations among the pixel circuits 112 , in terms of the threshold correction and the mobility correction of the drive transistor Tr 100 within the pixel circuit 112 , and moreover, variations in luminance among the pixels 113 may be reduced.
Further, in the inverter circuit 1 , only a single voltage line is provided on each of the low voltage side and the high voltage side and thus, there is no need to increase the withstand voltage of the inverter circuit 1 and also, it is possible to minimize an occupied area and thus, a narrower frame is realized.
The present invention has been described by using the embodiment, the modifications and the application example, but the present invention is not limited to the embodiment and like and may be variously modified.
For example, in the embodiment and the modifications described above, only a single voltage line is provided on each of the low voltage side and the high voltage side. However, for example, a voltage line connected to at least one of plural transistors on the high voltage side and a voltage line connected to other transistors on the high voltage side may not be a common line. Similarly, for example, a voltage line connected to at least one of plural transistors on the low voltage side and a voltage line connected to other transistors on the low voltage side may not be a common line.
For example, in the above-described application example, the inverter circuit 1 according to the above-described embodiment is used in the output stage of the write-line driving circuit 124 . However, this inverter circuit 1 may be used in an output stage of the power-source-line driving circuit 125 , instead of being used in the output stage of the write-line driving circuit 124 , or may be used in the output stage of the power-source-line driving circuit 125 in conjunction with the output stage of the write-line driving circuit 124 .
The present application contains subject matter related to that disclosed in Japanese Priority Patent Application JP 2010-085492 filed in the Japan Patent Office on Apr. 1, 2010, the entire content of which is hereby incorporated by reference.
It should be understood by those skilled in the art that various modifications, combinations, sub-combinations and alterations may occur depending on design requirements and other factors insofar as they are within the scope of the appended claims or the equivalents thereof. | An inverter circuit including: first to third transistors; first and second switches; and a first capacitive element. The first and second transistors are connected in series between a first voltage line and a second voltage line. The third transistor is connected between the second voltage line and a gate of the second transistor. The first and second switches are connected in series between a voltage supply line and a gate of the third transistor, and are turned on/off alternately to prevent the first and second switches from simultaneously turning ON. One end of the first capacitive element is connected to a node between the first and second switches. Off-state of the first transistor allows a predetermined fixed voltage to be supplied from the voltage supply line to the gate of the second transistor, via the first switch, the one end of the first capacitive element and the second switch. | 6 |
BACKGROUND OF THE INVENTION
The present invention generally relates to the field of manufacturing textiles using chains as a component. The use of chains as a component of a textile has typically been an industrial process of assembling chain links in both an X and Y orientation in order with separate rings interlocking the individual links in both the X and Y directions. The resulting textile is commonly known as “chain mail.” Historical uses of chain mail textile include armor, jewelry, bags, and pot scrubbers. But manufacturing of chain mail requires each link in the chains to accommodate two dimensions of connection. This requires a manufacturing process to start with creating the links in the chain mail. However, chains are typically manufactured with the links in a single, linear direction. The chain mail manufacturing techniques that are known in the art require individually linking each link with separate rings that can be opened and closed with commercially available metalworking tools such as pliers. In addition, many chains may have esthetic appearances that would be beneficial if incorporated into a textile, but in the form of an existing linear chain, cannot be used to create traditional chain mail. Therefore, there is a need for manufacturing a textile out of chains that uses pre-made chains and does not require individual link rings.
BRIEF SUMMARY OF THE INVENTION
The present invention provides a new, novel method and process of manufacturing chains to create a textile. The process involves use of a substrate on which chains can be set with a mounting frame and then interconnected. Once the chains are interconnected, the substrate may be removed from the textile through a method of separation such as dissolving the substrate in the case of a dissolvable substrate or melting the substrate in the case of a wax substrate.
DESCRIPTION OF THE FIGURES
FIG. 1 . Top view of finished chain textile.
FIG. 2 . Top view of substrate held in a mounting frame.
FIG. 3 . Top view of finished textile mounted on substrate.
FIG. 4 . Side view of the mounting frame with substrate.
FIG. 5 . Side view of the mounting frame with chain laid onto substrate.
FIG. 6 . Side view of the mounting frame with the stitching.
FIG. 7 . Side view of the mounting frame with the stitching tightened.
FIG. 8 . Side view of the mounting frame after the substrate has been dissolved in a solvent.
FIG. 9 . A close-up photograph of the finished textile.
The headings provided herein are for convenience only and do not necessarily affect the scope or meaning of the claimed invention. In the drawings, the same reference numbers and any acronyms identify elements or acts with the same or similar structure or functionality for ease of understanding and convenience. To easily identify the discussion of any particular element or act, the most significant digit or digits in a reference number refer to the Figure number in which that element is first introduced (e.g., element 204 is first introduced and discussed with respect to FIG. 2 ).
DETAILED DESCRIPTION OF THE INVENTION
Various examples of the invention will now be described. The following description provides specific details for a thorough understanding and enabling description of these examples. One skilled in the relevant art will understand, however, that the invention may be practiced without many of these details. Likewise, one skilled in the relevant art will also understand that the invention can include many other features not described in detail herein. Additionally, some well-known structures or functions may not be shown or described in detail below, so as to avoid unnecessarily obscuring the relevant description. The terminology used below is to be interpreted in its broadest reasonable manner, even though it is being used in conjunction with a detailed description of certain specific examples of the invention. Indeed, certain terms may even be emphasized below; however, any terminology intended to be interpreted in any restricted manner will be overtly and specifically defined as such in this Detailed Description section.
The chain component is typically a sequence of links, where a given loop of one link has a front and rear neighboring link that loops through the link. The chain component may be comprised of any durable solid material, including but not limited to metal, plastic, glass, rubber, ceramic, or fiber. However, in the textile, the two neighboring chains do not have chain links that connect them on the axis that is normal to the length of the chain. In one embodiment one or more threads pass through the links of neighboring chains so that they are stitched together tightly. As shown in FIG. 1 , the chains ( 100 ) are bound to each other by means of the threads ( 101 ) that run perpendicular to the longitudinal axis of the chains ( 100 ). As shown in FIG. 9 , the chains may be laid side by side and the threads intertwined with the links in order to form a flexible textile made up of the series of chains. In the preferred embodiment, the chains are selected where the chain links comprising the chains are shaped to lay flat against a planar surface, that is, the loop of the link is shaped to accommodate the intertwined links of its neighboring links along the chains' length. In the preferred embodiment, the thread is comprised of nylon, acetate or other strong materials that are resistant to water or other solvents. For example, these threads may also include cotton, wool, other natural fibers, polyester, rayon, silk, metal, rubber, latex, polypropylene, Kevlar®, Teflon®, or Nomex®, alone or in combination with other materials. In the preferred embodiment, the thread is resistant to the solvent that dissolves the substrate or the head used to melt the wax substrate.
The flexibility of a chain makes it difficult to sew one chain to its neighboring chain reliably and in a manner where the regularity of the link pattern is consistent both along the longitudinal axis of the chains as well as along the axis perpendicular to the chains' longitudinal axis. One object of the invention is to insure the regularity of the chain links comprising the textile in order that it is esthetically pleasing and functional.
In another preferred embodiment, the chain textile is fabricated using a multi-step process. The first step of the process is the selection of a substrate upon which manufacture of the textile takes place. The suitable substrate must be strong enough to withstand stretching in both dimensions along its planar surface without tearing. In addition, it must be sufficiently strong that while in the condition of being stretched, the process of sewing needles penetrating the substrate will not cause the substrate to fail. Finally, the substrate has to be soluble in a solvent or with a relatively low melting point. In the preferred embodiment, the substrate is a resinated paper that is water soluble. Other substrates may be used to accommodate different density of chains.
In the first step of the process, the substrate ( 200 ) is stretched within a frame, FIG. 2 . In one embodiment, a first set of threads ( 201 ) are run from the frame to the edges of the substrate and tension applied in order to establish a strong, substantially planar surface for the substrate. FIG. 4 shows a side view of the frame with the substrate. In the second step of the process, the chains ( 300 ) are laid out on the substrate side by side. See FIG. 3 . FIG. 5 shows a side view of the chains lying on the substrate. In one embodiment, the substrate is marked with registration marks in order to correctly position the chains. In another embodiment, pins are inserted at the end of the chains that pass through the substrate in order that the ends of the chains are fixed. In the third step of the process, a second set of threads ( 301 ) are passed through the links of the neighboring chain in order to bind the neighboring chains to the substrate and to each other. FIG. 6 shows a side view of the threading of the chain against the substrate. The thread ( 301 ) passes through the hole formed by the chain link, down through the substrate, and then back through the substrate into the next hole formed by the neighboring chain link. In one embodiment, the threads run along the axis perpendicular to the longitudinal axis of the chains. In this embodiment, each new loop of the thread is passing through the next neighboring chain link. In another embodiment, the threads run along a direction at a diagonal to the longitudinal axis of the chains. In either embodiment, threading that runs in both a perpendicular and diagonal direction may be used together. The specific pattern of threading may be varied, so long as the threading establishes that each chain is sufficiently bound to its two neighboring chains, except for the chains at the edge of the textile piece, which are bound to the single neighboring chain. FIG. 7 shows a side view down the longitudinal axis of the chains showing the chains being bound together on the substrate.
In the final step of the manufacturing process, the frame with the substrate and chain textile attached to it is placed into a bath containing a solvent that can dissolve the substrate without damaging either the chains, the chains' finish or the threads. In the preferred embodiment, the solvent is water. After the solvent has dissolved the substrate, all that remains is the manufactured textile piece. FIG. 8 . The textile piece may then be cleaned and prepared to be integrated into any kind of garment, jewelry, accessory, luggage or other item that textiles are useful for.
In another embodiment, in the last step of the manufacturing process, the solvent is applied to the substrate and chain textile. Such application can be by various methods, such as pouring, spraying or sponging the solvent onto the substrate. After the solvent has dissolved the substrate, all that remains is the manufactured textile piece. FIG. 8 . The textile piece may then be cleaned and prepared to be integrated into any kind of garment, jewelry, accessory, luggage or other item that textiles are useful for.
In another embodiment, the substrate may be a solid substance that can be dissolved or melted. In this embodiment of the invention, the chains may be pressed into the surface of the solid substrate, or the substrate may have channels pressed or otherwise formed in the surface of the substrate. The chains may then be laid into the channels. In one embodiment, the substrate is a wax. This approach permits the chains to be laid in circular or spiral patterns, or patterns involving a corner. Once the chains are laid into the substrate, the threading process is performed to sew the chains together into a textile. At that point, the substrate is removed by means of dissolving the substrate into the solvent or melting the substrate, as in the case of wax. The substrate has to be thin enough so that the thickness of the substrate does not impede the threading process by resisting the movement of the needle, nor introduce slack into the thread stitches when the substrate is removed. In one embodiment, this is accomplished by coating the dissolvable substrate with the solid substrate. In one embodiment, a wax layer is coated on dissolvable paper. In this embodiment, the wax can be patterned with the channels into which the chains are placed. When the textile has been assembled, the paper substrate is dissolved using water. If the water is heated to sufficient temperature above the melting point of wax, any wax residue on the chains can be removed.
It is appreciated that various features of the invention which are, for clarity, described in the context of separate embodiments may also be provided in combination in a single embodiment. Conversely, various features of the invention which are, for brevity, described in the context of a single embodiment may also be provided separately or in any suitable combination. It is appreciated that the particular embodiment described in the specification is intended only to provide an extremely detailed disclosure of the present invention and is not intended to be limiting. | A system and method is described for easily creating textiles out of chains connected by thread. A dissolvable or removable substrate on which chains can be set is used whereby the thread stitching passes through the substrate. After the textile stitching is completed, the substrate is then removed, including by use of a dissolving solvent or by melting. | 3 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is related to, and claims priority from U.S. patent application Ser. No. 10/938,868 “Method of Interactive System for Previewing and Selecting Eyeware” by Dr. Michael R. Neal filed Sep. 13, 2004. This application is also related to, and claims priority from U.S. Provisional Patent Application 60/659,605 “VIRTUAL MONITOR SYSTEM HAVING LAB-QUALITY COLOR ACCURACY” by Dr. Michael R. Neal filed Mar. 7, 2005.
FIELD OF THE INVENTION
[0002] The present invention relates to an interactive device which displays computer enhanced images, and more specifically to an interactive device which displays computer color-accurate enhanced images simulating a user wearing various products.
BACKGROUND OF THE INVENTION
[0003] There are several interactive computer systems generally known in the art to enable users to virtually view and select products. One such example exists in hair salons. A customer has their picture taken and displayed on a computer screen. The image is then computer enhanced to display different hair styles allowing the customer to select which hair style they prefer. This allows the consumer to view the hair design as it would look on them, without having to actually have their hair cut or styled.
[0004] A problem with the device described above, and similar devices is that these devices are typically not intuitively obvious to use and are typically operated by an employee, taking up the employee's time.
[0005] These images are also crude representations of the user and typically do not properly display the correct colors or overlay the computer enhancements. These do not give realistic representations, thereby distorting their color, thereby limiting their accuracy.
[0006] Typically when customers are shopping they would like an indication of how various products such as cosmetics, hair coloring, apparel, hats, jewelry, glasses, colored contacts etc. would look on them. Typically the process of trying on clothes, putting on makeup or glasses becomes time consuming, or sometimes is not possible (as in coloring your hair). Therefore, a system which would take a picture of the customer, and add overlays of various products and coloring would be useful, both to the customer and to the employees.
[0007] Currently there is a need for a device which may be easily operated by a customer, and provide an accurate image and colors of a customer wearing a product.
SUMMARY OF THE INVENTION
[0008] The present invention may be embodied as a method of providing a color accurate enhanced image of a user.
[0009] The environment is darkened and the only lighting used is specially designed lighting having a spectrum that most closely resembles that of daylight. This minimizes the color distortion introduced.
[0010] An input profile of an input device intended to be used is determined indicating the color distortion introduced by the input device and the lighting.
[0011] An image is acquired using the input device in a controlled lighting environment.
[0012] The color spectrum of at least one location of the acquired image is modified according to the input profile to create a workspace image.
[0013] Features, such as lips, hair or skin of the image are interactively selected by the user to modify their colors.
[0014] An output profile of an output device, such as a monitor, intended to display the workspace image, is calculated.
[0015] The spectrum of the workspace image is adjusted according to the output profile to result in an adjusted image; and
[0016] The adjusted image is displayed on the output device to the user to result in an image with substantially improved color accuracy relative to prior art devices.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] A complete understanding of the present invention may be obtained by reference to the accompanying drawings, when considered in conjunction with the subsequent detailed description, in which:
[0018] FIG. 1 is a perspective view illustrating a system compatible with the present invention.
[0019] FIG. 2 is a graph showing the spectral output of daylight vs. the SoLux™ light.
[0020] FIG. 3 is a graph showing the spectral output of daylight vs. incandescent light.
[0021] FIG. 4 is a graph showing the spectral output of daylight vs. fluorescent light.
[0022] FIGS. 5 a , 5 b and 5 c together are a flowchart illustrating the operation of a method according to the present invention.
[0023] FIG. 6 is a screen shot of monitor 11 shown having two images 610 and 620 of user 2 displayed side by side.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0000] Color Basics
[0024] The actual color of an object is a mixture of light rays of various visible light frequencies, with each frequency having a brightness or amplitude (a “spectrum”). Therefore, the color of an object at a specific point may accurately be described by its spectrum at that point.
[0000] Input Devices
[0025] Light is attenuated as it passes through various materials. Light waves at different frequencies are attenuated in different amounts as they pass through the same material. Therefore, light passing through lenses of a camera, or through the glass of a scanner attenuates some frequencies more than others. A measure of the attenuation over a visible range is defined as a light absorption profile.
[0026] Also, solid state devices which convert light into electric currents have a sensitivity which varies by the frequency of the light. The light sensors of a digital camera and scanner may have greater sensitivity to some frequencies, providing a strong signal when receiving these frequencies; however, it may be less sensitive when receiving other frequencies, producing a weaker electric signal. The sensor response over a range of visible light frequencies may be described by a sensor profile.
[0027] Light may also be reflected from mirrors which may distort the resulting amplitudes. These may also be described by a profile.
[0028] Similarly, light may pass through or reflect off of other surfaces in its path which could alter its intensities across the visible frequency band.
[0029] All of the elements which affect the resulting spectrum of the light should be taken into account to more accurately recover the original light spectrum.
[0000] Lighting
[0030] The ambient lighting present during the acquisition of an image affects the color spectra of the image. Lights illuminate with a spectral profile specific to each light. For example, if a light exhibits considerably amplified yellow frequencies relative to the remainder of the spectrum, it will cause an image acquired using this light to have amplified yellow frequencies as compared with the actual object.
[0031] In order to correct for the lighting profile, the present invention uses light which mimics the spectrum of daylight such as the specially designed SoLux™ light bulbs by Tailored Lighting, Inc. However, it is not possible to exactly replicate the spectrum of daylight; the lights influence the spectrum of an acquired image. These effects should also be taken into account.
[0032] A more complete description of the lighting spectra is provided at the website http://www.soluxtli.com/ hereby incorporated by reference as if set forth in its entirety herein.
[0000] Monitors
[0033] Synthetic devices which display images synthesize colors and hence images by trying to accurately reproduce these spectra at all locations of the image. CRT monitors create light with several different phosphors on their screen which illuminate when they are hit by a cathode ray. Each phosphor has a specific characteristic illumination spectrum. These phosphors are chosen to produce most of its illumination in a narrow range of the spectrum, for example a red spectrum range. Therefore, the object is to differentially illuminate each of the several phosphors to mix and provide a composite spectrum which most accurately represents the target color spectrum at a given point in the image. This is reproduced for all points (pixels) in the image.
[0034] Similarly, a liquid crystal display unit employs several different types of liquid crystals each which have characteristic illumination spectra. These are differentially illuminated to approximate a color at each screen location.
[0035] Since the monitors approximate the color using the tools (phosphors and liquid crystals) they have, they do not provide an exact reproduction of the original color. Therefore, it is possible to determine the characteristic output of each specific monitor to potentially correct for its imperfections.
[0000] Calibration of the Monitor
[0036] One way to calibrate a monitor is to provide the computer driving the monitor with an image having a known spectrum, display the spectrum and use a device to read the output of the monitor. The computer compares the readings to an intended spectrum to determine how much error is produced by the monitor. This results in a monitor profile.
[0037] The computer driving the image to the monitor typically has no information as to the type of monitor or its characteristic monitor profile. The signal is generated which is not adjusted to take into account the color inaccuracies of the monitor. The signal sent to the monitor is an internal or workspace representation of the signal, and has no color corrections built into it. Therefore, even if the colors in the computer are accurately represented; the color output of the monitor will be inaccurate based due to the color inconsistencies introduced by the monitor, according to the monitor profile.
[0000] Correction of Monitor Output
[0038] Therefore, using the monitor profile, the spectral frequencies where the monitor decreases the amplitude by an attenuation factor in the monitor profile, theoretically will be increased by that attenuation factor. Similarly, the spectral band where the monitor increases the amplitude by an amplification factor as per the monitor profile, will be attenuated by that amplification factor.
[0039] This corrected signal is then converted into an appropriate monitor signal (such as an RGB, composite video, etc) which is then displayed showing a more accurate representation of color.
[0000] Printers Similarly, printers using several different colors of ink, the most common being cyan, magenta, yellow, and black each having a specific color spectrum, may be mixed to approximate the target color.
[0040] Theoretically, many different colors of ink having their characteristic spectra may be combined to approximate a target color with each with varying degrees of accuracy.
[0000] Implementation
[0041] The present invention is such a device which is easy to operate and frees up the employees allowing them to take care of other tasks. It also allows the customer to view a larger number of products in a non-pressured environment. This device however must be very intuitive and provide accurate images, or its value will be significantly diminished.
[0042] Referring now to the several drawing figures in which identical elements are numbered identically throughout, a description of the preferred embodiment of the present invention will be provided. The preferred embodiment of the invention is described for illustrative purposes, it being understood that the invention may be embodied in other forms not specifically shown in the drawings or described hereinafter.
[0043] Referring now in detail to the drawings, FIG. 1 shows a virtual monitor system 1 having lab quality color accuracy according to one embodiment of the present invention. This includes a computer 10 with a digital camera 12 attached thereto. In the preferred embodiment, the computer 10 includes all the components of a typical computer system including a processor, memory storage devices and monitor 11 . The computer 10 also includes data input/output ports, such as a CD-ROM drive and serial and USB ports for connection to other devices. Additionally, monitor 11 of the computer 10 may be a touch screen display, through which the user can input data and/or make selections by touching the screen. Alternatively, a keyboard 31 and mouse 33 may be used for user input.
[0044] In the preferred embodiment shown in FIG. 1 , the camera 12 includes a Velcro™ attachment on the underside of its housing and is secured to the computer 10 via a corresponding Velcro™ attachment located thereon. The camera 12 is connected to the computer 10 by data cable 16 , as is well known in the art.
[0045] Typically, the computer 10 , will be set-up at a point of sale, such as an office of an eye care professional, a cosmetic counter, or apparel department, etc. where it would be useful to simulate products being used or worn by a user.
[0046] It should also be understood that the exemplary embodiments shown here are for illustrative purposes only, and are not meant to limit the scope of the invention. In particular, the wording, labels, arrangement and visual effects displayed on the monitor 11 are exemplary embodiments and may be changed or modified without departing from the scope of the invention.
[0047] Monitor 11 may display acquired images, overlays to images, text, buttons, icons etc. to interact with a user.
[0048] The virtual monitor system 1 may initially display a greeting, and accompanying sounds or speech, inviting a user to try the program and asking whether they are interested in a product being sold. The system of the present invention may also include a motion detection feature so that when a user passes in view of the camera 12 , the system will invite the user to try the virtual monitor system 1 .
[0049] Before the virtual monitor system 1 is used, the system must be calibrated for the specific input devices and output devices being used.
[0050] FIGS. 5 a , 5 b and 5 c together show a flowchart of the operation of one embodiment of the virtual monitor system 1 according to the present invention. The functioning will be described here with reference to this flowchart and with reference to parts of the invention shown in FIG. 1 ,
[0000] Input Device Calibration
[0051] As described above, camera 12 distorts the spectrum of light passing through it. Also, as mentioned above, the ambient lighting has an effect upon the spectrum of the acquired image. Therefore, the room is dark and lights 35 and 37 , specially designed to have the spectrum similar to that of daylight, are used as the sole source of light.
[0052] Since we're trying to determine how the camera sees light, we must calibrate the camera with a test pattern and an electronic representation of the spectra of each of the colors/locations on the test pattern. In step 501 , a test pattern specially manufactured to have accurate colors at specific locations of the pattern is provided, along with a corresponding color-accurate electronic representation of the test pattern.
[0053] In step 503 the test pattern is placed a fixed distance from camera 12 .
[0054] Camera 12 then acquires an image in step 505 by taking a picture of the test pattern. This image is stored in computer 10 as an electronic representation in computer 10 of spectra of each of the colors of the test pattern. Each location of the test pattern has a corresponding location on the acquired picture.
[0055] The electronic representation of the color at a location of the test pattern is compared to a corresponding location of the picture to determine the deviation in its color spectrum in step 507 .
[0056] Step 507 is repeated for different locations/ colors of the test pattern and the acquired picture to result in a file describing the deviation in color due to the camera operating in the given light conditions. This is referred to as the ‘camera profile’. One such commonly available software product which may be used to determine the camera profile is MonacoDC Color™ by X-rite Photo Marketing. A more detailed description of this subject is provided in the “MonacoOPTIX XR , Color Management Systems” publication by X-rite Photo Marketing, at the website http://www.xritephoto.com/product/DCcolor.com hereby incorporated by reference as if set forth in its entirety herein. A similar operation may be performed for other input devices such as a document scanner to determine the profiles of these input devices. Collectively these may be referred to as input profiles. These input profiles are specific not only to the type and model of input device used, but are specific to the input device itself This is because manufacturing differences and changes over time may cause lenses to become discolored, scratched, tinted and photo sensors may alter their sensitivity spectrum.
[0057] This input calibration must be performed whenever there is a change in performance, such as when a new camera is used, different lenses or filters are used, or the performance of the camera is otherwise changed. It is recommended that this calibration be performed when there is a noticeable difference in the color accuracy of the display.
[0058] A more complete description of the determination of an input profile is provided at the website http://www.xritephoto.com/product/dccolor/ hereby incorporated by reference as if set forth in its entirety herein.
[0000] Image Acquisition
[0059] In step 509 , the user 2 , stands in front of the camera at a specific distance and interacts with touch screen monitor 11 or keyboard 31 and mouse 33 to select an icon displayed on monitor 11 causing an image to be acquired of user 2 . This may include various prompts either visual on monitor 11 , or audible music, or voice instructing the user. An image is then acquired by the camera 12 and transferred to computer 10 . One such piece of software which would function is the Breeze Camera Control application.
[0000] Image Adjustment
[0060] The input profile of step 507 defines the color deviation of the acquired image from the actual objects. The actual color representation of the image may be corrected in step 511 using the input profile of step 507 to correct the effects introduced by the input device and the ambient lighting. The adjusted image is now defined to have a ‘workspace profile’. One such software product which will perform such correction is Adobe Photoshop, however others may be employed.
[0000] Overlay Selection
[0061] In step 520 the user is asked to select a feature of their image which they would like to modify. In the Referenced Application, the user selected different colored contact lenses which essentially changed the color of their eyes. An overlay was constructed which covered the irises of the user's eyes in the image, and the color of the overlays were interactively chosen.
[0062] The present application will perform this function in a more color-accurate manner. In addition, the present application allows for the user to select and change the color of other features of their image such as lip color, hair color, skin tone, blemishes, apparel, etc. and combinations of the above.
[0063] One such method of selecting the overlay of step 520 would be to provide a message to the user indicating a menu of features to be changed, with choices being, for example, lip color, hair color, skin color, eye color, etc. in step 521 .
[0064] Next, the user should choose a general area containing the feature in step 523 .
[0065] The user is prompted to select a point inside of the feature in the chosen area in step 525 .
[0066] In step 527 the computer determines a color characteristic which will be used to determine the extent of the feature, such as hue of the selected point, searches for, and selects connected pixels having the same hue, or connected pixels having a hue within a small range of the hue of the selected point.
[0067] In step 529 , the collection of all selected pixels would be highlighted to the user allowing the user to select this feature, modify it or start over again.
[0068] In step 531 a mask or overlay is constructed which has the same size and shape of the selected feature, which will be colored to overlay the selected feature.
[0069] Alternatively, in step 520 , a pre-defined overlay may be selected, such as for the iris of user 2 's eyes.
[0070] Processing continues on FIG. 5 b at the top marked “A”. After user 2 has selected the feature, user 2 then selects a color for the overlay in step 540 .
[0071] In step 540 user 2 may simply use mouse 33 driving a cursor on monitor 11 to select an approximate color from a color palate displayed on the screen. User 2 may also select any point on the image being displayed.
[0072] Alternately, in step 541 user 2 may select an icon on monitor 11 indicating that he/she would like to acquire another image from an input device. In this case, a picture may be scanned by a scanner 41 , or taken by camera 12 in step 543 . Each of these images is also corrected in step 545 by the appropriate corresponding input profile as described above.
[0073] The resulting image is then displayed on a portion of the screen allowing user 2 in step 547 wherein user 2 selects an approximate color on the second image in step 549 .
[0074] The overlays are merged into the workspace image in step 551 . Adobe Photoshop may be used to merge these.
[0075] The output profile of output devices is determined in step 560 . For example, if the output device, monitor 11 is a cathode ray tube display, the process is as follows.
[0000] Correction for Color Inaccuracy of the Monitor
[0076] Computer 10 is loaded with an electronic file of known accurate colors which will be displayed on the output device in step 561 . A colorimeter device is placed on the screen of monitor 11 and accurately detects a color spectrum in step 563 . The calorimeter has been pre-calibrated and is designed to function on a general purpose computer, such as computer 10 .
[0077] Computer 10 repeats steps 561 - 563 for various colors/frequencies across the visible spectrum in step 565 . The error introduced by the CRT monitor during display of the color is measured and stored in step 567 as an output profile.
[0078] Profiles may also be performed for other output devices, such as with an LCD monitor, plasma displays and printers, which shall be collectively referred to as “output profiles”.
[0079] MonacoOPTIXXR™ software from X-rite Photo Marketing is designed to profile monitor 11 's output.
[0080] After step 567 of FIG. 5 b , processing continues at the top of FIG. 5 c where it is marked “B”. The output profile is used to adjust the image file prior to display in step 581 .
[0081] The adjusted image is then displayed on monitor 11 in step 583 .
[0082] In step 590 , it is determined if the user would like to create any other overlays. If “no”, then the process stops at step 591 . If the answer to step 590 is “yes”, then processing continues at step 521 at the location marked “C” in FIG. 5 a . This allows the user to colorize other features, such as hair color, complexion, etc.
[0083] The present invention would also allow user 2 to select regions of skin, such as above the eyes and allow colors to gradually fade away in a given direction, to provide shading.
[0084] A use of the present invention would be to select all regions which appear to be skin tones, and to make them several shades darker, simulating a tan. This would be useful in selling tanning services.
[0085] Another use of the present invention would be to select regions of one's own skin which they prefer the color. The user may then virtually “brush on” the color to cover blemishes.
[0086] The color-accurate representation may be sent to a cosmetic manufacturer to have custom shades of makeup made. If connected to the internet the order may be sent immediately.
[0087] Once selected, these custom colors may be used to create custom makeup, or custom colored apparel.
[0088] The present invention is also capable of saving the images created and displaying them side-by-side. FIG. 6 a screen shot of monitor 11 is shown having two images 610 and 620 of user 2 displayed side by side. The present invention is capable of saving and displaying numerous images, which may be the original image and/or those that have been enhanced with one or more colored overlays as described above.
[0089] FIG. 6 also shows ‘before’ and ‘after’ images of a user with different color lipstick. It also shows software buttons 630 , 640 which, when clicked, cause the system to perform specified actions allowing the user to interact with the system. An instructional message 650 is shown on the left providing instructions to interact with user 2 .
[0000] Contact Lenses/Eyeglasses
[0090] The present invention has many uses, for example as stated above, it is useful in assisting customers select eyeglass frames, colorized contact lenses, and/or opaque novelty contact lenses, as set forth in U.S. patent application Ser. No. 10/938,868 “Method of Interactive System for Previewing and Selecting Eyeware” by Dr. Michael R. Neal filed Sep. 13, 2004 referred to in “Cross Reference to Related Applications” above, (the “Referenced Application”) and hereby incorporated by reference as if it were included at length in the body herein.
[0091] The Referenced Application describes a system which is used to allow patients to interactively select colorized contact lenses and view a virtual image of themselves wearing these selected lenses. Since many times the contact lens or eyeglass the patient is currently wearing does not have the proper prescription, the patient is forced to evaluate these products while his vision is impaired. Thus, the customer is unable to view his or her own image accurately, and will often rely on an employee of the store in making their purchasing decision.
[0092] Therefore, the systems described above, and other embodiments of the present invention depend upon accurate representation of the image including color accuracy.
[0000] Cosmetics
[0093] An example would be an embodiment intended to be used at a cosmetic counter. A customer would like to determine which shade of lipstick would best match her complexion. This typically would require trying on lipstick and viewing the result in the mirror. The lipstick would have to be removed, and the process repeated for the next color. This process either produces significant waste “test” products, or incurs the potential for transfer of diseases from one customer to another. It also requires significant input from the employees asking them which would look better since one must simply remember the previous colors.
[0094] The present invention will quickly and accurately provide a virtual image of the user and allow her to select different colors of lipstick and interactively view the results.
[0000] Apparel
[0095] The present invention may be used to color-coordinate clothes, hats and other apparel. It would allow one to quickly and accurately change the colors of clothing, and display images simultaneously to do a side-by-side comparison. This allows a customer to try on many different color combinations in a short period of time. Once selected, the customer needs to only try on the clothes to select the proper size.
[0096] Since the present invention will allow the colors of many features to be adjusted simultaneously, a user may color-coordinate colors of clothes with the proper colors of makeup, hair color, contact lens color, etc. to coordinate the entire look without actually changing anything on the user.
[0097] Having thus described the invention, what is desired to be protected by Letters Patent is presented in the subsequently appended claims. | The present invention provides a simple interactive device intended to be used by the customer for acquiring an image of the customer, interactively allowing the customer to try on virtual shades of lipstick, makeup, color contacts, hair color, and/or apparel at the same time to change their appearance. The present invention takes into account the deviations due to the input devices and the output devices thereby resulting in laboratory quality color accuracy and very realistic images. Since it is so accurate, customers may rely on the present invention instead of “trying on” the products. This allows a customer to view many different colors and color schemes in a fraction of the time, while freeing up store employees. The present invention may also display several images simultaneously to allow a customer to efficiently determine the best color scheme or look requiring minimal employee input. | 6 |
Priority is claimed under 35 U.S.C. 119 to Japanese Patent Application No. 2007-255160 filed Sep. 28, 2007, Japanese Patent Application No. 2008-021942 filed Jan. 31, 2008, and Japanese Patent Application No. 2008-021943 filed Jan. 31, 2008, the disclosure of which, including the specifications, drawings and claims, are incorporated herein by reference in its entireties.
BACKGROUND
The present invention relates to a liquid ejecting apparatus that ejects liquid droplets such as ink from a liquid ejecting head onto a sheet.
As general liquid ejecting apparatii, ink jet printers that perform a printing process on a sheet by moving a liquid ejecting head (ink jet head) and ejecting ink droplets relative to a sheet of printing material such as a paper sheet are known.
In these ink jet printers, a phenomenon known as cock ring may occur in a print process. Specifically, cock ring occurs when a paper sheet is swollen with ripples due to ink droplets ejected onto the paper sheet. When cock ring occurs, the paper sheet may get dirty from contact with the print head or a paper jam error may occur.
Thus, a printing apparatus having a transport mechanism that sucks the paper sheet to a platen side by sucking the inside of a vacuum belt having a plurality of suction ports formed therein and transporting the paper sheet with the paper sheet adsorbed to the vacuum belt is known (for example, see Japanese Patent No. 3195792).
In addition, a printing apparatus that transports a paper sheet in a state that the paper sheet is pressed to endless belts by arranging a plurality of the endless belts having a thin and long shape and sucking air from an air suction port disposed between the endless belts is also known (for example, see Japanese Patent No. 2902150).
However, in the printing apparatus having a vacuum belt, the paper sheet may be swollen due to cock ring that occurred on the paper sheet in spots other than suction ports of the vacuum belt. In such a case, an increase of the number of the suction ports or a method of disposing the suction ports may be considered. In order to suppress the cock ring, a very strong suction force is needed. However, when the suction force is increased, a friction force between the vacuum belt and a belt receiving part increases to increase a transport load. Accordingly, it is difficult to smoothly transport the paper sheet with high precision. In addition, since a suction device that is large and expensive is needed, the costs increase. In addition, when the paper sheet is thin, ripples are generated from the increased suction force and the printing quality is deteriorated.
In the printing apparatus in which air suction ports are disposed in the platen located between the plurality of endless belts having a thin and long shape, the paper sheet on which the cock ring has occurred is adsorbed to the air suction ports to generate friction. Accordingly, it is difficult to smoothly transport the paper sheet with high precision. In such a case, it is preferable that the suction ports are disposed far from the paper sheet with respect to the upper face of the belt, in consideration of the cock ring of the paper sheet. However, in that case, it is difficult for the suction force in the air suction port to act upon the paper sheet, and the paper sheet cannot be drawn sufficiently. Accordingly, contact between the paper sheet and the print head and the paper jam error cannot be prevented sufficiently.
SUMMARY
It is therefore an object of at least one embodiment of the invention to provide a liquid ejecting apparatus capable of ejecting liquid well by smoothly transporting the sheet at high precision with contact between the sheet and the liquid ejecting head and to prevent occurrence of a paper jam error.
According to an aspect of at least one embodiment of the invention, there is provided a liquid ejecting apparatus comprising: a transport mechanism that transports a sheet in a first direction; and a liquid ejecting head that ejects liquid onto the sheet; wherein the transport mechanism includes: a plurality of transport belts that transports the sheet and arranged in a second direction which is orthogonal to the first direction, each of the transport belts extending in the first direction and having a transport surface with which the transported sheet is brought into contact; a concave portion disposed between the transport belts adjacent to each other in the second direction; and a plurality of suction ports that sucks the sheet and disposed on both sides of the concave portion in the second direction; wherein a distance between the liquid ejecting head and a suction surface of each of the suction ports is longer than a distance between the liquid ejecting head and the transport surface; and wherein a distance between the liquid ejecting head and a bottom of the concave portion is longer than the distance between the liquid ejecting head and the suction surface.
According to the above-described liquid ejecting apparatus, a sheet is sucked by the suction ports disposed on both sides of the transport belt in the width direction (the second direction). Thus, even when ripples of the cock ring are generated in the sheet due to ejection of liquid droplets, the sheet is drawn to be curved in a direction (that is, the platen side) for departing far from the liquid ejecting head by the suction ports disposed on both sides of the transport belt in the width direction. Accordingly, while the sheet is sucked to be pressed so as to face the transport belt, the sheet can be transported without being brought into contact with the liquid ejecting head.
In addition, since the suction ports are in positions located farther from the liquid ejecting head than the transport surface of the transport belt, a sheet drawn in by the suction ports is not brought into contact with the suction ports. The curvature of the sheet due to suction may be easily increased between adjacent suction ports located between the transport belts. However, since the concave portion is disposed in a position located farther from the liquid ejecting head than the suction ports, the sheet is absorbed by the concave portion. Accordingly, contact between the curved sheet and a member such as a platen that forms the transport path is prevented. Thus, a problem that the transport resistance is increased by bring the sheet drawn in by the suction ports into contact with the member forming the transport path can be eliminated. In addition, by disposing the suction port in a position close to the transport surface so as not to influence the suction operation, a sheet in which cock ring occurs can be sucked assuredly, and thus the sheet can be curved to the gap enlarging part in the direction for departing far from the liquid ejecting head.
As a result, while contact between the sheet and the liquid ejecting head and occurrence of the paper jam error are prevented, the sheet is smoothly transported with high precision, and thereby liquid can be ejected well.
The liquid ejecting apparatus may further comprise a platen facing the liquid ejecting head, wherein the platen is formed with the suction ports and the concave portion.
The bottom of the concave portion may have a flat bottom face; and a distance between the liquid ejecting head and the flat bottom face of the concave portion may be longer than the distance between the liquid ejecting head and the suction surface.
In addition, the suction ports may be disposed in both side ends of each of the transport belts in the second direction to effectively adsorb the sheet to the transport surface of the transport belt.
In addition, the transport mechanism may have a pressing roller that presses the sheet toward the concave portion and disposed in a downstream side with respect to the liquid ejecting head in the first direction.
In such a case, since the pressing roller presses the sheet between the transport belts on the downstream side in the transport direction of the sheet (the first direction), the sheet is pressed between the transport belts in a direction for departing from the liquid ejecting head. Accordingly, swell-up of the sheet can be prevented more assuredly.
In addition, the transport belts may be arranged in the second direction such that the transport belts for transporting the sheets are disposed at least in the vicinity of both side ends of respective sheets when the transport belts transport the sheets having different size in the second direction with each other. The respective transport belts for transporting the sheets may be disposed in the vicinity of the both side ends of the respective sheets are disposed in symmetrical positions with respect to the both side ends of the respective sheets.
In the above-described liquid ejecting apparatus, loads on the both side-end parts of the sheet that are located on the left side and the right side can be uniform, and accordingly, the sheet of any type can be transported in high balance.
Accordingly, the sheet of any type is smoothly transported at high precision with contact between the sheet and the liquid ejecting head and occurrence of a paper jam error prevented, and accordingly, the printing operation and the like can be performed well.
In addition, in order to easily dispose the transport belts that are disposed near the side end parts of the sheet of any type symmetrically, the respective sheets having different size with each other may be transported along a common reference position.
In addition, the concave portion may be formed with a support member that supports the transported sheet and arranged along the first direction.
In such a case, the support part is disposed between the transport belts in at least an ejection area of the liquid ejecting head. Accordingly, even when the interval of cock rings in the sheet due to adherence of liquid increases, the sheet can be support by the support part between the transport belts. Thus, the interval of the cock ring in the sheet can be decreased, and a difference of heights of ripples formed on the surface of the sheet can be decreased, and thereby an excellent print state can be acquired. In other words, the sheet is smoothly transported with high precision by suppressing the contact between the sheet and the liquid ejecting head, occurrence of a jam error, and the difference of heights of ripples caused by the cock ring, and thereby a printing operation can be performed well.
In addition, the support member may include a rib protruded toward the liquid ejecting head. The support member may include a plurality of rollers, each of which is rotatably supported by an axis which extends in the second direction.
In the above-described liquid ejecting apparatus, a sheet curved between the transport belts in the ejection area can be sufficiently supported by the support part formed of a rib or a roller. Accordingly, the difference of heights of ripples formed on the surface of the sheet can be decreased, and thereby an excellent print state can be acquired.
In addition, a distance between one of the transport belts and one of the suction ports may be shorter than a distance between the support member and the one of the suction ports.
Accordingly, generation of ripples on the sheet can be suppressed by the support part while suction of the sheet in the suction port is sufficiently performed.
In addition, a distance between the liquid ejecting head and the support member may be longer than the distance between the liquid ejecting head and the transport surface.
In the above-described liquid ejecting apparatus, the support part is disposed farther from the liquid ejecting head than the transport surface of the transport belt for the sheet. Accordingly, unnecessary contact between the support part and a sheet in which cock ring scarcely occurs before adherence of liquid or the like can be suppressed, and thereby the sheet can be transported well.
According to another aspect of at least one embodiment of the invention, there is provided a liquid ejecting apparatus comprising: a transport mechanism that transports a sheet in a first direction; and a liquid ejecting head that ejects liquid onto the sheet; wherein the transport mechanism includes: a plurality of transport belts that transports the sheet and arranged in a second direction which is orthogonal to the first direction, each of the transport belts extending in the first direction and having a transport surface with which the transported sheet is brought into contact; an opening disposed between the transport belts adjacent to each other in the second direction; and a plurality of suction ports that sucks the sheet and disposed on both sides of the opening in the second direction; and wherein a distance between the liquid ejecting head and a suction surface of each of the suction ports is longer than a distance between the liquid ejecting head and the transport surface.
According to still another aspect of at least one embodiment of the invention, there is provided a liquid ejecting apparatus comprising: a transport mechanism that transports a sheet in a first direction; and a liquid ejecting head that ejects liquid onto the sheet; wherein the transport mechanism includes: a plurality of transport belts that transports the sheet and arranged in a second direction which is orthogonal to the first direction, each of the transport belts extending in the first direction and having a transport surface with which the transported sheet is brought into contact; a concave portion disposed between the transport belts adjacent to each other in the second direction; and a suction region that sucks the sheet toward the concave portion and disposed between the transport belts adjacent to each other in the second direction; wherein a distance between the liquid ejecting head and a suction surface of the suction region is longer than a distance between the liquid ejecting head and the transport surface; and wherein a distance between the liquid ejecting head and a bottom of the concave portion is longer than the distance between the liquid ejecting head and the suction surface.
BRIEF DESCRIPTION OF THE DRAWINGS
The above objects and advantages of the present invention will become more apparent by describing in detail preferred exemplary embodiments thereof with reference to the accompanying drawings, wherein:
FIG. 1 is an external perspective view of a printer as an example of a printing apparatus according to an embodiment of the present invention;
FIG. 2 is a schematic side cross-section view showing the internal configuration of the printer shown in FIG. 1 ;
FIG. 3 is a schematic plane cross-section view showing the internal configuration of the printer shown in FIG. 1 ;
FIG. 4 is a schematic side cross-section view of a printer showing a state in which a paper sheet can be fed from a main cassette;
FIG. 5 is a schematic plane section view showing a state in which a paper sheet can be fed from the main cassette;
FIG. 6 is a perspective view of a print processing unit;
FIG. 7 is a cross-section view of the print processing unit in the width direction;
FIG. 8 is a cross-section view of a suction port part of the print processing unit in the transport direction of a paper sheet;
FIG. 9 is a cross-section view of a transport belt part of the print processing unit in the transport direction of a paper sheet;
FIG. 10 is a plan view of a transport mechanism;
FIG. 11 is an enlarged side view of the transport belt part;
FIG. 12 is a cross-section view of a print processing unit according to a modified example of a transport mechanism in the width direction;
FIG. 13 is a cross-section view of a print processing unit in the width direction;
FIG. 14 is a schematic cross-section view of a print processing unit showing the state of generation of ripples of a paper sheet;
FIG. 15 is a cross-section view of a print processing unit in the width direction showing a modified example of the transport mechanism;
FIG. 16 is a cross-section view of the print processing unit according to a modified example of the transport mechanism between the transport belts in the transport direction of the paper sheet;
FIG. 17 is a cross-section view of a print processing unit according to a modified example of a transport mechanism in the width direction; and
FIG. 18 is a cross-section view of a print processing unit according to a modified example of a transport mechanism in the width direction.
DETAILED DESCRIPTION OF THE EMBODIMENTS
Hereinafter, an example of a liquid ejecting apparatus according to an embodiment of the present invention will be described with reference to the accompanying drawings. In this embodiment, an ink jet printer as the liquid ejecting apparatus will be described as an example.
The printer 1 according to this embodiment is a front-feed/rear-discharge type ink jet printer as an example. As shown in FIG. 1 , in the center of a front face (a left-side end face in FIG. 1 ) of a device case 4 , a sub cassette loading gate 5 is formed. As shown in FIG. 2 , in the sub cassette loading gate 5 , a sub cassette 6 that houses a paper sheet (sheet) P, which is a large printing material in the shape of a sheet, in a housing space S is loaded in a detachably attachable manner. A rear half portion of the sub cassette 6 is loaded into the inside of the device case 4 , and a front half portion thereof protrudes from the device case 4 .
As shown in FIG. 1 , on a side face (a front-side face in FIG. 1 ) of the device case 4 , a window part 8 having a gate 7 that can be opened or closed toward the outer side is disposed. In a state that the gate 7 is open, a main cassette 42 can be loaded or unloaded. As shown in FIG. 2 , in the main cassette 42 , paper sheets P that are small printing sheets are housed in a housing space S in a stacked state. In addition, on a rear face of the device case 4 (a right-end face in FIG. 1 ), a paper discharging tray 9 that receives a paper sheet P for which a printing process has been completed is disposed.
As shown in FIGS. 2 and 3 , a cassette installation unit 40 is disposed inside the device case 4 on the front part, and a paper feeding unit 10 is disposed on the downstream side (that is, the rear side) of the cassette installation unit 40 . In addition, a print processing unit 20 and a paper discharging unit 50 are disposed on the downstream side of the paper feeding unit 10 .
An opening/closing cover 5 a that can be turned inside the sub cassette loading gate 5 is disposed in the cassette installation unit 40 . The opening/closing cover 5 a is turned towards the interior of the device case 4 and brought into contact with the sub cassette 6 by loading the sub cassette 6 into the sub cassette loading gate 5 , and thereby opening the sub cassette loading gate 5 . On the other hand, the opening/closing cover 5 a is turned towards the loading gate 5 by unloading the sub cassette 6 from the sub cassette loading gate 5 , and thereby closing the sub cassette loading gate 5 .
In addition, an opening/closing cover detecting sensor 5 b that is turned on or off by opening or closing the opening/closing cover 5 a is disposed in the sub cassette loading gate 5 .
In a position on the front side and inside printer 1 , a sub cassette detecting sensor 5 c that is turned on or off by attaching or detaching the sub cassette 6 to/from the printer 1 is disposed in the loading direction of the sub cassette 6 .
In addition, a main cassette installation unit 41 is disposed inside the device case 4 . In the main cassette installation unit 41 , the main cassette 42 is housed in a detachably attachable manner.
The main cassette 42 has a housing space S in which small paper sheets P are stacked and housed therein. A paper elevating mechanism 43 is disposed inside the housing space S. The position of the uppermost part of the small paper sheets P that are housed inside the housing space S in a stacked state by the paper elevating mechanism 43 becomes a predetermined height position.
The main cassette installation unit 41 has an elevation plate 44 on which the main cassette 42 is placed. The elevation plate 44 is configured to be raised or lowered by the elevation mechanism 44 a.
In addition, a main cassette detecting sensor 46 that is turned on or off by a pin 45 that appears or disappears as the main cassette 42 is attached to or detached from the main cassette installation unit 41 is disposed on the elevation plate 44 .
As shown in FIGS. 4 and 5 , the main cassette installation unit 41 , by elevating the sub cassette 6 in a detached state using the elevation mechanism 44 a , the main cassette 42 on the elevation plate 44 is disposed in a paper feeding position. In this state, a pickup roller 13 can feed a paper sheet P.
On the contrary, when the elevation plate 44 is lowered by the elevation mechanism 44 a , the main cassette 42 is disposed in a standby position that is deviated from the paper feeding position. In this state, the main cassette 42 can be acquired through the window part 8 of the device case 4 . In addition, the sub cassette 6 can be loaded through the sub cassette loading gate 5 in a state that the main cassette 42 is disposed in the standby position.
In addition, a feed position detecting sensor 47 that detects disposition of the main cassette 42 in the paper feeding position and a standby position detecting sensor 48 that detects disposition of the main cassette 42 in the standby position are disposed in the main cassette installation unit 41 .
In the paper feeding unit 10 , a pickup roller 13 is disposed to be supported by a front end of a frame 12 that is supported to be able to pivot inside the device case 4 . By bring the pickup roller 13 into contact with a paper sheet P that is disposed downward, the uppermost sheet of the paper sheets P are continuously sent out to the rear side (the right side in FIGS. 2 and 3 ) one after another and are sent to the print processing unit 20 on the rear side.
In the print processing unit 20 , an ink jet head (print head) 22 , which prints a desired image by ejecting liquid droplets (ink droplets) of ink and moves relatively with respect to a supplied paper sheet P in the width direction of the paper sheet P, is disposed to be movable along guide shafts 21 and 21 that are disposed to be orthogonal to the paper feed direction.
As shown in FIG. 6 , the ink jet head 22 is fixedly attached to a part of a driving belt 64 wound over a driving pulley 62 and a driven pulley 63 that are rotated by a driving motor 61 . The ink jet head 22 is moved along the guide shafts 21 and 21 as the driving pulley 62 is rotated by the driving motor 61 and as the driving belt 64 travels. The ink jet head 22 according to this embodiment includes an area, in which an ink nozzle is formed, that has a length of 2 inches in the transport direction of the paper sheet and is relatively large as an ink jet head of an ink jet printer.
In addition, a transport mechanism 70 is disposed below the ink jet head 22 to transport a paper sheet P as a printing material and to support the paper sheet from below.
As shown in FIGS. 6 to 10 , the transport mechanism 70 has an upper face as a reference face that is a platen 71 for printing and includes a suction block 72 that faces the ink jet head 22 . The suction block 72 is in the shape of a box in which a space part S 1 is formed and includes a suction blower 74 that sucks air located inside the space part S 1 in the lower part thereof.
On the upstream side of the suction block 72 constituting the transport mechanism 70 , a plurality of tension pulleys 75 and guide pulleys 73 (see FIG. 11 ) are supported with an interval interposed therebetween. In addition, near the downstream side of the suction block 72 , a groove part 76 that opens toward the upper side is formed in the width direction of the suction block 72 (see FIGS. 8 and 9 ). A rotation shaft 78 is disposed on the groove part 76 . On the rotation shaft 78 , a same number of driving pulleys 79 as that of the tension pulleys 75 are disposed in positions facing the tension pulleys 75 . A transport belt 80 is wound over the driving pulley 79 , the tension pulley 75 , and the guide pulley 73 , and the transport belts 80 are arranged in the width direction of the suction block 72 with an interval interposed therebetween. While the driving pulley 79 and the guide pulley 73 have teeth on their outer peripheries, the tension pulley 75 does not have any tooth.
Here, the printer 1 performs a printing process for a plurality of types of paper sheets P having different widths. Accordingly, the plurality of the transport belts 80 that are disposed along the width direction with an interval interposed therebetween are disposed in correspondence with the different widths of various paper sheets P.
Hereinafter, disposition of the transport belts 80 will be described.
As shown in FIG. 10 , a reference C for position adjustment is set on one side (the right side in FIG. 10 ) of the platen 71 that is a reference face for printing for the upper face of the suction block 72 of the transport mechanism 70 . In the transport mechanism 70 , a paper sheet P having any width is transported with its one side aligned to and along the reference C for position adjustment
A paper sheet P used for printing may be a paper sheet that is a specific standard size such as a business card size having a width of W 1 , a post card size having a width of W 2 , an A4 size having a width of W 3 , an A3 size having a width of W 4 , or an A3-wide size having a width of W 5 .
In the transport mechanism 70 , the transport belts 80 are disposed in a position near both side-end parts of any of the above-described paper sheets P.
The transport belts 80 disposed near both ends of a paper sheet P of any type are symmetrically disposed along the width direction of the paper sheet P. The distance W 0 from each of the both end parts of the paper sheet P of any type to a transport belt 80 located nearby is about 10 mm. In addition, suction ports 102 to be described later are disposed below edges of the paper sheets P protruding toward the side from the transport belts 80 near the both end parts.
As shown in FIG. 11 , the transport belt 80 is a timing belt that has a plurality of teeth 80 a on its inner periphery side. The teeth 80 a of the transport belt 80 are engaged with teeth 73 a and 79 a of the guide pulley 73 and the driving pulley 79 . In addition, the tension pulley 75 is elastically biased in a direction (the right side in FIGS. 8 , 9 and 11 ) for departing from the driving pulley 79 to apply a predetermined tension to the transport belt 80 .
A pressing roller 81 that faces the guide pulley 73 is disposed on a part of the transport belt 80 located on the upstream side. The pressing roller 81 is rotably supported by a frame 82 and is biased to the guide pulley 73 side.
In addition, a plurality of pairs of transport rollers 83 and 84 that are disposed in positions for facing the transport belt 80 with spaced apart therebetween along the transport belt 80 and a pressing roller 85 disposed between the transport belts 80 are disposed on a downstream part of the transport belt 80 (see FIG. 9 ). The transport rollers 83 and 84 and the pressing roller 85 are rotably supported by a bracket 86 . The transport roller 83 is disposed directly above the driving pulley 79 and a paper sheet P is pinched between the transport roller 83 and the driving pulley 79 through the transport belt 80 . The transport roller 84 is disposed on the upstream side of the transport roller 83 . The transport roller 84 prevents swell of a paper sheet P on the transport belt 80 before the paper sheet reaches the transport roller 83 . The pressing roller 85 prevents swell of the paper sheet P between the transport belts 80 on the upstream side of the driving pulley 79 .
A transmission pulley 91 is disposed on one end part of the rotation shaft 78 . A transmission belt 94 is suspended over the transmission pulley 91 and a rotation pulley 93 of the transport motor 92 . In addition, , an encode plate 95 having a circular disk shape together with the transmission pulley 91 is disposed on the rotation shaft 78 . By detecting a plurality of slits (not shown in the figure) formed near the outer periphery of the encode plate 95 along the main direction by using a detector 96 , the rotation position of the rotation shaft 78 can be detected.
As shown in FIG. 7 , on the upper face of the suction block 72 , on both sides of each transport belt 80 along the width direction, a suction face 101 that is located farther from the ink jet head 22 than a transport surface 80 b in a (height) direction orthogonal to the width direction and the transport direction to be slightly lowered from the transport surface 80 b of the paper sheet P which is in a position having a same height as that of the upper face of the transport belt 80 is formed along the transport belt 80 . In the suction face 101 , a plurality of suction ports 102 that are communicated with the space part S 1 is formed along the transport direction. In addition, between suction ports 102 adjacent to each other in the width direction of the transport belt 80 , a concave part 103 that is a gap enlarging part is formed. A bottom face 103 a of the concave part 103 is disposed in a low position that is located farther from the ink jet head 22 than the suction face 101 . As shown in FIG. 7 , the concave part 103 is disposed between the transport belts which are adjacent to each other in the width direction of the transport belt 80 (in a direction orthogonal to the transport direction), and the suction ports 102 are disposed in both sides of the concave part 103 . In other words, the suction port 102 is disposed between the transport belts 80 which are adjacent to each other. However, in order to suck the sheet P toward the concave part 103 , the suction port 102 may be disposed in one side of the concave part 103 in the direction orthogonal to the transport direction. In addition, a suction region in which the suction port 102 is formed may be disposed in both sides of the concave part 103 in the transport direction. The suction region may be disposed in one side of the concave part 103 .
In this embodiment, as described above, the ink jet head 22 is relatively large, and thus, a gap (that is, a distance from the guide pulley 73 to the driving pulley 79 ) for pinching the paper sheet P on the upstream side of the ink jet head 22 and the downstream side is relatively long. Accordingly, the paper sheet P can be easily swelled when the paper sheet P is not sucked downward.
In the transport mechanism 70 , when the transport motor 92 is driven, the turning force of the rotation pulley 93 is transferred to the transmission pulley 91 through the transmission belt 94 , and rotates the rotation shaft 78 . Accordingly, the plurality of the transport belts 80 that are wound over the driving pulley 79 , the tension pulley 75 , and the guide pulley 73 travels.
Then, the paper sheet P that is transported between the transport belt 80 and the pressing roller 81 is pinched by the transport belt 80 and the pressing roller 81 to be sent to the rear side. Furthermore, the paper sheet P is transported downstream side by the transport belt 80 while a printing process is performed by the ink jet head 22 .
At that moment, cock ring in which the paper sheet P is swollen by ink droplets ejected from the ink jet head 22 may occur and causes ripples in paper sheet P. In the transport mechanism 70 according to this embodiment, when air inside the space part S 1 is sucked in by the suction blower 74 , the paper sheet P is sucked downward by the suction ports 102 that are disposed on both sides of the transport belt 80 in the width direction. Accordingly, even when the cock ring causes ripples in the paper sheet P, the paper sheet P is drawn downward on both sides of the transport belt 80 along the width direction to be curved. As a result, the swell of the paper sheet between the transport belts 80 is suppressed while the paper sheet P is transported in accordance with travel of the transport belt 80 with the paper sheet pressed to face the transport belt 80 from both sides of the transport belt 80 in the width direction. Accordingly, a problem that the paper sheet is brought into contact with the ink jet head 22 or the like is prevented.
In addition, since the suction face 101 is disposed in a position slightly lower than the transport surface 80 b , a relatively short distance between the paper sheet P and the suction port 102 is configured and contact between the suction face 101 and the paper sheet P prevented. Accordingly, it is possible to effectively apply a suction force to the paper sheet P without markedly increasing the suction force of the suction blower 74 . Since the paper sheet P is inclined to be curved toward the suction ports 102 near both side ends of the transport belt 80 , from the both side ends as reference points, the paper sheet P may be easily curved in the shape of a valley in a center portion between the transport belts 80 along the width direction. However, since the bottom face 103 a of the concave part 103 , which is disposed in the center of the transport belts 80 , is disposed in a position one step lower than that of the suction face 101 , the contact between the paper sheet P and the bottom face 103 a is reliably prevented. Thus, a problem that the paper sheet P drawn downward is brought into contact with the suction port 102 and the bottom face 103 a of the concave part 103 to increase the transport resistance does not occur.
Here, according to the printer 1 of this embodiment, the transport belts 80 of the transport mechanism 70 are symmetrically disposed in positions near both ends of the paper sheets P having different widths W 1 to W 5 . Accordingly, an edge that is an end of the paper sheet P is not loaded directly on the transport belt 80 and the edge of the paper sheet P is not disposed far from the transport belt 80 . In addition, the paper sheets P having the different widths W 1 to W 5 are smoothly transported in balance, and accordingly, the probability for a paper jam error caused by an unbalanced transport is reduced.
Thereafter, the paper sheet P is discharged to the paper discharging tray 9 while being pinched by the transport belt 80 and the transport rollers 83 and 84 .
At this moment, the paper sheet P is pressed downward between the transport belts 80 by the pressing roller 85 that is disposed in the center of the transport belts 80 . Accordingly, the paper sheet P in which the cock ring occurs is curved downward between the transport belts 80 more reliably.
As described above, according to the printer 1 of this embodiment, since the paper sheet P is sucked by the suction port 102 that is disposed in a position slightly lower than the transport surface 80 b disposed on both sides of the transport belt 80 in the width direction, the paper sheet P can be effectively sucked down with a relatively weak suction force. Accordingly, although the ink jet head 22 is large, the swell of the paper sheet P over the entire transport area due to the transport belt 80 can be prevented, and contact between the paper sheet P and the ink jet head 22 can be prevented. Thus, occurrence of a jam error can be prevented. In addition, since the bottom face 103 a of the concave part 103 located between the transport belts 80 is in a position lower than the suction port 102 , the paper sheet P curvature due to suction is not brought into contact with the platen side. Accordingly, the paper sheet P can be transported with high precision without increasing the transport resistance. As a result, a printing operation with high precision can be performed.
In addition, in the transport mechanism 70 , the pressing roller 85 presses the paper sheet P in a position facing the concave part 103 , on the upstream side of a position in which the paper sheet P is pinched on the downstream side in the transport direction, and accordingly, the swell of the paper sheet P between the transport belts 80 can be more reliably prevented.
In addition, by using a timing belt as the transport belt 80 , a transport operation can be controlled with high precision regardless of a thickness of the transport belt 80 . In addition, the precision of transport of the paper sheet P is increased without idle rotation the transport belt 80 , and accordingly, a printing operation with high precision can be performed.
In addition, according to the printer 1 of this embodiment, transport belts 80 are disposed at least near both side-end parts of various types of paper sheets P having different widths, and the paper sheet P is transported by the plurality of transport belts 80 including the transport belts disposed near the both ends of the paper sheet P. Accordingly, various types of paper sheets P having different widths can be transported with high degree of balance.
Furthermore, since the transport belts 80 disposed in positions near both ends of the paper sheet P to be transported are disposed in positions symmetrical with respect to the paper sheet P in the width direction, various types of paper sheets P having different widths can be transported with higher degree of balance.
As a result, various types of paper sheets P can be smoothly transported at high precision with contact between the paper sheet P and the ink jet head 22 and occurrence of a jam error prevented, and thereby a high-quality printing operation can be performed.
The present invention is not limited to the above-described embodiment and various changes can be made therein. For example, in the above-described embodiment, although a plurality of the transport belts 80 are disposed to be horizontally symmetrical in accordance with widths of a plurality of types of paper sheets P having different widths, the plurality of transport belts may be disposed to be equally spaced. In such a case, advantages of the present invention that a printing material is drawn to be curved in a direction apart away from the print head by the suction ports on both sides of the transport belts in the width direction and the printing material can be transported without being brought into contact with the print head, even in a case where ripples of cock ring are generated in the printing material can be acquired.
In addition, in this embodiment, the suction port 102 that is communicated with the space part S 1 is described to be formed along the transport direction in a position adjacent to the transport belt 80 . However, an example in which the position of the suction port is not limited to that of this embodiment will be described with reference to FIG. 12 .
As shown in FIG. 12 , in transport mechanism 120 , a plurality of communication holes 121 that are communicated with the space part S 1 is formed in a position below the center of the transport belt 80 along the width direction. The communication holes 121 are communicated with the outside in both ends of the transport belt 80 through gaps of the teeth 80 a of the transport belt 80 . The opening that is communicated with the outside is formed as a suction port 102 a located in a position slightly lower than the transport surface 80 b.
In this transport mechanism 120 , when air inside the space part S 1 is sucked by the suction blower 74 , the air is sucked in from the suction ports 102 a on both ends of the transport belts 80 through the communication hole 121 and the gaps of the teeth 80 a of the transport belt 80 .
In other words, in transport mechanism 120 , the suction ports 102 a are formed continuously in the transport direction of the transport belt 80 , and a uniform suction effect can be obtained over the transport direction.
As described above, according to a printer having the above-described transport mechanism 120 , gaps of the teeth 80 a disposed on the inner face of the transport belt 80 are communicated with the suction port 102 a . Thus, additional suction ports are not needed on both sides of the transport belt 80 , and accordingly, costs can be reduced by simplifying the structure thereof.
As shown in FIG. 12 , an example embodiment having one communication hole 121 , which is communicated with the space part S 1 and disposed in a position below the center of the transport belt 80 along the width direction, is communicated with two suction ports 102 a disposed on both ends of the transport belt 80 . However, each of the suction ports 102 a shown in FIG. 12 may be configured to be directly communicated with the space part S 1 . In such a case, the transport belt 80 does not need to be a timing belt. In addition, since the flow path of the sucked air becomes a straight line formed by the suction port 102 a and the space part S 1 , there is no loss, and thereby excellent efficiency is obtained.
In addition, the concave part 103 has the bottom face 103 a in this embodiment. However, a shape of the concave part 103 is not limited to the embodiment. As shown in FIG. 18 , the concave part 103 may be a concave part comprised of a single curved face 103 b . Further, an opening having no bottom face 103 a may be formed in the platen 71 in place of the concave part 103 . In such a case, it is necessary to replace the space part S 1 so that the opening is not communicated with the space part S 1 .
In addition, in this embodiment, the concave part 103 formed between the transport belts 80 is configured to have the shape of a simple concave part. However, when the gap between the transport belts 80 is widened, the interval of the cock ring of the paper sheet increases, and a difference of heights of ripples formed on the top face of the paper sheet may be increased.
When the difference of the heights of the ripples formed on the top face of the paper sheet is large, landing positions of ink droplets ejected from the print head are unbalanced to cause deterioration of the print quality. Accordingly, in response to the problem, as another example of this embodiment, a support member that supports the printing material may be disposed in at least one embodiment of the present invention.
This embodiment will now be described with reference to FIGS. 13 and 14 . For the description, to each component that is the same as that of the above-described embodiment or has the same function as that of the above-described embodiment, a same reference symbol is assigned, and a description thereof is omitted here. FIG. 13 is a cross-section view of a print processing unit in the width direction. FIG. 14 is a schematic cross-section view of the print processing unit showing the state in which ripples are generated in a paper sheet.
As shown in FIG. 13 , similarly to FIG. 7 described above, on the top face of a suction block 72 , a suction face 101 is formed along a transport belt 80 . In this suction face 101 , a plurality of suction ports 102 that are communicated with a space part S 1 is formed along the transport direction. In addition, a concave part 103 is formed between the suction ports 102 adjacent to each other in the width direction of the transport belt 80 .
In this embodiment, between the transport belts 80 , in at least a print area of the ink jet head 22 , a rib (support part) 110 is formed and disposed along the transport direction of the paper sheet P transported by the transport belt 80 . The rib 110 is installed on a bottom face 103 a of the concave part 103 facing the upper side.
Here, the top end of the rib 110 is positioned to be lower than the transport surface 80 b of the transport belt 80 and is positioned to be higher than the suction face 101 .
In addition, the rib 110 is formed in the center of the transport belts 80 , and a distance B between the center of the suction port 102 and the center of the rib 110 is configured to be longer than a distance A between the center of the suction port 102 and the center of the transport belt 80 .
In addition, between the transport belt 80 and the rib 110 , a pressing roller 85 is disposed.
As described above, when a printing operation for the paper sheet P is performed, there is a case where cock ring in which the paper sheet P is swollen with ripples generated by the ink droplets ejected from the ink jet head 22 may occur. However, the paper sheet P is sucked downward by the suction port 102 , and accordingly, swell of the paper sheet P from the transport belt 80 is suppressed. In a case where the rib 110 is not disposed, when the ripples of the paper sheet P are large, the difference of heights of the surface of the paper sheet P increases. Thus, the landing positions of the ink droplets ejected from the ink jet head 22 are unbalanced causes deterioration of the print quality.
However, in the printer 1 according to this embodiment, the rib 110 is disposed between the transport belts 80 , and accordingly, the paper sheet P is supported by the rib 110 that is disposed between the transport belts 80 .
FIG. 14 shows the state in which the ripples of the paper sheet P are generated. In FIG. 14 , a broken line represents a state of the paper sheet P for a case where the rib 110 is not disposed, and a solid line shows the state of the paper sheet P for a case where the rib 110 is disposed.
As shown in FIG. 14 , when the rib 110 is not disposed, the interval of the cock ring of the paper sheet P increases, and accordingly, the difference of heights due to ripples formed on the surface of the paper sheet P increases. On the other hand, when the rib 110 is disposed, the interval of the cock ring of the paper sheet P decreases, and accordingly, the difference of heights due to ripples formed on the surface of the paper sheet P decreases.
As described above, when a paper sheet P is transported in a transport mechanism in which the rib 110 is disposed, a support part formed of the rib 110 is disposed along the transport direction of the paper sheet P between the transport belts 80 in at least a printing area of the ink jet head 22 . Accordingly, even when the interval of the cock ring of the paper sheet P is increased due to adherence of ink, the paper sheet P can be supported by the rib 110 between the transport belts 80 . Accordingly, the interval of the cock ring of the paper sheet P can be decreased, and the difference of heights due to the ripples formed on the surface of the paper sheet P can be decreased, and thereby a quality print state can be obtained.
In other words, the paper sheet P is smoothly transported at high precision by suppressing contact between the paper sheet P and the ink jet head 22 , occurrence of a paper jam error, and the difference of heights of the ripples due to cock ring, and thereby performing a quality printing operation.
In addition, the bottom face 103 a of the concave part 103 located between the transport belt 80 and the rib 110 is positioned lower than the suction port 102 . Accordingly, contact between the paper sheet P curved by suction and the platen side does not occur, and transport resistance is not increased, and thereby the paper sheet P can be transported with high precision. As a result, a printing operation with high precision can be performed.
In addition, the distance A between the transport belt 80 and the suction port 102 is shorter than the distance B between the rib 110 and the suction port 102 . Accordingly, while the suction effect for the paper sheet P in the suction port 102 is well exhibited, the generation of the ripples of the paper sheet P can be suppressed by the rib 110 .
In addition, the height of the rib 110 is lower than the transport surface 80 b of the paper sheet P, which is formed by the transport belt 80 . Accordingly, unnecessary contact between the paper sheet P, in which cock ring scarcely occurs before adherence of ink or the like, and the rib 110 can be suppressed, and thereby the paper sheet P can be well transported.
In addition, in the transport mechanism 70 , on the upstream side of a position in which the paper sheet P is pinched on the downstream side in the transport direction, the pressing roller 85 presses the paper sheet P in a position facing the concave part 103 , and accordingly, the swell of the paper sheet P between the transport belt 80 and the rib 110 can be more reliably prevented.
In addition, by using a timing belt as the transport belt 80 , the transport operation can be controlled with high precision regardless of the thickness of the transport belt 80 . In addition, the precision of transport of the paper sheet P can be increased without idle rotating the transport belt 80 , and thereby a printing operation can be performed with high precision.
In addition, in the above-described embodiment, in order to suppress generation of the ripples of the paper sheet P due to the cock ring, the rib 110 is formed as the support part that supports the paper sheet P between the transport belts 80 . However, the support part for the paper sheet P is not limited to the rib. Thus, a support roller that turns about an axis line orthogonal to the transport direction of the paper sheet P may be arranged along the transport direction of the paper sheet P, or the rib and the support roller may be combined to be used.
In addition, the present invention is not limited to the above-described embodiment in which the rib is disposed, and various changes can be made therein. An example will be described with reference to FIGS. 15 to 17 . FIG. 15 is a cross-section view of a print processing unit according to a modified example of the transport mechanism, in the width direction. FIG. 16 is a cross-section view of the print processing unit according to a modified example of the transport mechanism between the transport belts in the transport direction of the paper sheet.
FIGS. 15 and 16 show examples in which the rib and the support roller are combined to be used.
As shown in FIGS. 15 and 16 , in this transport mechanism 130 , a receiving hole 111 that is dug downward is formed in a part of a position in which the rib 110 is formed. In addition, inside the receiving hole 111 , a support roller 112 that turns about an axis line orthogonal to the transport direction of the paper sheet P is disposed. In addition, the upper end of the support roller 112 coincides with the upper end of the rib 110 .
Even in a printer 1 having the above-described transport mechanism 130 , the paper sheet P can be well supported between the transport belts 80 by the support part that is formed by the roller 112 disposed between the transport belts 80 in at least a printing area of the print head 22 . Accordingly, the interval of cock ring of the paper sheet P can be decreased, and the difference of heights of the ripples formed on the surface of the paper sheet P can be decreased. Therefore, a quality print state can be obtained.
FIG. 17 shows another example of a transport mechanism that is appropriate for the above-described printer 1 .
As shown in FIG. 17 , in this transport mechanism 120 , a plurality of communication holes 121 that are communicated with the space part S 1 is formed in a position below the center of the transport belt 80 in the width direction. The communication holes 121 are communicated with the outside on both side-end parts of the transport belt 80 through gaps of the teeth 80 a of the transport belt 80 . In addition, an opening that is communicated with the outside thereof is formed as a suction port 102 a that is located in a position slightly lower than the transport surface 80 b. | A liquid ejecting apparatus is provided. A transport mechanism is that transports a sheet in a first direction. A liquid ejecting head is configured to eject liquid onto the sheet. The transport mechanism includes: a plurality of transport belts that transports the sheet and arranged in a second direction which is orthogonal to the first direction, each of the transport belts extending in the first direction and having a transport surface with which the transported sheet is brought into contact; a concave portion disposed between the transport belts adjacent to each other in the second direction; and a plurality of suction ports that sucks the sheet and disposed on both sides of the concave portion in the second direction. A distance between the liquid ejecting head and a suction surface of each of the suction ports is longer than a distance between the liquid ejecting head and the transport surface. A distance between the liquid ejecting head and a bottom of the concave portion is longer than the distance between the liquid ejecting head and the suction surface. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a transition metal compound useful as an olefin polymerization catalyst component, an olefin polymerization catalyst, using said transition metal compound and process for producing an olefin polymer using said olefin polymerization catalyst with a high activity.
2. Description of the Related Art
Many processes for producing an olefin polymer with a metallocene complex have been already reported. For example, a process for producing an olefin polymer with a metallocene complex and an aluminoxane is reported in Japanese Patent Publication (Kokai) No. 58-19306. The metallocene complex disclosed therein is a complex having only one transition metal atom in its molecule.
It is disclosed in Japanese Patent Publication (Kokai) No. 4-91095 to use a metallocene complex having a structure in which two transition metal atoms are contained in its molecule and two η′-cyclopentadienyl groups coordinate on each on each of the transition metal atoms, as an olefin polymerization catalyst component.
However, when these metallocene complexes having the structure in which two η′-cyclopentadienyl groups coordinate on one transition metal atom are used as the olefin polymerization catalyst component, there are problems that the molecular weight of an olefin polymer obtained is low and the comonomer reaction rate in copolymerization is low, and the more improvement of activity has been desired from an industrial viewpoint.
Although metallocene complexes in which two transition metal atoms are contained in its molecule and only one η 5 -cyclopentadienyl group coordinates on each of transition metal atoms are disclosed in Japanese Patent Publication (Kokai) Nos. 3-163088 and 3-188092, they are complexes having a peculiar structure in which excessive anionic ligands against the valence number of a transition metal atom are combined, and its polymerization activity is not confirmed.
Although a metallocene complex in which two transition metal atoms are contained in its molecule and only one η 5 -cyclopentadienyl group coordinates per one transition metal atom is disclosed in Japanese Patent Publication (Kokai) No. 7-126315, it is a complex having a structure in which those two η 5 -cyclopentadienyl groups are linked, and there are problems in that the olefin polymerization catalyst using it as a catalyst component has low comonomer reaction rate in copolymerization and the melting point of a copolymer improvement of activity has been desired from an industrial viewpoint.
SUMMARY OF THE INVENTION
Under these situations, the objects of the present invention are to provide a transition metal compound useful as a highly active olefin polymerization catalyst component at an efficient reaction temperature in the industrial process of important olefin polymerization from an industrial view point, and to provide a highly active olefin polymerization catalyst using said transition metal compound and a process for producing an olefin polymer using said olefin polymerization catalyst.
In order to attain the above-mentioned objects, the present inventors have intensively studied a process for producing an olefin polymer using a metallocene transition metal compound, in particular, a mono cyclopentadienyl transition metal compound as one of catalyst components, and have thus completed the present invention.
The present invention relates to a transition metal compound represented by the general formula [I] or [II] described below, an olefin polymerization catalyst component comprising said transition metal compound, an olefin polymerization catalyst prepared by a process comprising contacting a transition metal compound selected from the group consisting of transition metal compounds represented by the general formulas [I] and [II], and [(B) described below and/or (C)] described below, and a process for producing an olefin polymer with said olefin polymerization catalyst.
(wherein M 1 indicates a transition metal atom of the Group IV of the Periodic Table of the Elements; A indicates an atom of the Group XVI of the Periodic Table of the Elements; J indicates an atom of the Group XIV of the Periodic Table of the Elements; Cp 1 indicates a group having a cyclopentadiene type anion skeleton; each of X 1 , R 1 , R 2 , R 1 , R 4 , R 5 and R 6 independently indicates a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group or a di-substituted amino group; X 2 indicates an atom of Group XVI of the Periodic Table of the Elements; R 1 , R 2 , R 3 , R 4 , R 5 and R 6 may be optionally combined with each other to form a ring; and a plural number of M 1 , A, J, Cp 1 , X 1 , X 2 , R 1 , R 2 , R 3 , R 4 , R 5 and R 6 may be respectively the same or different.)
(B) at least one aluminum compound selected from (B1) to (B3) described below:
(B1) an organoaluminum compound indicated by the general formula E 1 a AlZ 3-a ;
(B2) a cyclic aluminoxane having a structure indicated by the general formula {—Al(E 2 )—O—} b ; and
(B3) a linear aluminoxane having a structure indicated by the general formula E 3 {—Al(E 3 )—O—} c AlE 3 2 (wherein each of E 1 , E 2 and E 3 is a hydrocarbon group, and all of E 1 , all of E 2 and all of E 3 may be the same or different; z represents a hydrogen atom or a halogen atom; and all of z may be the same or different; a represents a number satisfying an expression of 0<a≦3; b represents an integer of 2 or more; and c represents an integer of 1 or more).
(C) any one of boron compounds of (C1) to (C3) described below:
(C1) a boron compound represented by the general formula BQ 1 Q 2 Q 3 ;
(C2) a boron compound represented by the general formula G + (BQ 1 Q 2 Q 3 Q 4 ) − ; and
(C3) a boron compound represented by the general formula (L-H) + (BQ 1 Q 2 Q 3 Q 4 ) −
(wherein B is a boron atom in the trivalent valence state; Q 3 to Q 4 are a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a substituted silyl group, an alkoxy group or a di substituted amino group which may be the same or different; G + is an inorganic or organic cation; L is a neutral Lewis base; and (L H) + is a Brφnsted acid).
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a flow chart for assisting the understanding of the present invention. The flow chart is a typical example of the mode of operation of the present invention, but the present invention is not limited thereto.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is further illustrated in detail below.
(A) Transition Metal Compound
In the general formula [I] or [II], the transition metal atom represented by M 1 indicates a transition metal element of the Group IV of the Periodic Table of the Elements (Revised edition of IUPAC Inorganic Chemistry Nomenclature 1989), and examples thereof include a titanium atom, a zirconium atom, a hafnium atom and the like. A titanium atom or a zirconium atom is preferable.
Examples of the atom of the Group XVI of the Periodic Table of the Elements indicated as A in the general formula [I] or [II] include an oxygen atom, a sulfur atom, a selenium atom and the like, and an oxygen atom is preferable.
Examples of the atom of the Group XIV of the Periodic Table of the Elements indicated as J in the general formula [I] or [II] include a carbon atom, a silicon atom, a germanium atom and the like, and a carbon atom or a silicon atom is preferable.
Examples of the group having a cyclopentadiene type anion skeleton indicated as the substituent group, Cp 1 , include an η 5 -(substituted)cyclopentadienyl group, an η 5 -(substituted)indenyl group, an η 5 (substituted) fluorenyl group and the like. Specific examples include an η 5 -cyclopentadienyl group, an η 5 -methylcyclopentadienyl group, an η 5 -dimethylcyclopentadienyl group, an η 5 -trimethylcyclopentadienyl group, an η 5 -tetramethylcyclopentadienyl group, an η 5 -ethylcyclopentadienyl group, an η 5 -n-propylcyclopentadienyl group, an η 5 -isopropylcyclopentadienyl group, an η 5 -n-butylcyclopentadienyl group, an η 5 -sec-butylcyclopentadienyl group, an η 5 -tert-butylcyclopentadienyl group, an η 5 -n-pentylcyclopentadienyl group, an η 5 -neopentylcyclopentadienyl group, an η 5 -n-hexylcyclopentadienyl group, an η 5 -n-octylcyclopontadienyl group, an η 5 -phenylcyclopentadienyl group, an η 5 -napthylcyclopentadienyl group, an η 5 -trimethylsilylcyclopentadienyl group, an η 5 -triethylsilylcyclopentadienyl group, an η 5 -tert-butyldimethylsilylcyclopentadienyl group, an η 5 -indenyl group, an η 5 -methylindenyl group, an η 5 -dimethylindenyl group, an η 5 -ethylindenyl group, an η 5 -n-propylindenyl group, an η 5 -isopropylindenyl group, an η 5 -n-butylindenyl group, an η 5 -sec butylindenyl group, an η 5 -tert-butylindenyl group, an η 5 -n-pentylindenyl group, an η 5 -neopentylindenyl group, an η 5 -n hexylindenyl group, an η 5 -n-octylindenyl group, an η 5 -n-decylindenyl group, an η 5 -phenylindenyl group, an η 5 -mothylphenylindenyl group, an η 5 -naphthylindenyl group, an η 5 -trimethylsilylindenyl group, an η 5 -triethylsilylindenyl group, an η 5 -tert-butyldimethylsilylindenyl group, an η 5 -tetrahydroindenyl group, an η 5 -fluorenyl group, an η 5 -methylfluorenyl group, an η 5 -dimethylfluorenyl group, an η 5 -ethylfluorenyl group, an η 5 -diethylfluorenyl group, an η 5 n-propylfluorenyl group, an η 5 -di-n-propylfluorenyl group, an η 5 -isopropylfluorenyl group, an η 5 -diisopropylfluorenyl group, an η 5 -n-butylfluorenyl group, an η 5 -sec-butylfluorenyl group, an η 5 -tert-butylfluorenyl group, an η 5 -di-n-butylfluorenyl group, an η 5 -di-sec-butylfluorenyl group, an η 5 -di-tert-butylfluorenyl group, an η 5 -n-pentylfluorenyl group, an η 5 -neopentylfluorenyl group, an η 5 n-hexylfluorenyl group, an η 5 -n-octylfluorenyl group, an η 5 -n-decylfluorenyl group, an η 5 -n-dodecylfluorenyl group, an η 5 -phenylfluorenyl group, an η 5 -dipehnylfluorenyl group, an η 5 -methylphenylfluorenyl group, an η 5 -naphthylfluorenyl group, an η 5 -trimethylsilylfluorenyl group, an η 5 -bis-trimethylsilylfluorenyl group, an η 5 -triethylsilylfluorenyl group, an η 5 -tert-butyldimethylsilylfluorenyl group and the like. An η 5 -cyclopentadienyl group, an η 5 -methylcyclopentadionyl group, an η 5 -tert-butylcyclopentadienyl group, an η 5 -tetramethylcyclopentadienyl group, an η 5 -indenyl group or an η 5 -fluorenyl group is preferable.
As the halogen atom in the substituent, X 1 , R 1 , R 2 , R 3 , R 4 , R 5 or R 6 , a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are illustrated. A chlorine atom or a bromine atom is preferable and a chlorine atom is more preferable.
As the alkyl group in the substituent, X 1 , R 1 , R 2 , R 3 , R 4 , R 5 or R 6 , an alkyl group having 1 to 20 carbon atoms is preferred, and examples includes a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, a neopentyl group, a sec-amyl group, a n-hexyl group, a n-octyl group, a n-decyl group, a n-dodecyl group, a n-pentadecyl group, a n-eicosyl group and the like, and a methyl group, an ethyl group, an isopropyl group, a tert-butyl group or a sec-amyl group is more preferable.
All of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Examples of the alkyl group having 1 to 20 carbon atoms which is substituted with the halogen atom, include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, a dibromomethyl group, a tribomomethyl group, an iodomethyl group, a diiodomethyl group, a triiodomethyl group, a fluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, a pentafluoroethyl group, a chloroethyl group, a dichloroethyl group, a trichloroethyl group, a tetrachloroethyl group, pentachloroethyl group, a bromoethyl group, a dibromoethyl group, a tribromoethyl group, a tetrabromoethyl group, pentabromoethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluorooctyl group, a perfluorododecyl group, a perfluoropentadecyl group, a perfluoroeicosyl group, a perchloropropyl group, a perchlorobutyl group, a perchloropentyl group, a perchlorohexyl group, a perchlorooctyl group, a perchlorododecyl group, a perchloropentadecyl group, a perchloroeicosyl group, a perbromopropyl group, a perbromobutyl group, a perbromopentyl group, a perbromohexyl group, a perbromooctyl group, a perbromododecyl group, a perbromopentadecyl group, a perbromoeicosyl group and the like.
Further, all of these alkyl groups may be partially substituted with an alkoxy group such as a methoxy group, an ethoxy group or the like, an aryloxy group such as a phenoxy group or the like or an aralkyloxy group such as a benzyloxy group or the like, etc.
As the aralkyl group in the substituent, X 1 , R 1 , R 2 , R 3 , R 4 , R 5 or R 6 , an aralkyl group having 7 to 20 carbon atoms is preferable, and examples thereof include a benzyl group, a (2-methylphenyl)methyl group, a (3-methylphenyl)methyl group, a (4-methylphenyl)methyl group, a (2,3-dimethylphenyl)methyl group, a (2,4-dimethylphenyl)methyl group, a (2,5-dimethylphenyl)methyl group, a (2,6-dimethylphenyl)methyl group, a (3,4-dimethylphenyl)methyl group, a (3,5-dimethylphenyl)methyl group, a (2,3,4-timethylphenyl)methyl group, a (2,3,5-timethylphenyl)methyl group, a (2,3,6-timethylphenyl)methyl group, a (3,4,5-timethylphenyl)methyl group, a (2,4,6-timethylphenyl)methyl group, a (2,3,4,5-tetramethylphenyl)methyl group, a (2,3,4,6-tetramethylphenyl)methyl group, a (2,3,5,6-tetramethylphenyl)methyl group, a (pentamethylphenyl)methyl group, an (ethylphenyl)methyl group, a (n-propylphenyl)methyl group, an (isopropylphenyl)methyl group, a (n-butylphenyl)methyl group, a (sec-butylphenyl)methyl group, a (tert-butylphenyl)methyl group, a (n-pentylphenyl)methyl group, a (neopentylphenyl)methyl group, a (n-hexylphenyl)methyl group, a (n-octylphenyl)methyl group, a (n-decylphenyl)methyl group, a (n-dodecylphenyl)methyl group, a naphthylmethyl group, an anthracenylmethyl group an the like, and a benzyl group is more preferable.
All of these aralkyl groups may be partially substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkoxy group such as a methoxy group, an ethoxy group or the like, an aryloxy group such as a phenoxy group or the like or an aralkyloxy group such as a benzyloxy group or the like, etc.
As the aryl group in the substituent, X 1 , R 1 , R 2 , R 3 , R 4 , R 5 or R 6 , an aryl group having 6 to 20 carbon atoms is preferable, and examples thereof include a phenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, a 2,3-xylyl group, a 2,4-xylyl group, a 2,5-xylyl group, a 2,6-xylyl group, a 3,4-xylyl group, a 3,5-xylyl group, a 2,3,4-trimethylphenyl group, a 2,3,5-trimethylphenyl group, a 2,3,6-trimethylphenyl group, a 2,4,6-trimethylphenyl group, a 2,4,5-trimethylphenyl group, a 2,3,4,5-tetramethylphenyl group, a 2,3,4,6-tetramethylphenyl group, a 2,3,5,6-tetramethylphenyl group, a pentamethylphenyl group, an ethylphenyl group, a n-propylphenyl group, an isopropylphenyl group, a n-butylphenyl group, a sec-butylphenyl group, a tert-butylphenyl group, a n-pentylphenyl group, a neopentylphenyl group, a n-hexylphenyl group, a n-octylphenyl group, a n-decylphenyl group, a n-dodecylphenyl group, a n-tetradecylphenyl group, a naphthyl group, an anthracenyl group and the like, and a phenyl group is more preferable.
All of these aryl groups may be partially substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like, an alkoxy group such as a methoxy group, an ethoxy group or the like, an aryloxy group such as a phenoxy group or the like or an aralkyloxy group such as a benzyloxy group or the like, etc.
The substituted silyl group in the substituent, X 1 , R 1 , R 2 , R 3 , R 4 , R 5 or R 6 is a silyl group substituted with a hydrocarbon group, and examples of the hydrocarbon group include alkyl groups having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a n-pentyl group, a n-hexyl group, a cyclohexyl group and the like, and aryl groups such as a phenyl group and the like, etc. Examples of such substituted silyl group having 1 to 20 carbon atoms include mono-substituted silyl groups having 1 to 20 carbon atoms such as a methylsilyl group, an ethylsilyl group, a phenylsilyl group and the like; di-substituted silyl groups having 2 to 20 carbon atoms such as a dimethylsilyl group, a diethylsilyl group, a diphenylsilyl group and the like; and tri-substituted silyl groups having 3 to 20 carbon atoms such as a trimethylsilyl group, a triethylsilyl group, a tri-n-propylsilyl group, a triisopropylsilyl group, a tri-n-butylsilyl group, a tri-sec-butylsilyl group, a tri-tert-butylsilyl group, a tri-isobutylsilyl group, a tert-butyl dimethylsilyl group, a tri-n-pentylsilyl group, a tri-n-hexylsilyl group, a tricyclohexylsilyl group, a triphenylsilyl group and the like, and a trimethylsilyl group, a tert-butyldimethylsilyl group or a triphenylsilyl group is preferable.
All of the hydrocarbon groups of these substituted silyl groups may be partially substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkoxy group such as a methoxy group, an ethoxy group or the like, an aryloxy group such as a phenoxy group or the like or an aralkyloxy group such as a benzyloxy group or the like, etc.
As the alkoxy group in the substituent X 1 , R 1 , R 2 , R 3 , R 4 , R 5 or R 6 , an alkoxy group having 1 to 20 carbon atoms is preferable, and examples thereof include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a sec-butoxy group, a tert-butoxy group, a n-pentoxy group, a neopentoxy group, a n-hexoxy group, a n-octoxy group, a n-dodecoxy group, a n-pentadecoxy group, a n-eicosoxy group and the like, and a methoxy group, an ethoxy group or a tert-butoxy group is preferable.
All of these alkoxy groups may be partially substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like, an alkoxy group such as a methoxy group, an ethoxy group or the like, an aryloxy group such as a phenoxy group or the like or an aralkyloxy group such as a benzyloxy group or the like, etc.
As the aralkyloxy group in the substituent, X 2 , R 1 , R 2 , R 3 , R 4 , R 5 or R 6 , an aralkyloxy group having 7 to 20 carbon atoms is preferable, and examples thereof include a benzyloxy group, a (2-methylphenyl)methoxy group, a (3-methylphenyl)methoxy group, a (4-methylphenyl)methoxy group, a (2,3-dimethylphenyl)methoxy group, a (2,4-dimethylphenyl)methoxy group, a (2,5-dimethylphenyl)methoxy group, a (2,6-dimethylphenyl)methoxy group, a (3,4-dimethylphenyl)methoxy group, a (3,5-dimethylphenyl)methoxy group, a (2,3,4-trimethylphenyl)methoxy group, a (2,3,5-trimethylphenyl)methoxy group, a (2,3,6-trimethylphenyl)methoxy group, a (2,4,5-trimethylphenyl)methoxy group, a (2,4,6-trimethylphenyl)methoxy group, a (3,4,5-trimethylphenyl)methoxy group, a (2,3,4,5-tetramethylphenyl)methoxy group, a (2,3,4,6-tetramethylphenyl)methoxy group, a (2,3,5,6-tetramethylphenyl)methoxy group, a (pentamethylphenyl)methoxy group, an (ethylphenyl)methoxy group, a (n-propylphenyl)methoxy group, an (isopropylphenyl)methoxy group, (n-butylphenyl)methoxy group, a (sec-butylphenyl)methoxy group, a (tert-butylphenyl)methoxy group, a (n-hexylphenyl)methoxy group, a (n-octylphenyl)methoxy group, a (n-decylphenyl)methoxy group, a naphthylmethoxy group, an anthracenylmethoxy group and the like, and a benzyloxy group is more preferable.
All of these aralkyloxy groups may be partially substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkoxy group such as a methoxy group, an ethoxy group or the like, an aryloxy group such as a phenoxy group or the like or an aralkyloxy group such as a benzyloxy group or the like, etc.
As the aryloxy group in the substituent, X 1 , X 2 , R 1 , R 2 , R 3 , R 4 , R 5 or R 6 , an aryloxy group having 6 to 20 carbon atoms is preferable, and examples thereof include a phenoxy group, a 2-methylphenoxy group, a 3-methylphenoxy group, a 4-methylphenoxy group, a 2,3-dimethylphenoxy group, a 2,4-dimethylphenoxy group, a 2,5-dimethylphenoxy group, a 2,6-dimethylphenoxy group, a 3,4-dimethylphenoxy group, a 3,5-dimethylphenoxy group, a 2,3,4-trimethylphenoxy group, a 2,3,5-trimethylphenoxy group, a 2,3,6-trimethylphenoxy group, a 2,4,5-trimethylphenoxy group, a 2,4,6-trimethylphenoxy group, a 3,4,5-trimethylphenoxy group, a 2,3,4,5-tetramethylphenoxy group, a 2,3,4,6-tetramethylphenoxy group, a 2,3,5,6-tetramethylphenoxy group, a pentamethylphenoxy group, an ethylphenoxy group, a n-propylphenoxy group, an isopropylphenoxy group, a n-butylphenoxy group, a sec-butylphenoxy group, a tert butylphenoxy group, a n-hexylphenoxy group, a n-octylphenoxy group, a n-decylphenoxy group, a n-tetradecylphenoxy group, a naphthoxy group, an anthracenoxy group and the like.
All of these aryloxy groups may be partially substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkoxy group such as a methoxy group, an ethoxy group or the like, an aryloxy group such as a phenoxy group or the like or an aralkyloxy group such as a benzyloxy group or the like, etc.
The di-substituted amino group in the substituent, X 1 , R 1 , R 2 , R 3 , R 4 , R 5 or R 6 is an amino group substituted with two hydrocarbon groups, and examples of the hydrocarbon group include alkyl groups having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a n-pentyl group, a n-hexyl group, a cyclohexyl group and the like; aryl groups having 6 to 10 carbon atoms such as a phenyl group and the like; aralkyl groups having 7 to 10 carbon atoms, etc. Examples of such di-substituted amino group substituted with the hydrocarbon group having 1 to 10 carbon atoms include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, a di-sec-butylamino group, a di-tert-butylamino group, a di-isobutylamino group, a tert-butylisopropylamino group, a di-n-hexylamino group, a di-n-octylamino group, a di-n-decylamino group, a diphenylamino group, a bistrimethylsilylamino group, a bis-tert-butyldimethylsilylamino group and the like, and a dimethylamino group or an diethylamino group is preferable.
All of these di-substituted amino groups may be partially substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkoxy group such as a methoxy group, an ethoxy group or the like, an aryloxy group such as a phenoxy group or the like or an aralkyloxy group such as a benzyloxy group or the like, etc.
The substituent, R 1 , R 2 , R 3 , R 4 , R 5 or R 6 may be optionally combined with each other to form a ring.
Each of R 1 is preferably an alkyl group, an aralkyl group, an aryl group or a substituted silyl group, independently.
Each of X 1 is preferably a halogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a di-substituted amino group, independently. An alkoxy group is more preferable.
Examples of the atom of Group XVI of the Periodic Table of the Elements indicated as X 2 in the general formula [I] or [II] include an oxygen atom, a sulfur atom, a selenium atom and the like, and an oxygen atom is preferable.
Examples of such transition metal compound [I] include μ-oxobis{isopropylidene(η 5 -cyclopentadienyl)(2-phenoxy)titanium chloride}, μ-oxobis{isopropylidene(η 5 -cyclopentadienyl)(2-phenoxy)titanium methoxide}, μ-oxobis{isopropylidene(η 5 -cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium chloride}, μ-oxobis{isopropylidene(η 5 -cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium methoxide}, μ-oxobis{isopropylidene(η 5 -methylcyclopentadienyl)(2-phenoxy)titanium chloride}, μ-oxobis{isopropylidene(η 5 -methylcyclopentadienyl)(2-phenoxy)titanium methoxide}, μ-oxobis{isopropylidene(η 5 -methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium chloride}, μ-oxobis{isopropylidene(η 5 -methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium methoxide}, μ-oxobis{isopropylidene (η 5 -tetramethylcyclopentadienyl)(2-phenoxy)titanium chloride}, μ-oxobis{isopropylidene(η 5 -tetramethylcyclopentadienyl)(2-phenoxy)titanium methoxide}, μ-oxobis{isopropylidene(η 5 -tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl 2-phenoxy)titanium chloride}, μ-oxobis{isopropylidene(η 5 -tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium methoxide}, μ-oxobis{dimethylsilylene(η 5 -cyclopentadienyl)(2-phenoxy)titanium chloride}. μ-oxobis{dimethylsilylene(η 5 -cyclopentadienyl)(2-phenoxy)titanium methoxide}, μ-oxobis{dimethylsilylene(η 5 -cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium chloride}, μ-oxobis{dimethylsilylene(η 5 -cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium methoxide}, μ-oxobis{dimethylsilylene(η 5 -methylcyclopentadienyl)(2-phenoxy)titanium chloride}, μ-oxobis{dimethylsilylene(η 5 -methylcyclopentadienyl)(2-phenoxy)titanium methoxide}, μ-oxobis{dimethylsilylene(η 5 -methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium chloride}, μ-oxobis{dimethylsilylene(η 5 -methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium methoxide}, μ-oxobis{dimethylsilylene(η 5 -tetramethylcyclopentadienyl)(2-phenoxy)titanium chloride}, μ-oxobis{dimethylsilylene(η 5 -tetramethylcyclopentadienyl)(2-phenoxy)titanium methoxide}, μ-oxobis{dimethylsilylene(η 5 -tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium chloride}, μ-oxobis{dimethylsilylene(η 5 -tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium methoxide} and the like.
Examples of such transition metal compound [II] include di-μ-oxobis{isopropylidene(η 5 -cyclopentadienyl)(2-phenoxy)titanium}, di-μ-oxobis{isopropylidene(η 5 -cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium}, di-μ-oxobis{isopropylidene(η 5 -methylcyclopentadienyl)(2-phenoxy)titanium}, di-μ-oxobis{isopropylidene(η 5 -methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium}, di-μ-oxobis{isopropylidene(η 5 -tetramethylcyclopentadienyl)(2-phenoxy)titanium}, di-μ-oxobis{isopropylidene(η 5 -tetramethyl cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium}, di-μ oxobis[dimethylsilylene (η 5 -cyclopentadienyl)(2-phenoxy)titanium], di-μ-oxobis{dimethylsilylene(η 5 -cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium}, di-μ-oxobis{dimethylsilylene(η 5 -methylcyclopentadienyl)(2-phenoxy)titanium}, di-μ-oxobis{dimethylsilylene(η 5 -methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium}, di-μ-oxobis{dimethylsilylene(η 5 -tetramethylcyclopentadienyl)(2-phenoxy)titanium}, di-μ-oxobis{dimethylsilylene(η 5 -tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium} and the like.
The transition metal compound represented by the general formula [I] or [II] can be produced, for example, by reacting a transition metal compound obtained according to the method described in the WO 97/03992 with 0.5-fold by mole or 1-fold by mole of water. Wherein a method of directly reacting a transition metal compound with a required amount of water, a method of charging a transition metal compound in a solvent such as a hydrocarbon containing a required amount of water, or the like, a method of charging a transition metal compound in a solvent such as a dry hydrocarbon or the like and further flowing an inert gas containing a required amount of water, or the like, etc. can be adopted.
(B) Aluminum Compound
The aluminum compound (B) used in the present invention is at least one organoaluminum compound selected from (B1) to (B3) described below:
(B1) an organoaluminum compound indicated by the general formula E 1 a AlZ 3−a ;
(B2) a cyclic aluminoxane having a structure indicated by the general formula {—Al(E 2 )—O—} b ; and
(B3) a linear aluminoxane having a structure indicated by the general formula E 3 {—Al(E 3 )—O—} c AlE 3 2 (wherein each of E 1 , E 2 and E 3 is a hydrocarbon group; all of E 1 , all of E 2 and all of E 3 may be the same or different; Z represents a hydrogen atom or a halogen atom; all of Z may be the same or different; a represents a number satisfying an expression of 0<a≦3; b represents an integer of 2 or more and c represents an integer of 1 or more).
As the hydrocarbon group in E 1 , E 2 or E 3 , a hydrocarbon group having 1 to 8 carbon atoms is preferable and an alkyl group is more preferable.
Specific examples of the organoaluminum compound (B1), indicated by the general formula E 1 a AlE 3-a include trialkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, triisobutylaluminum, tri-n-hexylaluminum and the like; dialkylaluminum chlorides such as dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, di-n-hexylaluminum chloride and the like; alkylaluminum dichlorides such as methylaluminum dichloride, ethylaluminum dichloride, n-propylaluminum dichloride, isopropylaluminum dichloride, isobutylaluminum dichloride, n-hexylaluminum dichloride and the like; and dialkylaluminum hydrides such as dimethylaluminum hydride, diethylaluminum hydride, di-n-propylaluminum hydride, diisopropylaluminum hydride, diisobutylaluminum hydride, di-n-hexylaluminum hydride and the like, etc.
Trialkylaluminum is preferable and triethylaluminum or triisobutylaluminum is more preferable.
Specific examples of E 2 and E 3 in the cyclic aluminoxane (B2) having a structure indicated by the general formula {—Al(E 2 )—O—} b and the linear aluminoxane(B3) having a structure indicated by the general formula E 3 {—Al(E 3 )—O—} c AlE 3 2 include alkyl groups such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a n-pentyl group, a neopentyl group and the like. b is an integer of 2 or more, and c is an integer of 1 or more. Preferably, each of E 2 and E 3 is a methyl group or an isobutyl group, b is 2 to 40 and c is 1 to 40.
The above-mentioned aluminoxane is prepared by various methods. The method is not specifically limited, and the aluminoxane may be prepared according to publicly known processes.
For example, the aluminoxane is prepared by contacting a solution of a trialkylaluminum (e.g. trimethylaluminum or the like) dissolved in a suitable organic solvent (e.g. benzene, an aliphatic hydrocarbon or the like) with water. Further, there is exemplified a process for preparing the aluminoxane by contacting a trialkylaluminum (e.g. trimethylaluminum, etc.) with a metal salt containing crystal water (e.g. copper sulfate hydrate, etc.).
(C) Boron Compound
As the boron compound (C) in the present invention, any one of the boron compound (C1) represented by the general formula BQ 1 Q 2 Q 3 , the boron compound (C2) represented by the general formula G + (BQ 1 Q 2 Q 3 Q 4 ) − and the boron compound (C3) represented by the general formula (L—H) + (BQ 1 Q 2 Q 3 Q 4 ) − can be used.
In the boron compound (C1) represented by the general formula BQ 1 Q 2 Q 3 , B represents a boron atom in the trivalent valence state; Q 1 to Q 3 are respectively a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a substituted silyl group, an alkoxy group or a di-substituted amino group and they may be the same or different. Each of Q 1 to Q 3 is preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a substituted silyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or a di-substituted amino group having 2 to 20 carbon atoms, and each of more preferable Q 1 to Q 3 is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms. Each of the more preferable Q 1 to Q 2 is a fluorinated hydrocarbon group having 1 to 20 carbon atoms which contains at least one fluorine atom, and in particular, each of Q 1 to Q 4 is preferably a fluorinated aryl group having 6 to 20 carbon atoms which contains at least one fluorine atom.
Specific examples of the compound (Ci) include tris(pentafluorophenyl)borane, tris(2,3,5,6-tetrafluorophenyl)borane, tris(2,3,4,5-tetrafluorophenyl)borane, tris(3,4,5-trifluorophenyl)borane, tris(2,3,4-trifluorophenyl)borane, phenylbis(pentafluorophenyl)borane and the like, and tris(pentafluorophenyl)borane is most preferable.
In the boron compound (C2) represented by the general formula G + (BQ 1 Q 2 Q 3 Q 4 ) − , G + is an inorganic or organic cation; B is a boron atom in the trivalent valence state; and Q 1 to Q 4 are the same as defined in Q 1 to Q 3 in the above-mentioned (C1).
Specific examples of G + as the inorganic cation in the compound represented by the general formula G + (BQ 1 Q 2 Q 3 Q 4 ) − include a ferrocenium cation, an alkyl-substituted ferrocenium cation, a silver cation and the like, and the G + as the organic cation includes a triphenylmethyl cation and the like. G + is preferably a carbonium cation, and a triphenylmethyl cation is particularly preferred. As the (BQ 1 Q 2 Q 3 Q 4 ), tetrakis(pentafluorophenyl)borate, tetrakis(2,3,5,6-tetrafluorophenyl)borate, tetrakis(2,3,4,5 tetrafluorophenyl)borate, tetrakis(3,4,5-trifluorophenyl)borate, tetrakis(2,3,4-trifluorophenyl)borate, phenyltris(pentafluorophenyl)borate, tetrakis(3,5-bistrifluoromethylphenyl)borate and the like are mentioned.
These specific combinations include ferrocenium tetrakis(pentafluorophenyl)borate, 1,1′-dimethylferrocenium tetrakis(pentafluorophenyl) borate, silver tetrakis(pentafluorophenyl)borate, triphenylmethyl tetrakis(pentafluorophenyl)borate, triphenylmethyl tetrakis(3,5-bistrifluoromethylphenyl)borate and the like, and triphenylmethyl tetrakis(pentafluorophenyl)borate is most preferable.
Further, in the boron compound (C3) represented by the formula (L—H) + (BQ 1 Q 2 Q 3 Q 4 ) − , L is a neutral Lewis base; (L—H) + is a Brφnsted acid; B is a boron atom in the trivalent valence state; and Q 1 to Q 4 are the same as Q 1 to Q 3 in the above-mentioned Lewis acid (C1).
Specific examples of (L—H) + as the Brφnsted acid in the compound represented by the formula (L—H) + (BQ 1 Q 2 Q 3 Q 4 ) include a trialkyl-substituted ammonium, an N,N-dialkylanilinium, a dialkylammonium, a triarylphosphonium and the like, and examples of (BQ 1 Q 2 Q 3 Q 4 ) − include those as previously described.
These specific combinations include triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(3,5-bistrifluoromethylphenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, N,N-2,4,6-pentamethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bistrifluoromethylphenyl)borate, diisopropylammonium tetrakis(pentafluorophenyl)borate, dicyclohexylammonium tetrakis(pentafluorophenyl)borate, triphenylphosphonium tetrakis(pentafluorophenyl)borate, tri(methylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, tri(dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate and the like, and tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate or N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate is most preferable.
[Polymerization of Olefin]
In the present invention, the olefin polymerization catalyst is prepared by a process comprising contacting the transition metal compound (A) represented by the general formula [I] and/or [II] and [the above-mentioned (B) and/or the above-mentioned (C)]. In case of an olefin polymerization catalyst prepared by using the transition metal compound (A) and the above-mentioned (B), the fore-mentioned cyclic aluminoxane (B2) and/or the linear aluminoxane (B3) is preferable as (B). Further, as another preferable mode of an olefin polymerization catalyst, an olefin polymerization catalyst prepared by using the transition metal compound, (A), the above-mentioned (B) and the above-mentioned (C) is illustrated, and the fore-mentioned (B1) is also easily used as said (B).
In the present invention, the transition metal compound (A) represented by the general formula [I] and/or [II] and the above-mentioned (B), or further the above-mentioned (C) can be charged in an arbitrary order during polymerization to be used, but a reaction product obtained by previously contacting an arbitrary combination of those compounds may be also used.
The used amount of respective components is not specifically limited, and it is desirable to usually use the respective components so that the molar ratio of the (B)/transition metal compound (A) is 0.1 to 10000 and preferably 5 to 2000, and the molar ratio of the (C)/transition metal compound (A) is 0.01 to 100 and preferably 0.5 to 10.
When the respective components are used in a solution condition or a condition in which they are suspended or slurried in a solvent, the concentration of the respective components is appropriately selected according to the conditions such as the ability of an apparatus for feeding the respective components in a polymerization reactor. The respective components are desirable used so that the concentration of the transition metal compound (A) is usually 0.001 to 200 mmol/L, more preferably 0.001 to 100 mmol/L and most preferably 0.05 to 50 mmol/L; the concentration of (B) is usually 0.01 to 5000 mmol/L converted to Al atom, more preferably 0.1 to 2500 mmol/L and most preferably 0.1 to 2000 mmol/L; and the concentration of (C) is usually 0.001 to 500 mmol/L, more preferably 0.01 to 250 mmol/L and most preferably 0.05 to 100 mmol/L.
As olefins which can be applied to the polymerization in the present invention, olefins having 2 to 20 carbon atoms such as, particularly, ethylene and an α-olefin having 3 to 20 carbon atoms, diolefins having 4 to 20 carbon atoms and the like can be used, and two or more monomers can also be used, simultaneously. Specific examples of the olefin include straight-chain olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene-1 and the like; branched olefins such as 3-methylbutene-1, 3-methylpentene-1, 4-methylpentene-1, 5-methylhexene-1 and the like; vinylcyclohexane, etc., but the present invention should not be limited to the above-mentioned compounds. Specific examples of the combination of monomers in case of conducting copolymerization include ethylene and propylene, ethylene and butene-1, ethylene and hexene-1, ethylene and octene-1, propylene and butene-1 and the like, but the present invention should not be limited thereto.
The present invention can be effectively applied to the particular preparation of the copolymer of ethylene and an α-olefin such as in particular, propylene, butene-1, 4-methylpentene-1, hexene-1, octene-1 or the like.
Polymerization processes should not be also specifically limited, and there can be a solvent polymerization or slurry polymerization in which an aliphatic hydrocarbon such as butane, pentane, hexane, heptane, octane or the like; and aromatic hydrocarbon such as benzene, toluene or the like; or a halogenated hydrocarbon such as methylene dichloride or the like used as a polymerization medium. Further, high pressure ionic polymerization in which the polymerization of an olefin is conducted without a solvent under which an olefin polymer is melt in a high temperature and high pressure olefin in a supercritical liquid condition, and further, a gas phase polymerization in a gaseous monomer and the like are possible. Further, either of a continuous polymerization and a batch-wise polymerization are possible.
The polymerization temperature can be usually adopted at a range of 31 50° C. to 350° C. and preferably 0° C. to 300° C., and in particular, a range of 50° C. to 300° C. is preferable. The polymerization pressure can be adopted at a range of atmospheric pressure to 350 MPa and preferably atmospheric pressure to 300 MPa, and in particular, a range of atmospheric pressure to 200 MPa is preferable.
In general, the polymerization time is appropriately determined according to the kind of a desired polymer and a reaction apparatus, and the conditions are not specifically limited and a range of 1 minute to 20 hours can be adopted. Further, a chain transfer agent such as hydrogen or the like can also be added to adjust the molecular weight of a copolymer in the present invention.
The process for polymerizing the olefin polymer of the present invention is suitably carried out by a high-pressure ionic polymerization process, in particular.
Specifically, it is preferably carried out under a pressure of 30 MPa or more and at a temperature of 300° C. or more. It is more preferably carried out under a pressure of 35 to 350 MPa and at a temperature of 135 to 350° C.
The polymerization form can be carried out in either a batch-wise manner or a continuous manner, but the continuous manner is preferable. As a reactor, a stirring vessel type reactor or a tubular reactor can be used. The polymerization can be performed in a single reaction zone. Alternatively, the polymerization can also be performed by partitioning one reactor into a plurality of reaction zones or connecting a plurality of reactors in series or parallel. In case of using a plurality of reactors, a combination of a vessel reactor and a vessel reactor or a combination of a vessel reactor and a tubular reactor may be used. In a polymerization process using a plurality of reaction zones or a plurality of reactors, polymers having different characteristics can also be produced by changing the temperature, pressure and gas composition of respective reaction zones or reactors.
EXAMPLE
The present invention is further illustrated in detail according to Examples and Comparative Examples below, but the present invention is not limited thereto.
Properties of the polymers in Examples were measured according to methods described below.
(1) Melt index (MFR) was measured at 190° C. according to the method defined in JIS K-6760. (Unit: g/10 min.)
(2) Density was determined according to JIS K-6760.
Wherein the value of density described as density (without annealing) is a value obtained by measuring without an annealing treatment in JIS K-6760. (Unit: g/cm 3 )
(3) Melting point of copolymer: It was measured under the following conditions using DSC7 manufactured by Perkin-Elmer Co.
Heating: heating to 150° C. and maintaining until the change of calorie is stabilized
Cooling: 150 to 10° C. (5° C./min.) and maintaining for 10 minutes
Measurement: 10 to 160° C. (5° C./min.)
(4) Content of 60-olefin:
It was determined from the characteristic absorption of ethylene and 60-olefin using an infrared spectrometer (FT-IR7300, manufactured by NIPPON BUNKO Inc.) and was represented as a short-chain branch (SCB) number per 1000 carbon atoms.
(5) Weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw/Mn):
They were determined under the following conditions using gel permeation chromatography (150, c, manufactured by Waters Co.).
Column: TSK gel GMH-HT
Measurement temperature: set at 145° C.
Measurement concentration: 10 mg/10 ml ortho-dichlorobenzene
(6) Intrinsic viscosity ([η]):
100 mg of a copolymer obtained was dissolved in 50 ml of tetralin at 135° C. and the solution was set in an oil bath maintained at 135° C. Using an Ubbelohde viscometer, the intrinsic viscosity was determined by the falling speed of the tetralin solution in which said sample was dissolved. (Unit: dl/g)
REFERENCE EXAMPLE 1
[Synthesis of transition metal compound: dimethylsilylene(η 5 -tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dimethoxide)]
In a Schlenk tube, 0.131 g (4.1 mmol) of methanol was dissolved in 10 ml of anhydrous diethyl ether and a diethyl ether solution (3.9 ml, 4.1 mmol) of methyllithium having a concentration of 1.05 mol/L was added dropwise at −78° C. thereto. The resulting mixture was heated to 20° C., the formation of lithium methoxide was confirmed by gas generation, and the resulting reaction solution was again cooled to −78° C. Into the reaction solution, 20 ml of an anhydrous diethyl ether suspension liquid of 0.919 g (2.0 mmol) of dimethylsilylene (η 0 -tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride which was previously prepared in another Schlenk tube was transferred, and then, the resulting reaction mixture was gradually heated to room temperature to obtain a reaction solution. After concentrating the reaction solution, 20 ml to toluene was added and an insoluble product was separated by filtration. The filtrate was concentrated to obtain dimethylsilylene(η 5 -tetramethylcyclopontadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dimethoxide of yellow crystals (0.86 g, 95%).
1 NMR (270 MHz, C 4 D 5 ); δ7.26 (m, 2 H), 4.13 (s, 6 H), 2.33 (s, 3 H), 1.97(s, 6 H), 1.89(s, 6 H), 1.59(s, 9 H), 0.55(s, 6 H)
REFERENCE EXAMPLE 2
[Synthesis example of transition metal compound: μ-oxobis {dimethylsilylene (η 5 -tetramethyl cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide (Compound 1)}
Under a nitrogen atmosphere, 10.00 g of dimethylsilylene (η 5 -tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dimethoxide (the compound obtained by the same method as in Reference Example 1) was dissolved in 50 ml of heptane, 0.30 g of distilled water was added thereto, and the mixture was stirred at the same temperature for 12 hours. The solid produced was separated by filtration, rinsed with 5.0 ml of heptane, and then dried under vacuum to obtain μ-oxobis{dimethylsilylene(η 5 -tetramethyl cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide} of a yellow solid (5.51 g, 56%).
Mass spectrum (m/c) 855 Calculated value: 855
1 H-NMR (C 4 D 4 ); δ7.25 (d, J-2.0 Dz, 2 H), 7.16 (d, J=2.0 Hz, 2 H), 3.99 (s, 6 H), 2.32 (s, 6 H), 2.30 (s, 6 H), 2.06 (s, 6 H), 1.86 (s, 6 H), 1.71(s, 6 H), 1.27 (s, 18 H), 0.83 (s, 6 H), 0.63 (s, 6 H)
REFERENCE EXAMPLE 3
[Synthesis example of transition metal compound: di-μ-oxobis {dimethylsilylene (η 5 -tetramethyl cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium} (Compound 2)]
In a Schlenk tube, 1.50 g (3.3 mmol) of dimethylsilylene (η 5 -tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dimethoxide was dissolved in 20 ml of toluene, 10 ml of water was added thereto, and the resulting liquid mixture was stirred at 70° C. for 1 hour. After concentrating the organic layer which was obtained by phase separation, the concentrate was recrystallized from 10 ml of heptane to obtain di-μ-oxobis {dimethylsilylene(η 5 tetramethyl cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium} of yellow crystals (0.40 g, 33%). Mass spectrum (m/e) 808. Calculated value: 808
1 H-NMR (270 MHz, C 6 D 6 ); δ7.28 (m, 4 H), 2.32(s, 12 H), 1.97(s, 6 H), 1.78(s, 6 H), 1.59(s, 6 H), 1.53(s, 18 H), 0.78(s, 6 H), 0.58(s, 6 H)
EXAMPLE 1
Using an autoclave type reactor having an inner volume of 1 liter equipped with a stirrer, polymerization was carried out by continuously feeding ethylene and hexene-1 into the reactor. Regarding the polymerization conditions, the total pressure was set to 80 MPa and the concentration of hexene-1 based on the total of ethylene and hexene-1 was set to 28.8% by mole. A heptane solution (which was adjusted to be the concentration of Compound 1 of 0.185 μmol/g, the concentration of triisobutylaluminum of 18.5 μmol/g and a molar ratio of Al atom to Ti atom of 50. ) in which μ-oxobis {dimethylsilylene (η 5 -tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phonoxy) titanium methoxide} (Compound 1) and triisobutylaluminum were mixed and a toluene solution (0.90 μmol/g) of N,N-dimethylaniliniumtetrakis (pentafluorophenyl)borate were respectively prepared in separate vessels. Each of the solutions was continuously fed in the reactor at a feeding rate of 100 g/hour and 140 g/hour. The polymerization reaction temperature was set at 222° C., and a molar ratio of boron atom to Ti atom was set to 3.4. As a result, an ethylene-hexene-1 copolymer having MFR of 8.39, a density (without annealing) of 0.883 g/cm 3 , SCB of 36.0, a weight average molecular weight (Mw) of 62000 and a molecular weight distribution (Mw/Mn) of 1.9 was produced at a rate of 74 ton per 1 mole of Ti atom.
COMPARATIVE EXAMPLE 1
Using an autoclave type reactor having an inner volume of 1 liter equipped with a stirrer, polymerization was carried out by continuously feeding ethylene and hexene-1 into the reactor. The total pressure was set to 80 MPa and the concentration of hexene-1 based on the total of ethylene and hexene-1 was set to 34% by mole. A hexane solution (0.7 μmol/g) of dimethylsilylene (η 5 -tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, a heptane solution of triisobutylaluminum (33 μmol/g) and further a toluene solution (1.2 μmol/g) of N,N-dimethylaniliniumtetrakis (pentafluorophenyl)borate were respectively prepared in separate vessels and continuously fed into the reactor at feeding rates of 290 g/hour, 350 g/hour and 580 g/hour, respectively. The polymerization reaction temperature was set at 215° C., and a molar ratio of boron atom to Ti atom was set to 3.3. As a result, an ethylene-hexene-1 copolymer having MFR of 4.2, a density (without annealing) of 0.881 g/cm 3 , a melting point of 67.3° C., SCB of 40.4, Mw of 66000 and Mw/Mn of 1.8 was produced in a rate of 14 ton per 1 mole of Ti atom.
EXAMPLE 2
After replacing the atmosphere of an autoclave type reactor having an inner volume of 0.4 liter equipped with a stirrer with argon, 185 ml of cyclohexane as a solvent and 15 ml of hexene-1 as an α-olefin were charged and the reactor was heated to 180° C. After the elevation of temperature, ethylene was fed while adjusting at an ethylene pressure of 2.5 Mpa. After the system was stabilized, 0.2 mmol of triisobutylaluminum, 0.5 ml (namely, 0.5 μmol of Compound 1 and 25 μmol of triisobutylaluminum) of a heptane solution (which was adjusted to be the concentration of Compound 1 of 1 μmol/ml, the concentration of triisobutylaluminum of 50 μmol/ml and a molar ratio of Al atom to Ti atom of 25.) in which μ-oxobis{dimethylsilylene(η 5 -tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide} (Compound 1) and triisobutylaluminum were mixed, were charged and successively, 1.5 μmol of N,N-dimethylaniliniumtetrakis (pentafluorophenyl)borate was charged as a slurry in heptane. Polymerization was carried out for 2 minutes. As a result of the polymerization, 2.53 g of an ethylene-hexene-1 copolymer having [η] of 0.85 dl/g, SCB of 31.4 and melting points of 78.6° C. and 90.8° C. was obtained. Polymerization activity per 1 mole of Ti atom was 2.53×10 6 g-polymer/mol-Ti atom per 2 minutes.
EXAMPLE 3
After replacing the atmosphere of an autoclave type reactor having an inner volume of 0.4 liter equipped with a stirrer with argon, 185 ml of cyclohexane as a solvent and 15 ml of hexene-1 as an α-olefin were charged and the reactor was heated to 180° C. After the elevation of temperature, ethylene was fed while adjusting at an ethylene pressure of 2.5 Mpa. After the inner of system was stabilized, 0.2 mmol of triisobutylaluminum, 0.5 ml (namely, 0.5 μmol of Compound 1 and 25 μmol of triisobutylaluminum) of a heptane solution (which was adjusted to be the concentration of Compound 1 of 1 μmol/ml, the concentration of triisobutylaluminum of 50 μmol/ml and a molar ratio of Al atom to Ti atom of 25.) in which μ-oxobis{dimethylsilylene(η 5 -tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide } (Compound 1) and triisobutylaluminum were mixed, were charged and successively, 3 μmol of N,N-dimethylanilinium tetrakis (pentafluorophenyl)borate was charged as a slurry in heptane (a slurry concentration of 1 μmol/ml). Polymerization was carried out for 2 minutes. As a result of the polymerization, 5.33 g of an ethylene-hexene-1 copolymer having [η] of 0.67 dl/g, SCB of 35.0, melting points of 74.2° C. and 88.6° C., Mw of 43000 and Mw/Mn of 2.7 was obtained. Polymerization activity per 1 mol of Ti atom was 5.33×10 6 g-polymer/mol-Ti atom per 2 minutes.
EXAMPLE 4
After replacing the atmosphere of an autoclave type reactor having an inner volume of 0.4 liter equipped with a stirrer with argon, 185 ml of cyclohexane as a solvent and 15 ml of hexene-1 as an α-olefin were charged and the reactor was heated to 180° C. After the elevation of temperature, ethylene was fed while adjusting at an ethylene pressure of 2.5 Mpa. After the system was stabilized, 0.2 mmol of triisobutylaluminum, 0.5 ml (namely, 0.5 μmol of Compound 2 and 25 μmol of triisobutylaluminum) of a heptane solution (which was adjusted to be the concentration of Compound 2 of 1 μmol/ml, the concentration of triisobutylaluminum of 50 μmol/ml and a molar ration of Al atom to Ti atom of 25.) in which di-μ-oxobis{dimethylsilylene(η 5 -tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium} (Compound 2) and triisobutylaluminum were mixed, were charged and successively, 1.5 μmol of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate was charged as a slurry in heptane (a slurry concentration of 1 μmol/ml). Polymerization was carried out for 2 minutes. As a result of the polymerization, 2.55 g of an ethylene-hexene-1 copolymer having [η] of 0.84 dl/g, SCB of 30.7 and melting points of 80.2° C. and 93.0° C. was obtained. Polymerization activity per 1 mole of Ti atom was 2.55 ×10 6 g-polymer/mol-Ti atom per 2 minutes.
EXAMPLE 5
After replacing the atmosphere of an autoclave type reactor having an inner volume of 0.4 liter equipped with a stirrer with argon, 185 ml of cyclohexane as a solvent and 15 ml of hexene-1 as an α-olefin were charged and the reactor was heated to 180° C. After the elevation of temperature, ethylene was fed while adjusting at an ethylene pressure of 2.5 Mpa. After the system was stabilized, 0.2 mmol of triisobutylaluminum, 0.5 ml (namely, 0.5 μmol of Compound 2 and 25 μmol of triisobutylaluminum) of a heptane solution (which was adjusted to be the concentration of Compound 2 of 1 μmol/ml, the concentration of triisobutylaluminum of 50 μmol/ml and a molar ratio of Al atom to Ti atom of 25.) in which di-μ-oxobis{dimethylsilylene(η 5 -tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium} (Compound 2) and triisobutylaluminum were mixed, were charged and successively, 3 μmol of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate was charged as a slurry in heptane (a slurry concentration of 1 μmol/ml). Polymerization was carried out for 2 minutes. As a result of the polymerization, 3.92 g of an ethylene-hexene-1 copolymer having [η] of 0.73 dl/g, SCB of 33.0, melting points of 78.9° C. and 91.5° C., Mw of 48000 and Mw/Mn of 2.5 was obtained. Polymerization activity per 1 mole of Ti atom was 3.92×10 6 g-polymer/mol-Ti atom per 2 minutes.
As described above in detail, according to the present invention, a transition metal compound useful as a highly active olefin polymerization catalyst component at an efficient reaction temperature in the industrial process of an olefin polymerization, and a highly active olefin polymerization catalyst using said transition metal compound and a process of producing an olefin polymer using said olefin polymerization catalyst are provided. Further, the transition metal compound of the present invention is also effective as an olefin polymerization catalyst component having a high comonomer reaction rate in copolymerization and providing an olefin polymer with a high molecular weight, and has a remarkable value for utilization. | A specified transition metal compound having two transition metals and two cyclopentadiene type anion skeletone in tis molecule and said metals are linked through an atom of Group XVI of the Periodic Table of the Elements, and olefin polymerization catalyst component comprising said transition metal compound, an olefin polymerization catalyst comprising said transition metal compound, a specific organoaluminum compound, and a specific boron compound, and a process for producing an olefin polymer using said olefin polymerization catalyst. | 8 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U.S. nonprovisional application Ser. No. 12/928,812, filed Dec. 20, 2010, abandoned herewith.
BACKGROUND OF THE INVENTION
Field of the Invention
Embodiments relate to drain pipe closure protection devices which are used in conjunction with waste water-containing, pipe closures.
In particular, the prior art does not provide a drain pipe waste water closure protection device with the advantages of embodiments of the present disclosure, that of allowing full flow through the drain, full access to the waste water-containing closure for maintenance, protection of the waste water-containing, closure from evaporation, and protection of the structure from the escape of sewer gas if the waste water-containing, closure fails.
BRIEF SUMMARY OF THE INVENTION
The following embodiments and aspects thereof are described and illustrated in conjunction with systems, tool and methods which are meant to be exemplary and illustrative, not limiting in scope. In various embodiments, one or more of the above-described problems have been reduced or eliminated, while other embodiments are directed to other improvements.
Embodiments include a drain pipe waste water closure protection device comprising
a conical body having a drain water inlet and a drain water outlet. There is a corrosion resistant, radial compression cylinder embedded in the conical body near the inlet, the corrosion resistant, radial compression cylinder comprised of a strong, hard, resilient material. Two soft, flexible, resilient radial disc seals are located near the inlet of the conical body, the corrosion resistant, radial compression cylinder underlying the two radial disc seals. A quadruple pressure accumulating seal is located at the outlet of the conical body. All elements of the drain pipe waste water closure protection device except the compression cylinder manufactured of an elastomer imbibed with an adhesion prevention additive.
Embodiments also include a drain pipe waste water closure protection device which comprises a conical body having a drain water inlet and a drain water outlet. There is a radial compression cylinder embedded in the conical body near the drain water inlet comprised of stainless steel. Two radial disc seals are located near the drain water inlet of the conical body, and the radial compression cylinder is underlying the two radial disc seals. A quadruple pressure accumulating seal is comprised of four elliptical-parabolic double curved shaped pressure accumulating wall assemblies attached to the outlet of the conical body, each assembly comprised of an elliptical-parabolic double curved shaped pressure accumulating wall body comprised of a pressure accumulating wall shoulder, a left pressure accumulating section, and a right pressure accumulating section with a force accumulating outlet closure attached to each pressure accumulating section, wherein each force accumulating outlet closure is capable of interaction with an adjacent force accumulating outlet closure of an adjacent pressure accumulating wall body in a reversible sealing relationship. The conical body, radial disc seals, and quadruple pressure accumulating seal are collectively manufactured of a single piece elastomer imbibed with an adhesion prevention additive. The drain trap protection device is capable of mounting in a drain having a drain wall and the drain is attached to a waste water pipe. The radial disc seals are capable of having a sealing relationship with the drain wall, and the drain trap protection device is capable of allowing fluid flow through the drain into the waste water pipe when there is three ounces or more of water in the drain, and the drain pipe waste water closure protection device is capable of blocking backflow of gas or fluid from the waste water pipe into the drain when the pressure in the waste water pipe is equal to or higher than atmospheric pressure.
In addition to the exemplary aspects and embodiments described above, further aspects and embodiments will become apparent by reference to the drawings and by study of the following descriptions.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING(S)
FIG. 1 is a perspective side view showing the top of an embodiment drain pipe waste water closure protection device.
FIG. 2 is a perspective side view showing the bottom of an embodiment drain pipe waste water closure protection device.
FIG. 3 . is a top view of an embodiment drain pipe waste water closure protection device installed in a drain.
FIG. 4 is a cross-section of an embodiment drain pipe waste water closure protection device installed in a drain taken along line 4 - 4 of FIG. 3 .
FIG. 5 is a bottom view of an embodiment drain pipe waste water closure protection device.
FIG. 6 is a partial cross-section of an embodiment drain pipe waste water closure protection device taken along line 6 - 6 of FIG. 2 .
DETAILED DESCRIPTION OF THE INVENTION
In this disclosure, the following terms are used. “Waste water pipe” means a pipe leading from a drain to a sewer. “Drain pipe waste water closure protection device” means a seal structure located in a floor drain. “Water-containing pipe closure” means a generally U-shaped section of pipe containing water or another liquid located in a waste water pipe below a drain which prevents emission of gases from the waste water pipe through the drain.
“Pressure accumulating seal” means a seal manufactured of flexible material and comprised of two elliptical-parabolic double curved shaped pressure accumulating walls, each of which concentrates pressure exerted on the pressure accumulating wall on an attached force accumulating outlet closure, and which are each attached to a shoulder. The force accumulating outlet closures are together when the seal is closed and apart when the seal is open. A pressure accumulating seal is normally closed, blocking passage through the seal from either side.
“Quadruple pressure accumulating seal” means a seal comprised of four connected pressure accumulating seals.
FIG. 1 is a perspective side view showing the top of an embodiment drain pipe waste water closure protection device. FIG. 1 shows the exterior surfaces with the exception of the interior surface of the conical body 30 . Visible in FIG. 1 is an embodiment drain pipe waste water closure protection device 20 , rim 22 at the inlet of the conical body, upper radial disc seal 24 , lower radial disc seal 26 , and the conical body 30 , both radial disc seals located near the inlet of the conical body. Also visible is the first elliptical-parabolic cross section, double curved shaped pressure accumulating wall 40 comprised of first left pressure accumulating wall 44 , first left pressure accumulating wall, force accumulating outlet closure 48 , first assembly right pressure accumulating wall 46 with attached first right pressure accumulating wall, force accumulating outlet closure 42 . The fourth elliptical-parabolic cross section, double curved shaped pressure accumulating wall 70 is comprised of a fourth left pressure accumulating wall 72 (not visible in FIG. 1 ) with attached fourth left pressure accumulating wall, force accumulating outlet closure 76 (not visible in FIG. 1 ), fourth right pressure accumulating wall 74 with attached fourth right pressure accumulating wall, force accumulating outlet closure 78 . The first left pressure accumulating wall 44 is attached on one side to the first right pressure accumulating wall 46 . The first left pressure accumulating wall 44 is attached on the other side to the first shoulder 43 , which in turn is connected to the conical body 30 . The fourth left pressure accumulating wall 72 (not visible in FIG. 1 ) is attached on one side to the fourth right pressure accumulating wall 74 . The fourth left pressure accumulating wall 72 (not visible in FIG. 1 ) is attached on the other side to the fourth shoulder 73 , which in turn is connected to the conical body 30 .
The convex shape of the surface and the elliptical-parabolic outer margins of each pressure accumulating wall interact to concentrate forces exerted on the pressure accumulating wall surface onto the force accumulating outlet closure s, forcing them together, thereby insuring an effective seal between the force accumulating outlet closures.
FIG. 2 is a perspective side view showing the bottom of an embodiment drain pipe waste water closure protection device comprising a quadruple pressure seal. FIG. 2 shows the exterior surfaces of the drain pipe waste water closure protection device 20 . Visible in FIG. 2 is an upper radial disc seal 24 , lower radial disc seal 26 , and conical body 30 , both radial disc seals located near the inlet of the conical body. Also visible is the first elliptical-parabolic cross section, double curved shaped pressure accumulating wall 40 comprised of first left pressure accumulating wall 44 , first left pressure accumulating wall, force accumulating outlet closure 48 , first assembly right pressure accumulating wall 46 with attached first right pressure accumulating wall, force accumulating outlet closure 42 . The fourth elliptical-parabolic cross section, double curved shaped pressure accumulating wall 70 is comprised of a fourth left pressure accumulating wall 72 with attached fourth pressure accumulating wall left force accumulating outlet closure 76 , fourth right pressure accumulating wall 74 with attached fourth right pressure accumulating wall, force accumulating outlet closure 78 . Also visible in the third pressure accumulating wall, left force accumulating outlet closure 66 and the third right pressure accumulating wall, force accumulating outlet closure 68 . The second elliptical-parabolic cross section, double curved shaped pressure accumulating wall 50 is comprised of a second left pressure accumulating wall 52 with attached second left pressure accumulating wall, force accumulating outlet closure 56 , second right pressure accumulating wall 54 (not visible in FIG. 2 ) with attached second right pressure accumulating wall, force accumulating outlet closure 58 . The first left pressure accumulating wall 44 is attached on one side to the first right pressure accumulating wall 46 . The first left pressure accumulating wall 44 is attached on the other side to the first shoulder 43 , which in turn is connected to the conical body 30 . The fourth left pressure accumulating wall 72 is attached on one side to the fourth right pressure accumulating wall 74 . The fourth left pressure accumulating wall 72 is attached on the other side to the fourth shoulder 73 , which in turn is connected to the conical body 30 . Although not shown in FIG. 2 , the components of the second pressure accumulating wall and third pressure accumulating wall are connected to each other and to the second 53 and third 63 shoulders (both not visible in FIG. 2 ) in similar fashion. Seal 41 is formed by reversible interaction of force accumulating outlet closures 48 and 58 . Seal 51 is formed by reversible interaction of force accumulating outlet closures 52 and 68 . Seal 61 is formed by reversible interaction of force accumulating outlet closures 66 and 78 . Seal 71 is formed by reversible interaction of force accumulating outlet closures 42 and 76 . All four pressure accumulating wall seals intersect at the center 81 .
FIG. 3 is a top view of an embodiment drain pipe waste water closure protective device installed in a floor drain. Visible in FIG. 3 is an embodiment floor drain 10 without a drain strainer. Visible is a top rim 12 of the floor drain, a recess 14 for a drain strainer, a sloping drain mouth 16 , which connects with a vertical drain wall (not visible in FIG. 3 ). Features of the drain pipe waste water closure protection device 20 visible in FIG. 3 are the internal surfaces, with the exception of the rim 22 .
Visible in FIG. 3 is the upper radial disc seal 24 . Also visible is the first pressure accumulating wall 40 components, first left pressure accumulating wall 44 , first left pressure accumulating wall, force accumulating outlet closure 48 , first right pressure accumulating wall 46 , and first right pressure accumulating wall force accumulating outlet closure 42 . Also visible is the second pressure accumulating wall 50 components, second left pressure accumulating wall, 52 , second left pressure accumulating wall, force accumulating outlet closure 56 , second right pressure accumulating wall 54 , and second right pressure accumulating wall, force accumulating outlet closure 58 . Also visible is the third pressure accumulating wall 60 components, third left pressure accumulating wall 62 , third left pressure accumulating wall, force accumulating outlet closure 66 , third right pressure accumulating wall 64 , and third right pressure accumulating wall, force accumulating outlet closure 68 . Also visible is the fourth pressure accumulating wall 70 components, fourth left pressure accumulating wall 72 , fourth left pressure accumulating wall, force accumulating outlet closure 76 , fourth right pressure accumulating wall 74 , and fourth right pressure accumulating wall, force accumulating outlet closure 78 . A seal 41 is formed by the first left pressure accumulating wall, force accumulating outlet closure 48 and second right pressure accumulating wall, force accumulating outlet closure 58 . A seal 51 is formed by the second left pressure accumulating wall, force accumulating outlet closure 56 and the third right pressure accumulating wall, force accumulating outlet closure 68 . A seal 61 is formed by the third left pressure accumulating wall, force accumulating outlet closure 66 and the fourth right pressure accumulating wall, force accumulating outlet closure 78 . A seal 71 is formed by the fourth left pressure accumulating wall, force accumulating outlet closure 76 and the first right pressure accumulating wall, force accumulating outlet closure 42 . The seals meet at the center of the drain pipe waste water closure protection device 81 .
FIG. 4 is a cross-section of an embodiment drain pipe waste water closure protection device installed in a drain taken along line 4 - 4 of FIG. 3 . Visible in FIG. 4 is an embodiment floor drain 10 without a drain strainer. Visible is a top rim 12 of the floor drain, a recess 14 for a drain strainer, a sloping drain mouth 16 , which connects with a vertical drain wall 18 which connects with a drain pipe (not shown in FIG. 4 ). Features of the drain pipe waste water closure protection device 20 visible in FIG. 3 are the internal surfaces plus the rim 22 . Visible in the embodiment drain pipe waste water closure protection device in cross section in FIG. 4 is the drain pipe waste water closure protection device rim 22 , conical body 30 , inlet 32 of the conical body, and outlet 34 of the conical body. Also visible is the upper radial disc seal 24 and the lower radial disc seal 26 . The radial disc seals are shown bent upward by contact with the vertical drain wall 18 . Also visible is the radial compression cylinder 28 located in the conical body 30 and underlying the radial disc seals 24 and 26 . Also visible are the fourth left pressure accumulating wall 72 and the fourth right pressure accumulating wall 74 . The first right pressure accumulating wall 46 and attached first right pressure accumulating wall, force accumulating outlet closure 42 are shown. The third left pressure accumulating wall 62 and attached third left pressure accumulating wall, force accumulating outlet closure 66 are also show. All four pressure accumulating wall seals intersect at 81 .
FIG. 5 is a bottom view of an embodiment drain pipe waste water closure protection device 20 . Visible in FIG. 5 is a lower radial disc seal 26 . Also visible is the first elliptical-parabolic cross section, double curved shaped pressure accumulating wall 40 components, first left pressure accumulating wall 44 , first left pressure accumulating wall, force accumulating outlet closure 48 , first right pressure accumulating wall 46 , and first right pressure accumulating wall, force accumulating outlet closure 42 . Also visible is the second elliptical-parabolic cross section, double curved shaped pressure accumulating wall 50 components, second left pressure accumulating wall 52 , second left pressure accumulating wall, force accumulating outlet closure 56 , second right pressure accumulating wall 54 , and second right pressure accumulating wall, force accumulating outlet closure 58 . Also visible is the third elliptical-parabolic cross section, double curved shaped pressure accumulating wall 60 components, third left pressure accumulating wall 62 , third left pressure accumulating wall, force accumulating outlet closure 66 , third right pressure accumulating wall 64 , and third right pressure accumulating wall, force accumulating outlet closure 68 . Also visible is the fourth elliptical-parabolic cross section, double curved shaped pressure accumulating wall 70 components, fourth left pressure accumulating wall 72 , fourth left pressure accumulating wall, force accumulating outlet closure 76 , fourth right pressure accumulating wall 74 , and fourth right pressure accumulating wall, force accumulating outlet closure 78 . A seal 41 is formed by the first left pressure accumulating wall, force accumulating outlet closure 48 and second right pressure accumulating wall, force accumulating outlet closure 58 . A seal 51 is formed by the second left pressure accumulating wall, force accumulating outlet closure 56 and the third right pressure accumulating wall, force accumulating outlet closure 68 . A seal 61 is formed by the third left pressure accumulating wall, force accumulating outlet closure 66 and the fourth right pressure accumulating wall, force accumulating outlet closure 78 . A seal 71 is formed by the fourth left pressure accumulating wall, force accumulating outlet closure 76 and the first right pressure accumulating wall, force accumulating outlet closure 42 . The seals meet at the center of the drain pipe waste water closure protection device 81 . Also visible is the first shoulder 43 , second shoulder 53 , third shoulder 63 , and fourth shoulder 73 .
FIG. 6 is a partial cross-section of an embodiment drain pipe waste water closure protection device taken along line 6 - 6 of FIG. 2 . Visible in FIG. 6 is a second right pressure accumulating wall 54 with attached second right pressure accumulating wall, force accumulating outlet closure 58 , and the first left pressure accumulating wall 44 with attached first left pressure accumulating wall, force accumulating outlet closure 48 . Interaction between the force accumulating outlet closures form a reversible seal 41 .
Embodiment drain pipe waste water closure protection devices are made with the conical body, ring seals, or pressure accumulating seal comprised of any suitable soft, flexible, resilient material. Embodiments are made of acrylonitrile-butadiene rubber, polychloroprene, fluoroelastomers, ethylene propylene diene monomer, polyvinyl chloride, polyvinyl alcohol, high molecular weight polyethylene, perfluoroalkoxy polymer resin, fluorinated ethylene-propylene, or polytetrafluoroethylene. All materials of construction may be imbibed with adhesion prevention additive using compounds such as molybdenum sulfide or polytetrafluoroethylene.
Embodiments are made with the conical body, ring seals, or pressure accumulating seal comprised of acrylonitrile-butadiene rubber imbibed with adhesion prevention additive with molybdenum disulfide.
Embodiment drain pipe waste water closure protection devices are comprised of the conical body, ring seals, and pressure accumulating seal are collectively comprised of a single piece of material. In other embodiments the conical body, ring seals, or pressure accumulating seal are separately manufactured and subsequently assembled into an intact drain pipe waste water closure protection device.
Embodiment drain pipe waste water closure protection devices include a corrosion resistant, radial compression cylinder comprised of any suitable strong, hard, resilient material. Embodiments are manufactured of iron, stainless steel, cold rolled steel, cobalt, nickel, copper, or alloys thereof, or polystyrene, polyvinyl chloride, polypropylene, polyethylene, acrylonitrile butadiene styrene, polycarbonate, or polyamide.
Embodiment drain pipe waste water closure protection devices are intended for use with floor drain pipe waste water closure s. They act as a backup safety device to prevent backflow of gases or liquids from the waste water pipe into the structure. The primarily drain seal which prevents sewer gas backflow is a U-shaped water-filled pipe waste water closure in the waste water pipe below the drain pipe waste water closure protection device. Embodiments also help preserve the integrity of the primary drain seal by preventing air leakage or evaporation of water or other liquid from the primary drain seal.
Embodiment drain pipe waste water closure protection devices allow the flow of drainage to enter the plumbing drainage system without any undo reduction in flow capacity, in particular, embodiment drain pipe waste water closure protection devices open when there is 4 ounces or more of water in the drain and close at a downstream pressure of liquid or gases from the waste water pipe equal to or higher than atmospheric pressure. Embodiment drain pipe waste water closure protection devices also allow access to the primary drain seal for cleaning or inspection.
Embodiment drain pipe waste water closure protection devices include quadruple pressure accumulating seals. Such embodiments provide a greater diameter than simple pressure accumulating seals for maximum passage of liquids through the drain. In addition, quadruple pressure accumulating seals allow a maximum diameter opening for inspection and maintenance of the primary drain seal.
Embodiment drain pipe waste water closure protection devices protection devices are compliant with industry standards.
While a number of exemplary aspects and embodiments have been discussed above, those of skill in the art will recognize certain modifications, permutations, additions and sub combinations thereof. It is therefore intended that the following appended claims and claims hereafter introduced are interpreted to include all such modifications, permutations, additions and sub-combinations as are within their true spirit and scope. The applicant or applicants have attempted to disclose all the embodiments of the invention that could be reasonably foreseen. There may be unforeseeable insubstantial modifications that remain as equivalents. | An embodiment includes a drain pipe waste water closure protection device which allows passage of fluids through a drain into a pipe waste water closure and a waste water pipe while preventing backflow of fluid or gas from the waste water pipe and pipe waste water closure, as well as preventing evaporation of a water-containing pipe waste water closure located below the drain pipe waste water closure protection device in the waste water pipe. Embodiment drain pipe waste water closure protection devices are easily installed in existing or new drains. Embodiments have two radial disc seals which insure a strong seal between the drain pipe waste water closure protection device and the drain wall. Embodiments include a reinforcing band embedded below the radial disc seals which prevents failure of the radial disc seals.
Embodiments include a quadruple pressure accumulating seal which protects against the flow of gas or fluid from the waste water pipe. | 8 |
FIELD OF THE INVENTION
This invention relates generally to accessories for use in conjunction with quick-release hose couplings. More specifically, the invention relates to devices that improve grip and ergonomic function of annular, lateral displacement locking/unlocking collars used in conjunction with pneumatic and hydraulic hoses, including those commonly used in conjunction with pneumatic tools.
BACKGROUND OF THE INVENTION
Many types of rotating and reciprocating tools and machines are powered by air or other gasses flowing at high pressure. The high pressure air is delivered to the tool by means of a high pressure air line and the air line is coupled to the tools by means of a lockable, quick-release coupler. Typically, the coupler comprises a coupler nipple or stem, fixed on an end of a first air line and a coupler body, or coupling, fixed on an end of a second air line, The nipple and body are designed to cooperatively interact. The coupler body has an external annular collar or sleeve. The lateral movement of the sleeve along the long axis of the coupler body locks or unlocks the two hoses to each other and provides an airtight or watertight connection. The sleeve is laterally movable or slidable from a first locked position to a second unlocked position The sleeve is frequently biased toward the locked position by a coil spring so that the sleeve automatically closes. To couple the hoses, the nipple is inserted into the coupler body, displacing the sleeve from the first to second position thereby. Once the nipple is properly positioned within the coupler body, the sleeve returns from the second to first position, locking the two hoses and providing an air tight seal. To uncouple the hoses, the body is held in one hand, the sleeve is laterally displaced to the retracted, unlocked position with the second hand, and the hoses are separated. Many examples of such couplers are known in the art. See, e.g., U.S. Pat. No. 3,788,598. This type of coupler can also be adapted for use with high pressure fluid lines and are operated in a similar fashion. See, e.g., U.S. Pat. No. 4,596,272.
This type of coupler presents several operational problems. First, because the coupler diameter is relatively small, typically one-half to one and one-half inches, operators, particularly those with limited dexterity, have difficulty in sliding the coupling sleeve to the retracted position. Furthermore, the high velocity of gas or fluid moving through the coupler results in a sharp decrease in temperature—frequently below freezing. Since the coupler is typically metallic, the coupler itself becomes chilled, making manual operation of the coupler sleeve more difficult. Furthermore, pneumatic tools powered by the high pressure lines are frequently used outdoors, potentially in extremes of low temperature, exacerbating this problem. Similarly, users of such tool may have greasy or oily hands, making operation with two hands difficult and operation with one hand near impossible. Furthermore, in certain applications passage of hot gasses or fluids can cause the coupler to heat and this can make use of the coupler difficult and dangerous.
Another problem common to this type of coupler is that the coupler itself is sensitive to impact damage from being dropped repeatedly and care must be exercised to prevent dropping the coupler on a hard surface.
SUMMARY OF THE INVENTION
This invention describes a knob-like, lateral displacement assist collar device with a central open tube that is designed to fit around, and affix to the annular locking sleeve of a quick-release hose coupling. The device is designed to operate in combination with the locking sleeve and improve its operation. The device is contoured to ergonomically accommodate the hand grip of the operator, and facilitate one-handed operation of the locking sleeve by providing a secure purchase for the thumb of the hand that holds the coupler such that the sleeve can be laterally moved or retracted to release the coupled hoses. Typically, the collar is manufactured from rubber, silicone or similar soft plastic material that has impact shock absorbing characteristics and thereby provides protection against impact resulting from accidental dropping of the coupler, and thermal insulation to improve use under conditions in which the coupler is chilled or heated.
It is an object of this invention to provide a device that improves the one handed operation of the lateral displacement locking sleeve of a quick-release hose coupler.
It is a further object of this invention to provide a device that improves the one handed operation of the lateral displacement locking sleeve of a quick-release hose coupler when the coupler is above or below physiologic temperature.
It is a still further object of this invention to provide a device that absorbs the physical shock of impact resulting from accidental dropping of the coupler.
In accordance with the above objects and others, described herein, the lateral displacement assist collar device, for use in conjunction with quick-release hose couplers that have a laterally displaceable annular locking/unlocking sleeve, comprises a tube with an inner bore, an inner and outer side, and a first and second end with an interior region there between. This device is positionable and affixable upon the locking sleeve.
In an embodiment, the device is contoured such that the thickness from the inner to outer side of the tube is greater in the interior region than proximal to an end.
In another embodiment the device is permanently affixed to the annular locking sleeve.
In still another embodiment the device is removably affixed to the annular locking sleeve.
In yet another embodiment the device is composed of an elastic material that is radially stretchable such that the diameter of the inner bore is increased when the tube is radially stretched from a relaxed to a stretched position, said device being positionable around the annular locking sleeve when expanded to the radially stretched position, thereby gripably affixing to the sleeve after positioning.
DESCRIPTION OF THE DRAWINGS
FIGS. 1 -A&B are perspective views of the lateral assist collar.
FIG. 2 is a cross-sectional elevation of the lateral assist collar.
FIG. 3 is a cross-sectional elevation of the collar affixed to a quick-release hose coupler.
FIG. 4 depicts various contours of the interior region of the external side of the collar.
DETAILED DESCRIPTION OF THE INVENTION
The Quick-Release Coupler—Introduction
Pneumatic and hydraulic quick-release hose couplers are generally known and available. Hose couplers generally have two components—a coupler nipple which is attached to one hose end, and coupler body designed to receive the nipples which is attached to a second hose end. A generic quick-release coupler body is depicted in FIG. 3 . Typically, the body ( 4 ) has an annular sleeve ( 5 ) that can be laterally diplaced by hand. This activates a locking/unlocking mechanism within the body and this holds the nipple in place within the body.
A. Pneumatic Couplers. Pneumatic applications, such as connecting air tools, hoses or other implements to compressed air supplies generally use single shutoff couplings. They can be used with other gasses and low pressure fluids. The coupler body ( 4 ) contains the shutoff valve that is automatically opened when a mating nipple is inserted into the central orifice of the body, and is automatically closed when the nipple is removed. The coupler body is designed with an annular sleeve ( 5 ) that can be moved laterally along the long axis of the coupler body. The sleeve is associated with the locking mechanism of the coupler such that the nipple is locked in place in the coupler body when the sleeve is at a first extreme of its movement along the coupler body and the nipple is unlock and removable from the coupler body when the sleeve is at the second extreme of its movement. The sleeve can be biased toward the locked position by a spring mechanism.
Coupler bodies ( 4 ) can be designed in two ways. In the first design, the coupler body can automatically receive and lock the mating nipple in place when the nipple is inserted into the coupler orifice. Release of the nipple from the coupler body requires retraction of the annular sleeve ( 5 ). In the second design, the sleeve ( 5 ) of the coupler body ( 4 ) must first be retracted in order to receive the nipple and then returned to the unretracted position to lock the nipple in place.
Pneumatic couplers are available in any size. Standard sizes accommodate hoses that range from ⅛ inch to ¾ inch diameters. The diameter of the sleeve of the coupler body generally ranges from ½ inch to 2 inches. Coupler bodies and nipples are designed to attach to hoses in several ways including male and female threading, and hose barbs.
B. Hydraulic Couplers. Hydraulic couplers generally fall into one of two groups, based on the valving of the coupler—double shutoff or straight through. Double shutoff couplings are useful when it is important to minimize fluid loss upon disconnection. Both the coupler body ( 4 ) and the nipple contain shutoff valves that open automatically when the body and nipple are connected, and close automatically when the two halves are separated. Straight through couplings have no valves in either half, thereby maximizing flow, minimizing pressure drops and facilitating cleaning. Fluid flow must be shut off at a distal location before connecting or disconnecting. As with pneumatic couplers, the coupler body ( 4 ) has an annular sleeve ( 5 ) that displaces laterally and serves to operate the locking mechanism that holds the nipple in place.
Generally available sizes accommodate hoses that range from ⅛ inch to 1 inch. The diameter of the sleeve of the coupler body ranges from ½ inch to 4½ inches. Both hydraulic and pneumatic couplers are commercially available from a variety of US manufacturers. Common brand names include PFC from Parker Hannifin Corp., Tru-Flate, Industrial, ARO, Lincoln, Schrader, C J, and D M.
The Lateral Displacement Assist Collar
This invention describes a knob-like tube or collar that assists in the lateral displacement of the locking sleeve of a quick-release hose coupler. The collar comprises a tube with a central internal channel or bore, designed to surround and closely fit around and adhere to the annular sleeve of the coupler body (FIG. 3 ). The exterior of the tube is contoured to easily fit in the hand of the user. Features are provided on or integral to the external surface of the collar, in the region between the two ends of the tube, providing purchase for the thumb of the hand holding the connector. These features allows the user to grip the coupler with one hand and more easily operate the annular sleeve of the coupler with the same hand.
FIGS. 1 & 2 depict a design embodiment of the collar. The bore ( 1 ) is designed to accommodate a particular size of coupler. The interior region ( 2 ) of the external side of the collar is thicker than at least one end ( 3 ) of the collar, providing a contoured ridge for purchase of the user's thumb.
The coupler is typically made of metal, usually brass or steel. Consequently, couplers are good conductors of heat and, are heated and cooled to extremes of temperature during, and as a result of, use. The collar of this invention can be fabricated from a variety of materials that provide excellent thermal insulation—e.g. silicone, rubber and plastics. This quality further facilitates the operation of the coupler sleeve by insulating the operator from the temperature extremes of the coupler itself
These same materials also provide impact insulation for the coupler. Damage to quick-release couplers from the impact of being repeatedly dropped is one of the greatest contributors to the use durability of these couplers. Therefore, the instant invention extends the operational life of the coupler.
A. Design In an embodiment, the collar is designed to be placed on couplers as an after-market accessory. The collar is fabricated from an elastic material such as silicone, plastic or rubber. The collar is made in a variety of sizes such that the diameter of the central bore ( 1 ) is approximately the diameter of the sleeve upon which the collar will be used. The diameter of the central bore ( 1 ) is flexibly expanded as the collar is pushed upon sleeve and the collar is tightly positioned upon the sleeve such that the elasticity of the collar provides a frictional fit adequate to keep the collar registered to the sleeve during operation.
In a preferred embodiment, the collar is permanently affixed to the sleeve during manufacture of the coupler, using adhesives compatible with both the metal coupler and collar. Such adhesives are well known in the industry and readily available.
The overall size of the collar will vary depending on the size of the coupler for which the collar is designed. The largest diameter of the collar ranges from 1 inch to 5 inches. One inch collars are designed to be used with ⅛ inch couplers and 5 inch collar are designed to be used with 4.5 inch couplers. Typically, collar diameter will ranged from 1.5 to 2.5 inches.
The thickness of the collar itself ranges from 0.2 inches in the thin body ( 3 ) of the collar near an end, up to 1 inch in the meatiest part of the largest collars ( 2 ). The thickness of the interior region is proportional to the overall size of the collar.
The external surface of the collar is designed to fit comfortably in the hand of the user. The region between the two ends of the bore, i.e. the internal region ( 2 ), is contoured to provide grip and purchase for the thumb of the hand holding the coupler. Several contour profiles provide adequate purchase. Some of the envisioned profiles are shown in FIG. 4 . It is desirable to have a profile that is thicker in a portion of the internal region ( 2 ) than at at least one end ( 3 ) of the collar. The collar profile shown in FIG. 4D is the best mode. The profile in FIG. 4B is another preferred contour.
B. Fabrication
The collar can be fabricated from a variety of materials. In an embodiment, the collar is made from natural rubber. The bore is drilled to specification and the peripheral contour is turned on a lathe.
In another embodiment, the collar is fabricated from silicone, such as Dow Corning #795®. The material is applied to the collar, molded to the desired shape, and allowed to set at room temperature. In this embodiment, the collar is permanently affixed to the sleeve. In an alternative embodiment, the 795 material is molded around a form and removed from the form after curing. The form may be pretreated with a releasing agent.
In a preferred embodiment, the collar is fabricated in an injection molding system using a polymer resin, such as a plastic manufactured by General Electric. Cycolac® ABS resin is the resin of choice, however, other resins could be substituted. The process is well known in the industry.
EXAMPLES
Example 1
An after market lateral assist collar is fabricated to accommodate a pneumatic coupler with a ¼ inch body. The coupler is 1.95 inches overall length and the coupler sleeve is about 0.9 inches. The diameter of the coupler sleeve is 0.94 inches. The collar is fabricated from Cycolac® ABS resin by injection molding process. The overall length of the collar is 0.75 inches. The central bore is 0.8 inches, however, due to the elasticity of the material, the collar can be expanded to fit around the sleeve. Generally the collar is 0.25 inches thick; however, there is an external ridge in the interior region of the collar. The thickness of the collar at the ridge is 0.50 inches. The overall diameter at the ridge is 1.8 inches. The external profile of the collar is similar to that shown in FIG. 4 D.
In the foregoing, the present invention has been described with reference to suitable embodiments, but these embodiments are only for purposes of understanding the invention and various alterations or modifications are possible so long as the present invention does not deviate from the claims that follow. | The present invention discloses a knob-like collar device adapted to fit securely around the lateral displacement locking sleeve of a quick-release hose coupler. The device promotes one-hand operation of the coupler by providing purchase and grip for the thumb of the hand holding the coupler thereby facilitating the lateral displacement of the locking sleeve. The device is particularly useful when the coupler is very cold, a condition that commonly results from the high velocity passage of fluids or gasses through the coupler. The device also absorbs mechanical shock resulting from the accidental dropping of the coupler on a hard surface, thereby protecting the coupler from damage. | 5 |
This is a continuation of copending application Ser. No. 07/534,159 filed on Jun. 6, 1990 (now abandoned) which is a continuation of Ser. No.: 07/457,359 filed Dec. 12, 1989 (now U.S. Pat. No. 5,000,307 granted Mar. 19, 1991) which is a continuation of Ser. No.: 07/299,944 filed Jan. 6, 1989 (now abandoned).
FIELD OF THE INVENTION
The present invention relates to a method and apparatus for the conveying of material using two spiral conveyors.
DESCRIPTION OF PRIOR ART
A need exists in many connections for the conveying of material, e.g., of bulk material, and not only of homogeneous goods but also of material which includes components of varying size, density, elasticity, moisture etc. Examples of such material are coal, coke, grain, refuse, wood chips etc. In many applications it is also necessary to convey articles from a lower level to a higher one. For reasons of space it is frequently important for the conveying to take place substantially vertically or along a steeply inclined path.
The type of conveyors appropriate in the abovementioned connection are scraper conveyors, screw conveyors or belt conveyors etc. Such conveyors are then arranged in inclined position and lift the material to the desired higher level.
In applications where screw conveyors are used a spiral-form thread (screw) provided with a center shaft is present which is enclosed in a casing wherein the thread (screw) rotates. The arrangement represents a rigid and a heavy construction which even for relatively short conveying distances is supported at least at both its ends. The unloading, therefore, except where very short screws of a maximum length of 2-3 m are concerned, has to take place through an opening in the sides of the casing.
Conventional screw conveyors provided with a mechanical shaft which are used for vertical or steeply inclined conveyors have a number of well-known disadvantages, e.g.:
They have low efficiency and have to operate at high speed, normally 300-500 rpm.
The high speed causes high energy consumption and as a rule leads to rapid wear.
Unloading is rendered difficult and requires a large space, since it has to be done sideways.
The rigid construction in fixed supports and the limited space between threads, shaft and casing wall means that the material easily jams.
The rotating shaft renders impossible the transport of material which can twist itself round the shaft.
Moist smearing material tends to cake onto the inner wall of the casing and continuously reduce the "clearance" between screw and casing. Thus it is well-known for the rotation of the screw to be rendered difficult or hindered by this phenomenon.
The aforesaid disadvantages of vertical screw conveyors have the effect that conveyors for the transfer of material between different levels are built with a relatively small angle of inclination (normally 15°-45°) which naturally means a larger space requirement. The consequence are large buildings with high investment and operating costs associated therewith.
An application which generally occurs is the unloading to transport containers when the goods have to be lifted by at least 2 m. An inclined conveyor has the disadvantage that as a rule it makes it difficult to fill a container completely, since the conveyor has a limited unloading area. For bulk material the containers often have base dimensions 2×6 m. Likewise, it will be appreciated that the problem is accentuated when e.g. at a transloading station several containers placed adjoining one another are to be filled.
Generally it is so, that in a screw conveyor provided with a mechanical shaft--or in a spiral conveyor without a mechanical shaft--the conveying takes place in that the material transported rests against, and slides along, a driving surface of a screw (or of an endless scraper) which forms an oblique angle with the direction of conveying. If this relative movement between the material and the driving surface fails to take place, that is to say if the material sticks to the screw, no conveying of material whatever occurs in the direction towards the discharge end of the conveyor, but the material rotates around with the screw in a circular movement. To insure conveying towards the discharge end of the conveyor it is necessary, therefore, for the movement of the material in the circumferential direction of the screw to be Slowed down so that the screw during its rotation pushes the material towards the discharge opening. In other words, in order that the material should be conveyed in the direction towards the discharge end, the sum of the friction forces between the goods transported and the rotating screw must be less than between the goods and the stationary casing.
It is evident that in a vertical or steeply inclined conveyor, which comprises a casing enclosing a screw provided with shaft, as a rule the forces with which the material is pressed against the casing will be less than the forces with which the material adheres to the screw. If no special measures are adopted to compensate this relationship, the result will be that the friction forces between the goods transported and the vertical casing will be smaller than the friction forces between the goods and the rotating means. To establish the preconditions for the transport of the material towards the discharge end, consequently, the friction between the material and the casing has to be increased, In accordance with prior art this is accomplished by choosing a high speed for the rotation of the screw and, throwing, with the help of centrifugal force the material against the casing of the conveyor, Vertical screw conveyor operate therefore, as already mentioned, at a high speed with the associated disadvantages in the form of high power consumption, rapid wear and low filling ratio and/or efficiency.
To a vertical conveyor, which includes a casing and a screw equipped with a shaft located in the casing, the material which is to be lifted is supplied as a rule by means of a short screw which through an opening in the casing projects the material towards the center shaft of the screw. As a result the material at least partly fills the feed-in zone of the conveyor and is forced out towards the inner boundary surface of the casing, thus creating the pre-conditions for the conveying of the material to the upper part of the conveyor and the discharge opening located there. However, the center shaft on the vertical conveyor of the conventional screw conveyor constitutes an obstacle to a good filling of the feed zone though, and besides it is a fact that the total surface of the threads and the shaft of the screw together with the ductlike shape of the space between threads cause the material to stick to the screw and rotate with it which means that no conveying of material in the direction towards the discharge end is taking place. In addition to hindering the filling of the feed section of the screw conveyor and the increase of the friction forces between material and screw which the center shaft of the rotating screw brings about, it also renders impossible the conveying of material which can be twisted round the shaft and limits, moreover, greatly the conveying of material in large pieces.
It has been known previously that for the conveying of, among other things, the type of materials mentioned earlier in a horizontal plane or at a relatively small angle to it (maximum 30°-40°) a spiral-form thread without mechanical center shaft may be used, the thread rotating in a casing. The spiral thread is supported then only at one end of the spiral. The use of such shaftless spiral thread eliminates a number of the disadvantages of the conventional screw conveyor. A conveyor with shaftless spiral thread makes possible extremely light and compact constructions and, moreover, is appreciably more capacious than the "screw conveyor", as it lacks the obstacles which the center shaft and bearing constitute. This makes it possible to make use of appreciably higher filling ratios during transport and to operate with the same dimensions and transport capacity as a screw conveyor with shaft but at considerably lower speed. It may be used trouble-free for entangling or smearing goods or for goods of varying piece sizes. Moreover, it operates at low speed which ensures long operating life, high reliability, low maintenance cost and low power consumption.
SUMMARY OF THE INVENTION
The present invention seeks to provide a method and apparatus in which the aforementioned requirements are met, the disadvantages described are eliminted and where the advantages described in the preceding section of a conveyor with shaftless spiral thread are maintained on conveying material from a lower to a higher level at steep inclination or substantially vertically. In accordance with the invention this is achieved with a method and an apparatus which control the magnitude of flow in two conveyers with shaftless spiral threads.
In an embodiment of the invention a third upper conveyor (combination of shaftless spiral and track) is arranged which comprises a shaftless spiral without mechanical center shaft, where the spiral is located inside a means comprising a track whose cross-section in its lower part is of substantially circular shape with a diameter slightly exceeding the diameter of the spiral so as to allow the spiral to rotate in the track while being in contact with the inner boundary of the track. The third upper conveyor is fed by the second conveyor with material from underneath through an opening in the track. By rotating the third conveyor around the geometric axis of the discharge part of the second conveyor the discharge part of the third conveyor is adjusted to the desired direction.
DESCRIPTION OF THE FIGURES OF THE DRAWING
The invention is described in more detail in connection with the figures of the drawing, where
FIGS. 1a, 1b show a section in the vertical plane through an arrangement in accordance with the invention in alternative embodiments,
FIG. 2a-e show sections A--A, B--B, C--C, D--D and E--E in FIG. 1a and FIGS. 1b, respectively,
FIGS. 3a, 3b show the distribution of the material conveyed in the lower, substantially horizontal part of the arrangement in accordance with FIG. 1a and 1b, respectively,
FIG. 4 shows a section in the vertical plane of an embodiment of the arrangement with a substantially horizontally directed upper conveying means and
FIGS. 5a, 5b show the arrangement in accordance with FIG. 4 seen from above.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
FIGS. 1a and 1b illustrate the invention in an embodiment which shows the main construction and function of the invention. In the Figures will be found a first conveyor or combination 1 comprising a first tubular casing 10 and a first shaftless spiral 11, forming a screw-blade 57 with a boundary (edge) 54 facing towards the center and a boundary (edge) 64 facing away from the center, located in the casing. The casing as a rule has a substantially horizontal orientation. At one end the casing forms a feed section 19 provided with one or more feed openings 12 which as a rule connect to an upwardly directed feed drum or feed hopper 13, A motor 14 drives the shaftless spiral 11 via a change-gear and bearing assembly. The other end of the casing constitutes the discharge section 16 of the combinations with its discharge opening 17. The spiral is solely supported in conjunction with the change-gear and bearing assembles while the end 51 of the spiral which is located in the discharge section is entirely free. As a consequence of the elasticity of the spiral in the radial direction, the boundary 64 of the spiral facing away from the center rests against the casing in the base area of the latter except nearest the change-gear and bearing assembly 15.
In the discharge section the casing always has a substantially circular cross-section and surrounds the shaftless spiral with slight play. In the embodiment shown in FIG. 1b a substantially cylindrical body 50 is arranged in the discharge section 16 and located in the region of the geometric center axis of the spiral. The body is located in the central passage of the spiral and is surrounded by the spiral, In this embodiment too the spiral terminates with a free end 51 in the discharge section 16.
In FIG. 1a and 1b can be found also a second conveyor or combination 2 of a construction substantially corresponding to that described above for the first combination. The second combination thus comprises a second casing 20 and a second shaftless spiral 21 located therein forming a screw blade 58 of, as a rule, substantially rectangular cross-section and a boundary (edge) 55 facing towards the center and a boundary (edge) 65 facing away from the center. The longitudinal axis of the casing in the second combination is of a substantially vertical orientation or forms a relatively large angle with the horizontal. As a rule the angle exceeds 50°, preferably 70° and is frequently 90°. In the lower section of the combination 2 will be found a feed section 29 with a feed opening 22 which overlaps the discharge opening 17 of the first casing. The spiral is driven by a motor 24 via a change-gear and bearing assembly 25 located in the lower section of the combination below the region of the feed opening 22. The speed of rotation of the spiral is adjustable to the desired value by changing the gear ratio and/or the motor speed. At the other end of the casing can be found the discharge section 26 of the casing with a discharge opening 27 which in the embodiment shown is located in the axial direction of the shaftless spiral. The shaftless spiral terminates in the discharge section with a free end 52.
In the first combination in the region of the discharging section 16 the geometric center axis of the spiral and/or a central axis of the discharge section are directed towards the geomtric center axis of the spiral 21 of the second combination. The area of the cross-section of the discharge opening 17 of the first casing 10 as a rule corresponds substantially to the area of the cross-section of the receiving casing 20, at least in the region of the feed section of the receiving casing, the two casings as a rule being tightly joined to one another. In some embodiments the discharge opening 17 is smaller. The free end 51 of the first spiral as a rule terminates closely adjoining the region through which passes the screw-blade 58 of the spiral 21 of the second combination.
Seen in axial direction of the first casing 10 the first combination 1 of shaftless spiral and casing is divided into a charging zone 18a, a discharge zone 18c which terminates with the discharge opening 17 and in some embodiments with a conveying zone 18b therebetween.
In FIG. 2a-2c are shown examples of the cross-sections of the respective zones. As a rule the cross-section of the casing in the conveying zone of the first casing is chosen to be U-shaped whereas in its discharge zone 18c it is as a rule circular. The casing encloses the spiral with slight play in the discharge zone. In applications where goods in large pieces are included in the material which is to be conveyed, the play is chosen to be relatively large so as to avoid any danger of jamming. In certain applications the casing has a substantially circular cross-section in the charging zone as well as in the discharge zone, the size of the cross-section of the respective zones as a rule being in agreement.
FIG. 2d shows an embodiment of the casing 20 of the second combination wherein the casing along its inner boundary surface is provided with at least one riblike means 23 which extends substantially in the longitudinal direction of the casing. The casing encloses the spiral 31 with relatively slight play.
FIG. 2e shows an alternative embodiment of the casing 21 of the second combination 2 where the cross-section of the casing is of an irregular shape and as a rule has one or several relatively sharp corners 28, as indicated in the figure.
The riblike means in FIG. 2d and the irregular shape or corners respectively in FIG. 2e serve to increase the friction between the respective casing and the material which abuts against the same.
FIG. 3a and 3b show how during the conveying the material 40 in the first combination in the region adjoining the discharge opening 17 of the casing fills substantially all the available space in the discharge section 16 of the combination. The cylindrically shaped body 50 according to the embodiment in FIG. 1b to a certain extent hinders material in the feed section of the second combination from falling back into the discharging section of the first combination.
In FIG. 4 is shown an embodiment wherein the above described combinations 1 and 2 are completed by a third conveyor or combination 3 which also comprises a casing 30 and arranged in the casing is a rotating shaftless spiral 31 forming a screw-blade of as a rule substantially rectangular cross-section and with a boundary (edge) 56 facing towards the center and a boundary (edge) 66 facing away from the center. The spiral is driven via change-gear and bearing unit 35 by a motor 34 placed as a rule in conjunction with the feed end 39 of the casing, The speed of rotation of the spiral is adjustable by control of the speed of the motor and/or alteration of the gear ratio in the change-gear and bearing unit 35. The third combination is arranged in conjunction with the discharge section 26 of the second combination and is connected to the casing 20 of the second combination via a coupling and/or bearing unit 60 of circular cross-section. A joint 33, likewise of circular cross-section, encloses the discharge section 26 of the second casing and the third combination is rotatably adjustable in relation to the discharging section of the second casing, The joint in its section located adjoining the third casing forms a feed opening 32 to the third casing, this feed opening constituting a downwards facing opening in the third casing. In the region nearest the feed opening rotates the free end 52 of the second spiral as a rule closely adjoining the path or track of the screw-blade of the third spiral, As a consequence of the elasticity of the spiral in the radial direction the boundary 66 of the spiral facing away from the center rests against the casing in the bottom region of the latter except nearest the change-gear and bearing unit 35. The material which is conveyed through the discharge opening 27 of the second casing passes through the joint 33 and from underneath into the third casing through its feed opening.
The casing of the third combination is provided in its discharge section 36 with one or more discharge openings which are located one after the other in the longitudinal direction of the casing. As a rule one discharge opening 37 is located in the axial direction of the casing, whereas one or more discharge openings 38 form openings in the casing facing downwards. The shaftless spiral 31 terminates in the discharge section of the casing with a free end 53 which is facing towards the discharge opening 37 located in axial direction of the casing. FIG. 4 shows an embodiment wherein the first combination is provided with a cylindrical body 50. In certain applications the first combination 1 has the construction shown in FIG. 1a, that is to say the combination lacks the cylindrical body 50.
As shown in the FIGS. 5a, 5b the discharge section 36 of the third combination is movable along periphery of a circle when the third casing is turned in the bearing 60. As a result the third combination is adjustable as required to deliver material to containers placed arbitrarily around the arrangement. The dispersed locations of the discharge openings mean that each discharge opening is moved along the periphery of a circle 5a-5b specific for the discharge opening making it feasible to obtain on unloading to a receiving container 4 a good distribution of the goods which are supplied to the container.
Material which is supplied to the first combination 1 through the feed opening 12 in the casing 10 is conveyed by means of rotation of the spiral 11 in the direction towards the discharge opening 17 of the first casing. As is evident from FIGS. 3a and 3b a certain accumulation of material is taking place in the region adjoining the discharge opening 17 of the first casing. As a result the material after it has passed out through the discharge opening of the first combination and into the casing 20 of the second combination 2, will substantially fill the space of the receiving casing in the region of the feed opening of the casing, since the relatively thin screw-blade 58 of the shaftless spiral 21 in the second casing in reality does not constitute an obstacle to the conveying of the material. The material passes into the second casing underneath as well as above the screw-blade 58 of the rotating spiral 21. Material supplied in the region of the feed opening 22 of the second casing forms material bridges with material passing in as well as with material already present in the second casing. As a result action of forces arise between the screw-blade 58 of the shaftless spiral and the material which is present in the casing and between material acted on by the screw-blade and material which surrounds the material acted on by the screw-blade, which also refers to material adjoining the inner boundary of the casing. The surrounding material, and to a certain degree also the material directly acted on by the spiral, abut against the inner boundary of the casing and are hindered by the friction effect from accompanying the spiral in its rotation. This brings about a relative movement between the screw-blade 58 of the second spiral and the material. Now, when the spiral thread passes through the material, it is lifted up accordingly, and subsequently, after the spiral has passed by, it falls back towards the lower end of the casing. During the period when the material is lifted up by the spiral, however, material is supplied from the discharge section 16 of the first casing into the cavities which are formed underneath the material lifted up by the thread in the second casing, at the same time as the friction-promoting bridges mentioned are formed, underneath as well as above the screw-blade of the spiral thread, between material abutting against the screw-blade and surrounding material. Through successive rearrangement and injection of material from the first combination, the whole space in the casing of the second combination is thus gradually filled with material.
One precondition for the material to be lifted is that the capacity of the material to accompany the spiral in its rotation has to be reduced, and this can be achieved provided the distribution of friction forces indicated in the foregoing passage exists. It thus has been found surprisingly that the supply of material provided by means of the first spiral, and which in the first instance goes into the cavities formed underneath the rotating thread of the second spiral, establishes friction forces between material bodies and between the material and its environment (including the inner boundary of the casing) of a magnitude and direction which causes the material in the casing of the second combination to moves at a slower speed in the direction of rotation of the spiral than the spiral itself and, at least in certain parts, to be completely slowed down. As a result a substantially coherent material body is formed from the bottom of the casing, and this material body is moved towards the discharge end of the casing. It has been found surprisingly that when supply of material through the discharge opening 17 of the first casing ceases, the movement of material in the vertical direction also stops, since on rotation of the second spiral only a rearrangement of the material takes place, and, by and large, no vertical conveying of the same, is taking place.
The shaftless spiral of the second combination is dimensioned so as to have a pitch, a blade width, a cross-section and/or a speed of rotation of the spiral which causes the transport capacity of the second combination exceed the conveying capacity to which the first combination has been adjusted. As a result a compression of material following accumulation of material in the discharge section 16 is avoided. Such a compression could lead to great mechanical stresses on the casing as well as spiral and could lead to these means having to be overdimensioned at least in the transition region in order to obtain the necessary mechanical stability. As a rule the conveying capacity of the second combination is regulated in each application by means of the speed of rotation and/or the thread pitch of the second spiral.
As an example of suitable data for the second combination the spiral may be rotated at a speed of approx. 30-80 rpm, preferably 40-50 rpm, the spiral may have a diameter of approx. 150-400 mm, preferably approx. 200-300 mm, the ratio between the pitch of the spiral and its diameter may be greater than approx. 0.30, as a rule greater than aprox. 0.50 and preferably greater than approx. 0.75, and the width of the screw-blade may constitute approx. 20-40%, preferably approx. 25-35% of the spiral diameter. The width of the screw-blade here refers to the extension of the screw-blade in a direction corresponding substantially to a radial direction from the geometric center axis of the spiral. For certain materials extremely large thread pitches may be used, for example, a thread pitch of the order of magnitude of the outer diameter of the spiral. By using a large thread pitch the spiral is stiffened.
In the embodiments where the discharge section of the second casing 20 is connected to a subsequent combination of casing 30 and spiral 31 it has been found surprisingly to be possible to allow the second casing as described above to open from underneath into the casing of the third combination (see FIG. 4), that is to say to allow the casing of the third combination to lack a boundary surface in the region of the discharge opening of the second casing. The reason is that, surprisingly, it has been found that on rotation of the third spiral around its axis, and on feeding of material into the third casing through a feed opening arranged as described above, the material present in the second combination and in the joint hinders the material introduced into the third casing from falling back down into the second casing, as a result of which on rotation of the third spiral the supplied material is conveyed in the direction towards the discharge end of the third casing.
In FIG. 5a is shown how the arrangement co-operates with two receiving tanks 4, whereas FIG. 5b shows how the arrangement equally simply co-operates with several, for example four, such receiving tanks. Because the combination 3 is turnable, and as a rule is provided with a number of unloading openings, it will be evident that it is easy to achieve good filling even with material which has steep drop surfaces. Owing to the combination 3 being provided with a spiral capable of pushing and a spiral end free at the discharge end with axial discharge facilities, it is also evident that in certain applications the tanks are filled by the material being pressed out into the tanks. The arrows A in FIG. 5a, 5b mark the path of movement of the material.
The casing cross-section in the third combination is preferably U-shaped. In applications where the material is to be pressed out into the tanks a substantially circular cross-section is chosen as a rule, at least in the discharge section of the arrangement.
In the above description it is specified that the first combination 1 comprises a spiral thread 11 lacking a mechanical central shaft. It is the task of the first combination to constitute the feeding means for the supply of material into the casing 20 of the second combination 2 through the feed opening 22 of the latter. It will be obvious to those skilled in the art that the invention embraces the possibility, especially when the first combination is short, to allow the first spiral thread to be a conveyor screw provided with shaft. The essential point for the effect aimed at is that the first spiral thread terminates closely adjoining the region through which passes the screw-blade 58 of the spiral 21 of the second combination.
The above detailed description made reference only to a limited number of embodiments of the invention, but it will be readily appreciated by those skilled in the art that the invention embraces a great number of embodiments within the scope of the following claims. | A conveying apparatus for particulate material comprises a first conveyor combination including a first casing and a first shaftless spiral drive element, a second conveyor combination coupled to said first conveyor combination and including a second casing and a shaftless spiral drive element; and a elongated body coaxially arranged with respect to the first shaftless spiral. | 1 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] Not applicable.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] Not applicable.
BACKGROUND OF THE INVENTION
[0003] 1. Field of the Invention
[0004] The present invention generally relates to an interface control between one or more input/output (“I/O”) devices and a host system. More particularly, the invention relates to interface logic between I/O devices and a host system that provides a single communication link to the host system. More particularly still, the invention relates to a universal control circuit that provides a single communication link to a digital host system for a plurality of I/O devices and a display for showing information provided by the host system. The invention also relates to the synchronization of volume level visual indications on the display and a separate television monitor.
[0005] 2. Background of the Invention
[0006] Consumers today have numerous types of devices at their disposal-personal computers, televisions, VCRs, DVDs, camcorders, cameras, cable set top boxes, satellite receivers, and the like. Information is available to consumers over a wide variety of media. Television programming, for example, is available over conventional wireless broadcasting, cable, and satellite. Static information is readily available in the form of data transmissions over the Internet, and Internet connections may be over standard telephone lines using modems, dedicated high speed land lines, satellite, and digital transmissions at higher frequencies on standard telephone cables, to name a few. Consumers thus have a wealth of information available to them in various formats and requiring different devices to receive, process and view the information.
[0007] In the face of the multimedia explosion, the “set top box” has been developed to simplify a user's access and control to the multimedia-based information. A set top box connects typically to a television monitor, an Internet medium (e.g., a DSL telephone line), and a television programming channel (e.g., a cable TV connection). A wireless keyboard can be provided to permit a user to operate the set top box. The set top box itself includes a host system typically comprising a central processing unit (“CPU”), memory, a fixed disk storage device, a floppy disk drive, and possibly a DVD player or other types of devices as desired. Using the wireless keyboard to control the set top box, a user can watch television programing or use the television and set top box together as a computer to perform conventional computer processing tasks, such as word processing, email, and the like. In short, the set top box and television effectively can perform the same functions as a television and separate computer system. The set top box can operate as a conventional computer system or as a consumer electronics device (e.g., DVD player). It is highly desirable in the consumer electronics market, including set top boxes, to make the equipment as “user friendly” and robust as possible. To make it easier on the user to operate the set top box, the keyboard, as noted above, may have a wireless link to the set top box. The wireless link may be a radio frequency (“RF”) or infrared (“IR”) link between the keyboard or handheld remote controller and the set top box. Other devices, such as a mouse, may also have an RF or IR link to the set top box. Having wireless links between the control devices the user operates and the set top box eliminates annoying cables draped across the room in which the user has the television and set top box (e.g., living room or bed room).
[0008] To further make operation of the set top box as user friendly as possible and in case of a battery failure or damaged remote control, one or more controls may be placed on the front panel of the box itself. Such controls may be used to operate the set top box's DVD player, and, accordingly, the buttons may be for functions such as “stop,” “play,” “pause,” “fast forward,” and the like. These types of buttons should be as easy to use as the comparable buttons on a conventional VCR.
[0009] The set top box also includes a host system board on which the CPU, memory and other digital electronic components are mounted. To protect the digital signals on the host system board from outside RF interference, the host system board preferably is contained within a metal housing. The metal surface of the housing acts as a shield against the intrusion and containment of electromagnetic interference. Although desirable to shield the digital electronics, the metal housing presents a problem for the wireless communication to the keyboard, remote control, or other peripherals. Both devices must have an antenna to provide the communication link. The RF antenna or IR receiver mounted in the set top box, however, cannot be located inside the metal housing, otherwise the metal housing will preclude RF signals from the keyboard from reaching the set top box antenna, and vice versa.
[0010] A solution to this problem is to locate the antenna outside the metal enclosure. One suitable solution would be to provide the metal set top box with an electromagnetically transparent front panel (i.e., one that is made from a material that does not interfere dramatically with the RF link). The set top box's RF antenna can then be mounted on the inside of the front panel. The front panel also provides a convenient location to mount the various buttons noted above (play, pause, etc.). All of the controls, however, must be electrically coupled in some way to the host system board located inside the metal enclosure. Routing numerous electrical lines from potentially numerous controls through openings in the metal enclosure tends to decrease the ability of the metal housing to adequately shield the electronics. Accordingly, a solution to this problem is needed.
[0011] Also, it would be desirable to provide a consumer electronics device, such as a set top box, with a display that includes controls (e.g., buttons, knobs) that can control the presentation of multimedia and provide a visual indication of changes in settings on a local display and/or television monitor. For example, if the consumer electronics device includes a volume knob for controlling the volume level of sound associated with a video, it would be desirable for the consumer device to provide an indication of the change in volume level locally and/or on the television monitor.
BRIEF SUMMARY OF THE INVENTION
[0012] The problems noted above are solved in large part by a consumer electronics device that includes a universal control logic unit to interface a plurality of input controls, a display and an antenna to a host system via a bus. The host system is located within a shielded enclosure, while the remaining components (e.g., input controls, display, antenna, universal control logic) are located outside the shielded enclosure. Because a single bus preferably is used to interface the various input/output components located outside the shielded enclosure to the shielded host system, the host system can be more easily and effectively shielded than if numerous separate electrical lines and busses were used to directly connect the various input/output devices to the host system.
[0013] An embodiment of the invention is in the context of a “set top” box which couples to a television monitor, a pair of speakers and other multi-media devices. The set top box also includes a mass storage device, a DVD drive and other components as desired. The input controls and display preferably are located on the front panel of the set top box. The front panel preferably comprises a material through which wireless signals (e.g., radio frequency) can propagate. Behind the front panel is a metal enclosure which houses the host system. The universal control logic is located within the interstitial space between the metal enclosure and the front panel. In the context of a set top box, the input controls may be used for such functions as “play,” “stop,” “fast forward,” and the like. A volume knob also is provided on the front panel to control the level of sound to the speakers.
[0014] With the structure described herein, the universal control logic circuit can accommodate input and output devices having varying types of electrical interfaces. The universal control logic provides a single common interface to the host system. The host system preferably responds to user activation of the input controls and generates the information to be shown on the display.
[0015] The universal control logic preferably connects to the host system via a universal serial bus (“USB”) and preferably includes a USB hub, a USB interface circuit and a microcontroller. The input/output devices connect to general purpose input/output pins on the microcontroller. Status flag registers internal to the microcontroller are associated with each of the input and output devices. Whenever a user activates an input device (as detected by the microcontroller), the microcontroller sets the status flag associated with the activated input control. The microcontroller then alerts the host system over the single bus connection that a control has been activated and the host system determines which control was activated and performs the function associated with that particular control.
[0016] These and other advantages will become apparent upon reviewing the following description and drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] For a detailed description of the preferred embodiments of the invention, reference will now be made to the accompanying drawings in which:
[0018] [0018]FIG. 1 shows a block diagram of a set top box of the preferred embodiment;
[0019] [0019]FIG. 2 shows the front panel of the preferred set top box;
[0020] [0020]FIG. 3 shows a block diagram of an interface control circuit including a universal control logic unit;
[0021] [0021]FIG. 4 shows a block diagram of the universal control logic unit of FIG. 3;
[0022] [0022]FIGS. 5 and 6 show preferred methods illustrating the operation of the set top box and, in particular, the universal control logic;
[0023] [0023]FIGS. 7A and 7B illustrate the operation of the volume control on the set top box; and
[0024] [0024]FIG. 8 illustrates synchronizing dual volume level indicators on the set top box and a television monitor.
NOTATION AND NOMENCLATURE
[0025] Certain terms are used throughout the following description and claims to refer to particular system components. As one skilled in the art will appreciate, different companies may refer to a component by different names. This document does not intend to distinguish between components that differ in name but not function. In the following discussion and in the claims, the terms “including” and “comprising” are used in an open-ended fashion, and thus should be interpreted to mean “including, but not limited to . . . ”. Also, the term “couple” or “couples” is intended to mean either an indirect or direct electrical connection. Thus, if a first device couples to a second device, that connection may be through a direct electrical connection, or through an indirect electrical connection via other devices and connections.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0026] The following description describes the preferred embodiment of the invention in the context of a set top box. However, it should be noted that the principles described herein are not limited to just set top box technology. In general, the apparatus and methods described herein can be applied to numerous types of consumer electronics and computer devices.
[0027] Referring now to FIG. 1, set top box 100 constructed in accordance with the preferred embodiment generally includes an enclosure 102 , a front bezel member 118 and various electrical and mechanical components. As shown in the exemplary embodiment of FIG. 1, such components may include a host control system 110 , a mass storage device 113 , a universal control logic unit 116 , a video device (e.g., DVD) 126 , and various controls 120 and 130 . Host system 110 preferably couples to the mass storage device 113 , universal control logic unit 116 , and DVD 126 . One or more connectors 134 coupled to host system 110 may also be provided if desired. Host system 110 also provides a video and/or audio interface connection 106 to a television monitor (not shown). As such, interface 106 may comprise a video interface and right and left audio channels. The television interface may be the well-known NTSC standard or any other suitable television interface now known or later developed and used anywhere in the world. One or more audio speakers (not shown) can be coupled to the host system 110 via one or more audio connections 112 .
[0028] Enclosure 102 in the preferred embodiment is manufactured from metal, such as bent sheet aluminum, to shield electronics contained therein, such as host system 110 and mass storage device 113 as shown. However, it should be understood that the enclosure 102 may also be constructed of other materials such as alloys, composites, or polymer-based materials, provided the internal electronics are adequately shielded. The bezel 118 preferably is constructed of plastic, or other material through which energy (e.g., RF energy) can propagate. Bezel 118 may also provide a “window” transparent to IR energy for communication with an IR control device. The front bezel 118 defines an interstitial space 101 between the bezel 118 and the front face 114 of enclosure 102 . Various components such as universal control logic 116 discussed below are located within interstitial space 101 . Those components are generally not shielded, but the components located within the enclosure 102 are shielded.
[0029] Referring still to FIG. 1, host system 110 preferably comprises a suitable type of control logic. One suitable implementation of host system 110 comprises a microprocessor and associated devices such as random access memory, bridge devices, modems, network interface devices, audio controllers, and the like. Other implementations, such as those including discrete devices and analog circuitry are also permissible.
[0030] Mass storage device 113 preferably comprises a suitably-sized hard disk drive. Other types of mass storage devices (e.g., CD ROM) can also be used as a mass storage device. Mass storage device could also comprise a floppy drive if desired, or alternatively, set top box 100 may include a floppy drive in addition to a hard drive 113 . Host system 110 preferably communicates with mass storage device 113 to retrieve information from the storage device and store information on the storage device.
[0031] A DVD drive 126 is preferably also included to permit a user to watch video on a monitor (not shown) coupled to set top box 100 via interface connector 106 . For ease of use, DVD drive 126 is located at or adjacent the front bezel 118 . Connectors 134 are used to provide connectivity for IEEE 1394 and USB interfaces, or other types of interfaces.
[0032] Referring now to FIG. 2, the front bezel 118 of set top box 100 is shown. As shown, various input/output devices are included to permit a user to control the operation of the set top box. As can be seen, DVD 126 , input controls 120 , a display 124 , volume control 130 , and connectors 134 preferably are provided. Input controls 120 preferably comprise push buttons, but can be implemented as any suitable type of input control. Volume control 130 preferably comprises a knob that can be turned one way to increase volume and the other way to decrease volume. Display 124 preferably comprises a liquid crystal display (“LCD”) or other suitable type of display device. Each of the input/output devices 120 , 126 , 124 , and 130 preferably is electrically coupled to host system 110 located inside the metal enclosure 102 .
[0033] The functions performed by the buttons 120 preferably are identified on the display 124 . In accordance with the preferred embodiment of the invention, the display 124 is mounted adjacent buttons 120 to permit the host system 110 to display suitable information on the display 124 to inform the user as to the function performed by each button. As shown, the display is mounted immediately over the buttons, but many other configurations are possible as well. The 13 buttons 120 shown in FIG. 1 may be associated with the following 13 functions:
[0034] 1. Play
[0035] 2. Stop
[0036] 3. Pause
[0037] 4. Fast Forward
[0038] 5. Reverse
[0039] 6. Eject
[0040] 7. DVD
[0041] 8. Internet
[0042] 9. TV
[0043] 10. Games
[0044] 11. CD
[0045] 12. My Media (Files, JPEGs, etc)
[0046] 13. AUX-auxiliary Host system 110 can cause the word “PLAY” or the well-known play-icon (rightward pointing arrow) to be displayed adjacent the button 120 identified to perform the play function. The functions performed by the other buttons 120 are similarly identified by descriptive words or symbols shown adjacent the buttons. Further, the function associated with the selected button can be shown on the television monitor coupled to the set top box 100 by overlaying such information on the video signal provided to the monitor over interface 106 .
[0047] If desired, during operation of the set top box, the functions associated with the buttons 120 can be altered via programming executed by the host system. A change in functions can be identified to the user by changing the words or symbols shown on display 124 adjacent the effected buttons.
[0048] The host system 110 preferably includes an audio controller (i.e., an audio driver) to drive one or more speakers connected to ports 112 . As noted above, volume control 130 preferably permits a user to adjust the volume level of sound generated by the speakers. A graphic representation of the level of sound preferably is shown on display 124 and changed as the volume control 130 is adjusted.
[0049] The DVD 126 preferably includes a dedicated eject button 128 that causes a tray (not specifically shown) to extend out to the user. As is well known, the tray is used to hold the disk. After a disk is placed on the tray by the user, pressing the button 128 again causes the tray to retract into the DVD device 126 in accordance with customary operation of DVD/CD ROM devices.
[0050] Referring now to FIGS. 1 and 3, the problem noted above regarding the need to adequately shield the electronics in the metal enclosure 102 despite numerous input/output devices (e.g., buttons 120 , display 124 , volume control 130 ) need to be coupled to the host system 110 are solved by including a universal control logic unit 116 (referred to herein as “UCL 116 ”). Broadly, UCL 116 interfaces the various input/devices on front bezel 118 to the host system 110 located inside the metal enclosure via preferably a single communications link 122 . In accordance with a preferred embodiment of the invention discussed in greater detail below, communications link 122 comprises a standard bus connection such as a universal serial bus (“USB”), although other types of links now known or later developed can be used as well. Accordingly, UCL 116 performs one or more of the following functions:
[0051] Provides a single communication link to the host system 110 from a plurality of input/output devices;
[0052] Translates multiple disparate electrical input/output devices to a common format over the communication link;
[0053] Permits information shown on display 124 to be synchronized with comparable information shown on a television monitor coupled to the set top box 100 . As shown in FIG. 3, UCL 116 bridges a plurality of input devices 120 , 130 , a display 124 and a communication unit 134 to single communication link 122 . The communication link 122 may comprise a standard bus (e.g., USB) as noted above and, as such, may comprise a multi-conductor connection. Although link 122 may include more than one conductor, it still nevertheless comprises a single coordinated communication link.
[0054] Communication unit 134 preferably comprises a transceiver 136 coupled to an antenna 138 . Antenna 138 may include a patch antenna or any other antenna suitable for RF communication. Transceiver 136 may be any suitable transceiver for driving RF energy through the antenna 138 and receiving RF signals from the antenna from external sources.
[0055] Referring now to FIG. 4, UCL 116 is shown as comprising a USB hub 140 , a USB interface 144 , and a microcontroller 146 . USB hub 140 couples to the transceiver 136 , communication link 122 and USB interface 144 . USB interface 144 couples to the microcontroller 146 which also couples to the inputs 120 , 130 and display 124 . Microcontroller 146 can be any suitable type of microcontroller such as Intel's 8051 microcontroller. The USB interface 144 preferably is the PDIUSBD12 provided by Philips, but other suitable USB interface circuits may be acceptable as well. Among other things, the USB interface 144 includes an interrupt bit 152 which preferably is periodically checked by the host system 110 to determine whether it is set. When the interrupt bit 152 is set, the host system 110 determines that the UCL 116 requests a service of some type from the host system 110 . The USB interface 144 thus can use the interrupt bit 152 to initiate communication with the host system 110 . The USB hub 140 preferably is the ISP1122 provided by Philips, but can be implemented with any suitable interface device. The datasheet for the ISP 1122 is incorporated herein by reference in its entirety.
[0056] In accordance with the preferred embodiment of the inventor, host system 110 generally receives indications from the UCL 116 when the inputs 120 , 130 are activated (i.e., a button 120 is pressed or volume knob 130 is turned). Host system 110 preferably coordinates the activities of the set top box 100 to perform the functions intended by the user when activating controls 120 , 130 . For example, if the user presses the “play” button for the DVD, host system 110 responds by causing DVD 126 to enter its play mode. Similarly, if the user turns the volume knob 130 in the direction of increased sound level, the host system 110 responds by causing the sound level to increase by a corresponding amount.
[0057] Referring still to FIG. 4, microcontroller 146 preferably facilitates communication of input control information between inputs 120 , 130 and the host system 110 . Preferably, microcontroller 146 includes one or more registers 148 for registering when an input control as been activated by a user. Register 148 preferably comprises a means for storing information which identifies when an input control has been activated and which control was activated. One suitable embodiment of register 148 is for the register to include at least one bit (and more if desired) associated with each input control 120 , 130 . As such, the “play” button has an associated bit as well as the “rewind” button, “pause” button, etc. The input signals from the controls 120 , 130 preferably are provided to general purpose inputs of the microcontroller 146 . The microcontroller 146 maps the general purpose inputs to corresponding bits in register 148 . The bits in register 148 are referred to herein as “status flags.”
[0058] The microcontroller 146 executes code which may be stored in internal or external ROM (external ROM not shown in FIG. 4). At least one of the functions of the code is to “poll” the input signals from the input controls 120 , 130 . Polling means that the microcontroller periodically checks each input signal to determine which, if any, signal is asserted. Preferably, each input control signal normally is in an unasserted state (e.g., logic low) when the buttons are not pressed. When a button is pressed by a user, the input signal to the microcontroller 146 from the pressed button transitions to an asserted state (e.g., logic high). By repeatedly checking each input signal, the microcontroller will detect an asserted signal when the button associated with that input signal has been pressed. Because microcontrollers typically operate much faster than a human being is capable of pressing a button, it is virtually impossible for a human being to press and release a button before the microcontroller has an opportunity to check that signal.
[0059] When the microcontroller determines that a particular input signal is asserted (caused by its associated input control having been activated), the microcontroller sets the bit in register 148 associated with the activated input control. FIG. 5 illustrates this in greater detail.
[0060] Referring now to FIG. 5, and in conjunction with FIG. 4, method 200 comprises an exemplary method for the UCL 116 to determine when an input control as been activated and alert the host system 110 . In step 202 , the microcontroller 146 at a suitable time, such as during initial power up, initializes the status registers 148 . For example, the microcontroller 146 may clear all bits associated with input controls 120 , 130 to a logic 0 state (or logic 1, if the opposite polarity is implemented). Then, in step 206 the microcontroller 146 cycles through each input signal to determine if the input is asserted. If no input control is asserted, the process in step 206 loops back and repeats itself. If, however, the microcontroller 146 detects that a button has been pressed, the microcontroller, through well-known code, performs a switch debouncing function in step 210 . Often, when a user presses a button, the contacts in the button close and open multiple times in a transitional state between open and close, or vice versa. Debouncing a switch via hardware or software is well-known to those of ordinary skill in the art to prevent the system from reacting multiple times during this transitional episode.
[0061] In step 214 , the microcontroller 146 sets the status flag in register 148 associated with the activated input control 120 , 130 . Finally, in step 218 , the microcontroller 218 communicates with the USB interface 144 to cause the interrupt bit 152 in the interface to be set. The response of the host system 110 to a set interrupt bit 152 is illustrated in method 300 (FIG. 6).
[0062] Referring now FIG. 6, the host system 152 , as noted above, periodically polls the interrupt bit 152 via the USB bus 122 . When the host system 110 detects that the interrupt bit 152 is set, the host system 110 sends a USB formatted request command to the UCL 116 . In step 302 in method 300 , the UCL 116 receives the USB command from the host system 110 . In accordance with a preferred embodiment of the invention, the host system 110 sends two general types of USB commands to the UCL 116 : one type includes a request to send the states of the status flags in registers 148 to the host system 110 and the other type is to display information on the display 124 (FIG. 3) coupled to the set top box 100 . These two types of messages are differentiated by different command identifiers, such as operational codes (“opcodes”), embedded in accordance with well-known techniques in the messages themselves. In step 306 , the microcontroller 146 in the UCL 116 examines the USB message's opcode to determine the message type.
[0063] Decision step 310 determines whether the opcode is a request for the UCL 116 to send the status flags or for the UCL 116 to display information on the display 124 . If the USB message is of the former type, step 314 is performed whereby the microcontroller 146 sends a USB message back to the host system 110 that includes all of the status flags. The host system 110 can then examine the status flags to determine which is set, determine which function (e.g., play, pause, etc.) is associated with that flag and perform the requested function. Alternatively, the UCL 116 may send only an indication of which button has been pressed and not all of the status flags. In general, the UCL 116 provides any suitable type of information to the host system 110 for the host system to ascertain what input control 120 , 130 has been activated.
[0064] The other type of command message the host system 110 can provide to the UCL 116 —display information on display 124 —is determined in decision step 310 . Preferably, the information to be displayed is included in the message itself from the host system 110 (e.g. ASCII or other suitable type of format). If the message type is, in fact, a display command, then in step 318 the UCL 116 extracts the information to be displayed from the message and displays it on the display 124 . The information to be displayed may include graphics information, text information, information as to location on the display 124 for the displayed information, etc.
[0065] Referring briefly to FIG. 3, in accordance with the preferred embodiment of the invention, volume control 130 preferably includes a pair of signals 130 A and 130 B to the UCL 116 (and preferably the microcontroller 146 shown in FIG. 4). In accordance with the preferred embodiment, the volume control 130 comprises any suitable type of digital volume control such as that described in U.S. Pat. No. 5,963,652, incorporated herein by reference. As described in U.S. Pat. No. 5,963,652, volume control 130 includes a shaft encoder which monitors rotation of the volume knob. Through signals 130 A and 130 B, the volume control 130 informs the UCL 116 which direction the knob is being rotated (i.e., clockwise or counter-clockwise) by a user as the user attempts to increase or decrease the volume level. When the volume control 130 is stationary, the signals 130 A and 130 B are held at a constant level (e.g., logic 0 ). The control 130 includes a plurality of indents or clicks throughout its rotation. When the control 130 is turned, each discrete incremental click produces one pulse on each of the signals 130 A and 130 B. The two pulses are out of phase with respect to each other. The phase difference encodes the direction of rotation of the volume control 130 . Preferably, the UCL 116 detects the phase difference and causes an appropriate response in the sound level to occur.
[0066] [0066]FIGS. 7A and 7B shown one exemplary embodiment of how signals 130 A and 130 B can be encoded to indicate direction of rotation of volume control 130 . For example, as shown in FIG. 7A, if the user turns the volume knob clockwise, the pulse on signal 130 A may lead the pulse on signal 130 B. The UCL 116 detects that the pulse on signal 130 A leads the pulse on signal 130 B and determines that the user wishes to increase the volume level by one increment. One or more of the status flags in register 148 can be allocated for the purpose of the UCL 116 to communicate a new desired volume setting to the host system 110 . In the manner described above, the host system 110 reads the status flag register 148 to determine the new desired volume setting and increases the volume level to the speakers (not specifically shown) appropriately. If, however, the user turns the volume control 130 counter-clockwise (volume decrease), the pulse on signal 130 B leads the pulse on signal 130 A (FIG. 7B) indicating the user's desired to decrease the volume level. This information is communicated to the host system 110 as described above and the volume to the speakers is decreased accordingly.
[0067] In addition to changing the volume level, the UCL 116 preferably also displays a suitable graphic depicting the volume level on display 124 to provide a visual indication to the user of that the system has responded or is responding to the user's request. Any suitable type of graphic is acceptable. One such suitable graphic includes a bar graph (horizontally or vertically oriented). The length of the bar indicates absolute or relative volume level. Thus, as the user turns the volume control clockwise to increase the volume level at the speakers, the bar graph on the display 124 also increases in length to provide a visual feedback to the user. The opposite is true when the user turns the volume control 130 counter-clockwise-the bar decreases in length.
[0068] In accordance with the preferred embodiment, the graphic feedback to the user is provided by the host system 110 . In the manner described above regarding providing text information to be shown on display 124 , the host system 110 preferably provides graphical information regarding the volume bar to the UCL 116 via the USB bus 122 .
[0069] In addition to displaying volume information on display 124 , set top box 100 preferably provides volume graphical information (e.g., a bar graph) over the television connection 106 (FIG. 1) to the television monitor (not shown). Such graphical information preferably is provided by superimposing the graphical information on the video signal to the television monitor in accordance with known techniques. As such, when the user turns the volume control 130 on the set top box, three things happen: (1) the sound level changes, (2) a visual feedback is provided to the user on the set top box display 124 , and (3) visual feedback also is provided to the user on the television monitor. Thus, the user will, not only hear the volume change, but also see the bar graphs on both the set top box 100 and television monitor change in unison. This is illustrated in FIG. 8 in which the set top box 100 responds to a user adjusting volume control 130 by displaying a “4 bar” volume line 125 on set top box display 124 and, at substantially the same time, a 4 bar line 84 on the screen 82 of a television monitor 80 . Of course, the number of bars in each volume line 125 and 84 need not be identical. In fact, the size and shape of the lines can be whatever is desired. Preferably, however, a change in volume level is shown in some suitable format on both display 124 and monitor 80 at substantially the same time. “Substantially the same time” means simply that both visual representations of volume 125 and 84 are shown soon enough after the user turns volume control 130 to provide suitable feedback information to the user. It should be understood that other types of information can be originated by the set top box 100 and displayed on the television monitor as well, such as various DVD functions (e.g., play, pause, fast forward, etc.).
[0070] As shown herein, UCL 116 is suitable to interface input controls having disparate electrical properties to a host system via a single communications link 122 . For example, volume control 130 has a different electrical interface than buttons 120 . In general, one or more of the controls 120 , 130 may have different electrical interfaces for which UCL 116 has to account. UCL 116 , in effect, has to translate these varying electrical interfaces to a common format to communicate the control information over the single communication link.
[0071] The above discussion is meant to be illustrative of the principles and various embodiments of the present invention. Numerous variations and modifications will become apparent to those skilled in the art once the above disclosure is fully appreciated. It is intended that the following claims be interpreted to embrace all such variations and modifications. | A consumer electronics device includes a universal control logic unit to interface a plurality of input controls, a display and an antenna to a host system via a bus. The host system is located within a shielded enclosure, while the remaining components (e.g., input controls, display, antenna, universal control logic) are located outside the shielded enclosure. Because a single bus preferably is used to interface the various input/output components located outside the shielded enclosure to the shielded host system, the host system can be more easily and effectively shielded than if numerous separate electrical lines and busses were used to directly connect the various input/output devices to the host system. | 7 |
FIELD OF THE INVENTION
[0001] The invention relates to a method for controlling piezoelectric drives in filling level measuring devices.
[0002] Such a method is disclosed, for example, in German Patent Application DE 19 621 449 A1 in the name of the applicant. The design principle of a fork resonator is described there, and hereby incorporated by reference.
[0003] In reducing the size of tuning fork systems as far as very short fork prong lengths, the basic problem arises that in addition to the prong length the size of the remaining components must also be reduced to a corresponding extent, in order to obtain equivalent vibratory properties apart from the clearly higher frequency. While a corresponding reduction in the overall length of the piezoelectric drive unit is possible in principle, other components and parameters exist which do not change together in a suitable ratio.
[0004] Thus, for example, the diaphragm thickness is 1 mm for standard tuning forks with a prong length of approximately 100 mm. However, a diaphragm thickness of 0.4 mm would need to be targeted in the case of a tuning fork shortened to 40 mm. Since, however, a minimum material thickness of 1 mm is prescribed by statute for recognizing the diaphragm as explosion zone separation, the result is a crass disproportion between prong length and diaphragm thickness.
[0005] This problem is still further intensified in that the diameter of the central tension bolt on the diaphragm likewise cannot be reduced in size, since it would otherwise not be of sufficient tensile strength for the mechanical tensile stress applied by the drive system.
[0006] A weaker design of the drive system is, however, not possible since the diaphragm stiffness has increased owing to the constant diaphragm thickness in conjunction with a simultaneously reduced diameter. Since, in the case of a reduced diaphragm diameter, the tension bolt requires a larger area in relative terms, it leads to a further increase in the diaphragm flexural strength.
[0007] It is an undesired consequence of the diaphragm flexural strength, which is substantially too high by comparison with the fork prongs, that the fork prongs themselves take over a substantial portion of the overall flexural vibration of the vibration resonator. It is a particularly disturbing fact that, particularly in the case of a tuning fork covered by filling material, in addition to the fundamental vibrational mode vibration nodes also form on the fork prongs, with the undesired consequence of harmonic resonances.
[0008] In accordance with the prior art, a fundamental bandpass filter is fitted in the feedback oscillator which serves to excite the vibration resonator, and so the resonance circuit is reliably prevented from latching on to a harmonic. The partial formation of harmonic vibration nodes cannot, however, be excluded in this way, the result being a negative influence on the fundamental vibration.
[0009] The harmonic vibrations which occur have the effect that as the tuning fork dips into and out of the filling material the vibrational frequency changes not continuously but suddenly, with the formation of a hysteresis. In the case of viscous filling materials, it is even possible for the frequency profile to be inverted, since with increasing covering by filling material the influence of harmonic resonances grows. When the tuning fork dips into the filling material the frequency firstly drops—as desired—but with increasing cover there is then a rise in frequency under the influence of the high-frequency harmonics which, in the case of a completely covered tuning fork, can lead to a frequency value such as corresponds to an uncovered fork. If the fundamental bandpass filter is tuned lower, the problem arises that the fork resonator no longer starts to vibrate automatically when the power supply is switched on.
[0010] In the known solutions, a rectangular signal is used to control the piezoelectric element. However, since the rectangular signal has a very strong harmonic content in addition to the fundamental, harmonic resonances which are present, but undesired, in the fork resonator are excited.
[0011] The use of a harmonic-free sinusoidal excitation signal would certainly solve the problem theoretical, but in practice it is exceptionally complicated in terms of circuitry and very unfavourable in terms of energy. In addition to the power consumption of the sinusoidal generator, which can be controlled by frequency and phase in a variable fashion, sinusoidal output stages have a poor efficiency in principle and require a supply voltage which is increased by {square root}2 so that a sinusoidal output signal of the same voltage-time area as a rectangular signal is generated. Furthermore, no method is known at present which permits the electronic separation of drive signal and detection signal in the case of sinusoidal excitation.
SUMMARY OF THE INVENTION
[0012] It is therefore the object of the method according to the invention to specify a method for controlling a piezoelectric drive in filling level measuring devices which, in conjunction with a minimum outlay on components and energy as well as the possibility of simultaneous use of a piezoelectric element for exciting and detecting vibrations, permits the fork resonator to be excited in a fashion attended by few harmonics.
[0013] This object is achieved by means of the features of claim 1 Developments of the invention are the subject matter of the dependent claims.
[0014] Thus, the method according to the invention achieves the object by virtue of the fact that an at least approximately trapezoidal signal is generated as excitation signal. The excitation signal can comprise, for example, two phases with approximately constant high or low potential which are interrupted by in each case a phase of defined period and a rate of signal change which is limited in a defined fashion. Use is preferably made for this purpose of a rail-to-rail integrator driven to the limit.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] The method according to the invention is explained with the aid of an exemplary embodiment in conjunction with two figures, in which:
[0016] [0016]FIG. 1 shows a block diagram of a vibration filling level limit switch according to the invention, and
[0017] [0017]FIG. 2 shows the time profile of a plurality of signals of the circuit illustrated in FIG. 1.
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0018] In the following exemplary embodiment of FIG. 1, a single piezoelectric element is shown as excitation and detection element. However, this can be replaced by a similarly acting transducer (for example a plurality of piezoelectric elements, inductive transducers or the like).
[0019] The block diagram, illustrated by way of example in FIG. 1, of a vibration filling level limit switch has an amplifier device 1 , 2 , 3 in whose feedback circuit a transducer device 7 , preferably a piezoelectric transducer device, is connected. In detail, the amplifier device comprises an amplifier 3 with a downstream fundamental bandpass filter 2 and a downstream zero crossing detector 1 , respectively a square-wave generator stage 1 . The input of an integrator is connected with the output of the zero crossing detector 1 . This integrator has an operational amplifier 6 . The non-inverting input of this operational amplifier 6 is connected to reference potential. The inverting input is firstly connected to the output of the operational amplifier 6 via a capacitor 5 , and secondly connected to the output of the zero crossing detector 1 via a resistor 4 . The output of the operational amplifier 6 of the integrator is connected to one pole of the transducer device 7 via a supply lead 17 . The other pole of the transducer device 7 is connected to one terminal of a resistor 8 via a supply lead 18 . The other terminal of the resistor 8 is at reference potential. The connecting point between the resistor 8 and the supply lead 18 is, moreover, connected to one input terminal of a changeover switch 9 . A further input terminal of the changeover switch 9 is at reference potential. The output terminal of the changeover switch 9 is in contact with the input of the amplifier 3 . The changeover switch 9 is switched over by a control signal D that is tapped at the output of an EXOR gate 16 . A first input of this EXOR gate is connected to the output of the zero crossing detector 1 and, simultaneously, to the free terminal, not connected to the operational amplifier 6 , of the resistor 4 . A second input of the EXOR gate 16 is connected to the output of a comparator 15 whose non-inverting input is at reference potential and whose inverting input is likewise connected to the output of the zero crossing detector 1 via a resistor 13 . A capacitor 14 is connected between reference potential and the inverting input of the operational amplifier 15 or comparator 15 .
[0020] In addition, the line 18 is connected to a comparator 11 , which is affected by hystereses, said connection being effected by the line 18 being in contact with the inverting input of the comparator 11 . The non-inverting input of this comparator 11 is firstly connected to reference potential via a resistor 10 , and secondly connected to the output of the comparator 11 via a further resistor 12 . The output of the comparator 11 is connected to a frequency evaluation stage 20 . The frequency evaluation stage 20 generates an optical and/or acoustic interference alarm signal when, in a way still to be explained below, it is established that the transducer device 7 is not correctly connected, or that there is a line defect in the circuit arrangement illustrated in FIG. 1.
[0021] The following functional sequence arises for the circuit shown in FIG. 1.
[0022] The vibration detection signal amplified by the input amplifier 3 is fed to the fundamental bandpass filter 2 which generates the filtered and phase-corrected, approximately sinusoidal intermediate signal E. The latter is converted by the zero crossing detector 1 into a rectangular signal A. In known sensors, this signal A would be used as excitation signal for the piezoelectric element 7 .
[0023] The signal A is fed for the purpose of reducing its harmonic content to an integrator 4 , 5 , 6 which generates the trapezoidal signal B. The integration time constant is selected by means of the components 4 , 5 in such a way that, after 15 to 30%, preferably approximately 25%, of the half period T/2 of the signal A, the operational amplifier 6 reaches its maximum or minimum final value Emax, Emin. Since the operational amplifier 6 preferably has a rail-to-rail output stage, these values respectively correspond to the positive and/or negative operating voltage U−, U. The signal B therefore reaches the full operational voltage range and, owing to the integration operation, has an edge steepness defined by means of the resistor 4 and capacitor 5 . By contrast with the rectangular signal A, the trapezoidal signal B is greatly reduced in harmonics, such that an only slight mechanical harmonic component is excited in the piezoelectric vibration element 7 .
[0024] The voltage-time area of the signal B is certainly somewhat reduced by comparison with that of the rectangular signal A, but substantially greater than in the case of a sinusoidal signal. By comparison with a sinusoidal signal, for the same supply voltage the signal B permits an advantageously higher excitation power.
[0025] The current flow through the piezoelectric element 7 is measured at the measuring shunt 8 . It is composed of the charge-reversal current, caused by the excitation signal, of the piezoelectric element 7 , and by the piezoelectric charging quanta generated on the basis of the mechanical fork resonator vibration. The signal C shows the superposition of the two current components. The separation of the vibration detection signal and operating signal is performed by means of the changeover switch 9 . It blanks out the undesired charge-reversal current in the detection signal in accordance with a control signal D by connecting the signal input of the input amplifier 3 to a frame potential during the time of the charge-reversal phase. The control signal B required for this purpose is derived from the signal A by using the resistor 13 , capacitor 14 and comparator 15 to generate an inverted auxiliary signal which is phase-shifted relative to A and produces the signal D at the EXOR gate 16 by exclusive ORing with the signal A. The low phase of the control signal D defines the time of the signal blanking and is always selected to be somewhat longer than the rising or falling signal phase in signal B.
[0026] The signals B and C are transmitted to the piezoelectric element 7 by means of lines 17 , 18 . If one of these lines is disconnected from the electronics, the oscillator vibration is interrupted, and this is detected by the downstream electronic evaluation system as a fault state. If the interruption occurs on the piezoelectric side, however, then starting from a certain cable length of the lines 17 , 18 the oscillator continues to vibrate, since it remains in feedback owing to the remaining cable capacitance.
[0027] The vibrational frequency is a function of the remaining cable length and of the electromagnetic parasitics, and may be in the range of nominal operating of the tuning fork, and so the defect may not be detected by the downstream frequency evaluation electronics, as the case may be.
[0028] In order to monitor the functioning of the piezoelectric element supply leads 17 , 18 , the capacitance between them is measured simultaneously during the vibration process.
[0029] The piezoelectric capacitance is typically approximately 2 nF, and the cable capacitance is typically at most approximately 0.5 nF. It is therefore clearly possible to use the capacitance value to distinguish whether the piezoelectric element is connected.
[0030] For this purpose, the signal C containing the piezoelectric charge-reversal currents and which is tapped at the measuring shunt 8 is evaluated by means of a comparator 10 , 11 , 12 , which is subject to hystereses. The resistors 10 , 12 lend the comparator 11 a switching hysteresis which is symmetrical relative to frame potential. During the rising or falling signal phase of B, voltage amplitudes occur at the measuring shunt 8 which are proportional to the rate of signal rise of signal B and the total capacitance of the piezoelectric element 7 and lines 17 , 18 . The switching hysteresis of the comparator 11 is selected to be so large that the capacitance of the lines 17 , 18 cannot effect switching over of the comparator 11 , whereas with the piezoelectric capacitor connected the comparator 11 flips into the inverted position in each case when signal B changes edge. The result at the output of the comparator 11 is a signal which, apart from differences in propagation time, corresponds to the signal A, and is fed to a fault evaluation unit not illustrated in more detail.
[0031] The input of the frequency evaluation stage is not now, as would correspond to the prior art, connected to the signal A, rather to the output signal of the comparator 11 . An interruption in the piezoelectric circuit therefore results in that the vibration failure monitor responds in the frequency evaluation stage.
[0032] Since the normal measurement signal runs through the comparator circuit 10 , 11 , 12 and the measuring shunt 8 permanently, it is impossible not to notice failure of this circuit part. Suitability in terms of TUV requirement category 3 is therefore obtained.
[0033] Whereas only indirect checking of the supply of power to the piezoelectric element takes place in the case of circuit monitoring methods by means of parallel resistors or fed-back lines, the method described permits direct monitoring of the piezoelectric element for physical presence in the circuit by measuring the capacitance of the piezoelectric element.
[0034] [0034]FIG. 1 illustrates a practical exemplary embodiment of an arrangement in which a piezoelectric element is excited electrically with few harmonics, a detection signal for the mechanical vibration is derived by the same piezoelectric element with the aid of the piezoelectrically generated charge quanta, and the self-capacitance is measured by the same piezoelectric element during the vibration process.
[0035] Exciting the piezoelectric element with few harmonics can, of course, also be employed without the line breakage detection described in the exemplary embodiment. Moreover, it is also possible to employ a plurality of piezoelectric elements instead of a single piezoelectric element. Finally, excitation with few harmonics is also possible wherever one or more piezoelectric elements are employed exclusively to excite vibrations. | A method for controlling piezoelectric drives in filling level measuring devices, in the case of which a piezoelectric device ( 7 ) is coupled to a fork resonator, and this piezoelectric device ( 7 ) is used to excite and detect vibrations. The excitation signal (B) is an at least approximately trapezoidal signal, as a result of which the generation of undesired harmonic resonances in the fork resonator can be effectively avoided. The excitation signal preferably comprises two phases with approximately constant maximum and minimum levels, respectively, which are interrupted in each case by a phase of defined period and defined limited rate of signal change. | 6 |
FIELD OF THE INVENTION
This invention relates generally to overhead valve engines, and more particularly, to an improvement in rocking arms and securement components used in overhead valve engines.
BACKGROUND INFORMATION
Internal combustion engines are used as the primary power plant for vehicles. An energy source such as gasoline or diesel fuel is used to cause expansion of fuel vapors or gases within cylinder chambers wherein pistons, connecting rods, and a crankshaft convert the pressure produced by the expansion into rotation movement. Control of the cylinder chamber is performed by sequential operation of intake and exhaust valves positioned into each chamber.
The valves are mechanically operated through a transfer of motion from a camshaft having eccentric oval shaped lobes. In overhead valve (OHV) engines, the camshaft lobes lift push rods which engage rocker arms mounted at the head of the cylinders. The rocker arms allow pivoting of the arm so as to rock up and down which in turn depress the biased intake and exhaust valve.
While this transfer of motion is effective, it does place a strain of the rocker arms and their related components during conditions of high torque such as when the engine is used for high performance applications including aircraft, automotive, marine, motorcycle and off-road use. During such use, even slight offset movement of rocker arm components may lead to incorrect tolerances multiplying efficiencies and causing burnt valves or possible cylinder destruction.
One such problem is the stud used for securing each rocker arm to the cylinder head. The typical rocker arm mounting stud is a steel threaded bolt used as the sole mounting device. A rocker arm can be secured to the stud with or without a means for adjusting operating clearances. A rocker arm design having adjustment ability will only control rocker arm loads from one direction while under load. However, when the rocker arm is in between operating cycles, and not underload, the rocker arm will "float" providing a lack of support to un-reciprocated component weight. A rocker arm design without adjustment is typically mounted in a fixed support position relying upon alternative methods of adjustment, such as the cam follower or hydraulic lifter, to provide a constant variable pre-load.
No device is known to combine the adjustability of floating rocker arms in combination with solid fixed mounts in the securement of the top and bottom of the rocker arm. The principle of the rocker arm retainment is to secure the rocker arm to the cylinder head limiting its upward motion at the pivoting point as retained by a single mounting stud that attaches to the cylinder head. Prior art single-stud designs are limited in attachment in a single direction, upward, away from the cylinder head and mounting stud and employ a single nut assembly atop the rocker arm for use as the locking device so as to securely attach the rocker arm to the mounting stud. This attachment allows the rocker arm to float when there is no upward load by the rotational action of the camshaft and its related components. There are two conventional design variations which affix the rocker arm to the cylinder head on a single stud mount design. The first design requires rocker arm adjustment. In such cases having a single rocker arm mounted to a single stud the design requires an adjustability of the rocker arm to provide for proper operating clearances to the related components thereby facilitating the adjustability of its installed height to the assembly of components. The second traditional design variation requires no rocker arm adjustment. In prior designs which have a single rocker arm mounted to a single stud for this operating method, the elimination of the need for adjustability for the rocker arm to provide for proper operating clearances rely upon a "bolt like" attachment to draw the rocker arm assembly down to a fixed and predetermined position whereby the required adjustability of the assembly of components is handled automatically by a hydraulic adjustment within a cam follower. This is also known as a lifter. In this type of design the rocker arm is pulled down upon a mounting stand that does not allow the rocker arms body to float as with the rocker arms that require providing a more permanently fixed attachment directly to the cylinder head. The hydraulic lifter does improve overall operation of the assembly but merely offers a decrease in assembly time by elimination of tolerance adjustment to the rocker arms. Thus, what is needed in the art is a rocker arm mounting stud which effectively combines adjustability with solid fixed blocking of the rocker arm to the cylinder head.
Still another problem with rocker arms is the pivoting action the rocker arm places on the mounting studs. Especially in high torque, high performance applications such as racing vehicles. In such application, demands are made that the rocker arm pivot point is maintained in a stable position. Misalignment of only a fraction of an inch can translate into incomplete operation of the intake or exhaust valve.
Attempts at increasing the rocker arm stability include the use of thicker castings which translates to heavier engines and heat dissipation problems. In single stud designs, a known device for stabilizing the upper end of the stud is a stud girdle. This device is secured by means of a horizontal clamping force placed around the stud mounting bolts by the use of straddling bars of metal, usually aluminum. The force is applied by simply coupling two or more adjusting nuts by use of a common bolt placed between them which would draw or tighten the two sides of the two piece girdle together. The result is a straddling of the adjusting nuts into a retained position by the use of clamping force.
The girdle is mounted on top of the rocker arm assembly, securely fastening to the rocker arm studs wherein deflection of one rocker arm stud is translated to the remaining rocker arm studs thereby strengthening and effectively eliminating any deflection. The problem with known stud girdles of the prior art is that by simply attaching a girdle to the rocker arm studs will not prevent stud deflection in all applications and may even lead to stud deflection if improperly installed. Further, it has been found that the use of stud girdles are ineffective in a number of high torque, high performance situations as the stud girdle typically comes in two piece sections that are required to be bolted together providing an area of expandability since the stud girdles use fasteners to hold the girdle together as well as incorporating the use of the studs to fasten the stud girdle to the cylinder head.
Thus what is needed in the art is a solid bar that applies a direct force between two or more studs in lieu of a girdle.
Another problem with rocker arms of the prior art is the metal on metal contact of a conventional non-roller rocker arm tip. Rocker arm designs without a roller tip are attached to the cylinder head in a number of ways to provide a reciprocal action to open the valves. Typically the roller tip rocker arm is mounted in a fashion so that its rotational motion is perpendicular to the linear path of the valve, providing a valve tip surface to have full contact across the width of the roller tip.
Numerous applications of American made overhead valve engines such as the 350 cubic inch "CHEVROLET" engine as well as the 302 and 351 cubic inch "FORD WINDSOR" engines have wedge combustion-chamber cylinder head designs wherein offset changes of the rocker arm between its mounting points to the head in the contact angle of the valve has introduced a misalignment of the normal rotational motion of the rocker arm. The misalignment has a significant increase in wear, thereby decreasing both longevity and performance. Prior known art to correct this situation has been to completely remachine the mounting angle of the rocker arm to the exact fraction of a third dimensional rotation. Alternatively, the rocker arm mounting system can be offset so as to keep the rocker arms access on a two plane rotational movement. Thus, what is needed in the art is a rocker arm providing a third dimensional rotation to compensate for misalignment.
SUMMARY OF THE INVENTION
The instant invention teaches an improved rocker arm assembly. One aspect of the invention is a rocker arm stud that provides both adjustability and fixed mounting of top and bottom when combined with a unique trunnion that is matched to provide the necessary contact surface of both sides. The combination provides a simple, single, locking mounting stud that secures the rocker arm from both above and below while also serving as an adjusting device for that retainment. The studs of the instant invention are used in combination with a double flat trunnion especially designed for coupling to the studs.
A stud lock bar of the instant assembly provides a direct pressure to mounting studs with a force provided by overlapping components, providing ultimate retainment of the rocker arms mounting studs in a rigidity similar to the base mount of the mounting studs.
A radius roller tip rocker arm of the instant invention provides a third dimension principle by making the contact point of the diameter of the roller tip, a radius, lean on its pivoting access to a controlled misalignment away from a limiting two dimensional plane. This provides a rotation of the rocker arms pivotal access without offsetting the contact points of the rocker. Further, the teaching of a roller tip rocker arm which can instruct the operator of its use and installation upon an engine to assure a minimum of wear to the components of the valve train.
Therefore, an objective of the instant invention is to improve the stability and accuracy of rocker arms and their interrelated components thereby increasing the performance and longevity rocker arm related assembly.
Still another objective of the instant invention is to provide for the adjustability of the rocker arm on a fixed single mounting stud and retainment of said adjustability so as to prevent loss of performance throughout the engines performance range. The adjustability of the rocker arm on single mounting stud designs is desirable in optimizing the variables of engine operation, the accuracy of this adjustment is directly related to the performance and longevity of components.
Yet another objective of the instant invention is to provide for a one piece stud lock to eliminate the need for stud girdles of the prior art.
Another objective of the instant invention is to provide a radius roller tip rocker arm providing a pivoting access to accommodate misalignment of rocker arms in relation to the intake and exhaust valve placement.
Yet another objective is to use the rocker arm body as an instrument for the installation geometry of the rocker arm upon the engine.
Still another objective is to teach an improvement to the roller arm which accepts the standards of: establishing that the least amount of radial motion occurs at a 90 degree angle to the axis of rotation; that installation of the roller rocker arm must be placed upon the valve to accommodate a "pivot point" which provides the axis to be 90 degrees to the angle of axis rotation; and correct assurance of this geometrical point of installation must symmetrically divide this 90 degree point to the amount of radial motion.
Other objects and advantages of this invention will become apparent from the following description taken in conjunction with the accompanying drawings wherein are set forth, by way of illustration and example, certain embodiments of this invention. The drawings constitute a part of this specification and include exemplary embodiments of the present invention and illustrate various objects and features thereof.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side view of a single stud having an upper and lower adjusting nut;
FIG. 2 is an exploded view of FIG. 1;
FIG. 3 is a partial cross Sectional front view of a single stud having an upper and lower adjusting nut coupled to a rocker arm;
FIG. 4 is a partial cross sectional side view of FIG. 3;
FIG. 5 is a partial cross sectional side view of a single stud having a lower adjusting nut and an elongated upper adjusting nut coupled to a rocker arm and support by a stud lock bar;
FIG. 6 is an exploded side view of stud lock assembly;
FIG. 7 is a top view of FIG. 6;
FIG. 8 is a top view of a stud lock bar with stud locks coupled to stud mounts;
FIG. 9 is a side view of FIG. 8;
FIG. 10 is a pictorial view of a V-8 engine illustrating the assembly of the instant stud lock, stud adjustment bolts, and improved rocker arms;
FIG. 11 is an end view of a conventional roller tip rocker arm having a flat roller;
FIG. 12 is an end view of a conventional roller tip rocker arm having a flat roller in a misaligned state;
FIG. 13 is an end view of a roller tip rocker arm having a beveled roller of the instant invention;
FIG. 14 is an end view of a roller tip rocker arm having a beveled roller of the instant invention in a misaligned state; and
FIG. 15 is a side view of a roller tip rocker arm having a top portion of the rocker arm parallel to the roller tip datum line of motion.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Although the invention has been described in terms a specific embodiment, it will be readily apparent to those skilled in this art that various modifications, rearrangements and substitutions can be made without departing from the spirit of the invention. The scope of the invention is defined by the claims appended hereto.
Now referring to FIG. 1 shown is a rocker arm stud 10 of the instant invention consisting of a fully threaded mounting stud 12 having a lower portion 14 for threadingly engaging the cylinder head of a conventional overhead valve engine. Nut 16 is threaded onto the stud 12 locking engagement with lower adjusting nut 18. Tightening the locking nut 16 and adjusting nut 18 together provides a means for securing the enlarged threads 14 into the cylinder head to securely lock the stud 12 into the cylinder head. The lock nut 16 and lower adjusting nut 18 can then be loosened allowing the adjusting nut 18 to be positioned for placement of a rocker arm, not shown, by use of a rocker arm tolerance check device. The lower adjusting nut 18 includes sleeve 20 available for engaging a trunnion 25 which is the main axial component of a rocker arm which is used to hold the rocker arm in place allowing it to pivot upon bearings. With the lower adjusting nut 18 providing rocker arm body support from beneath the body, upper adjusting nut 22 is used to clamp the rocker arm between the two nuts 18 and 22. The upper adjusting nut utilizes a sleeve type shape allowing the nut to fit within the cradle of a conventional rocker arm wherein tightening is preferably performed by an aircraft type twelve point crown 24.
FIG. 2 sets forth an exploded view of FIG. 1 wherein optional locking screw 26 provides frictional engagement of threads located on the inner surface of the upper adjusting nut 22 so as to securely engage the upper portion 28 of the threaded mounting stud 12 upon engaging the lower surface 29 of the screw 26. Use of an allen wrench fitting socket 31 allows the screw 26 to be threaded within the interior chamber provided by the upper adjusting nut 22. Beginning with the upper portion 28 of the threaded mounting stud 12, shown is a fine thread placed along a substantial portion of the bolt 12. The lower portion 14 of the threaded mounting stud 12 employs the thread as typically found on a conventional cylinder head. Upon installation the adjusting nut 18 is set at a precise height wherein the sleeve, respective of the rocker arm design, allows adjustment of the upward movement of the lower adjusting nut 18 for securement by lock nut 14. The bottom surface 23 of the trunnion 25 engaging the upper surface 27 of the sleeve 20 providing a base for support of the trunnion allowing the rocker arm to pivotedly rotate around an axis of rotation provided by the trunnion. The trunnion holds the rocker arm body on engagement of the upper adjusting nut 22 wherein adjustment between the two nuts 22 and 18 now provide for a means of exact placement of the rocker arm body. The locking allen screw 26 can then be used to prevent any further movement of the upper adjusting nut while the lower nut 16 can be used to prevent any further movement of the lower adjusting nut 18.
Now referring to FIG. 3 shown is a partial cross-sectional side view of an assembled stud 10 with a rocker arm body 30 wherein the sleeve 18 and the body of the upper adjusting nut 22 fit within the confines of the rocker arm body 30 for engagement of the trunnion 25 allowing pivotal movement of the rocker arm in accordance with the push rod lifting and valve spring counter reaction. The trunnion 22 thereby holds the rocker arm body 30 in a vertical position as determined by the aforementioned adjusting nuts numerals 18 and 22. The sleeve 18 and upper adjusting nut 22 provides a vertical alignment for the rocker arm. The interior chamber 33 of the upper adjusting nut 22 is threaded further allowing insertion of allen screw 26 where the lower surface 29 frictionally engages the stud providing a secure lock.
FIG. 4 sets forth yet another view of the adjustable stud lock 10 wherein the rocker arm body 30 is clearly depicted with push rod support 32 located at one end of the rocker arm body and a roller tip 34 contact located at the opposite end of the rocker arm body. The engagement of the adjusting nuts 16 and 22 with the trunnion 25 illustrate the adjustability along the stud. Pivotal action of the rocker arm 30 is provided by cavity 35 for the upper nut 22 and cavity 37 for the sleeve 18 of the lower nut 16.
Now referring to FIG. 5 shown is a stud lock 50 of the instant invention which engages the stud bolt of the instant invention by use of a modified upper adjusting nut 52 for locking the trunnion 22 in a fixed position. On a typical engine, the stud lock is a 17 inch long piece of solid metal, such as aluminum, 1 inch high and 1.250 wide. The upper adjusting nut 52 includes an elongated length of 2.250 inches and similar to the normal adjusting nut 22 includes a 7/16 inch-20 threads per inch, female, with a 0.609 outer diameter sleeve having a 16-24 micron finish. Chambers for receipt of the sleeve of the adjuster nut are drilled, reamed, or bored to 0.611±0.002 inches and placed in accordance with the stud mounting location of the particular engine.
FIG. 6 is an end view of the stud lock 50 wherein the upper adjusting nut 52 preferably utilizes a 12 point crown 54 and an allen screw 56 in a similar manner as set forth above. In this particular embodiment a horizontally placed engagement bolt 58 is placed through the stud lock block 50 wherein a cutout 60 will engage the side surface 62 of the upper adjusting nut 52. The engagement bolt 58 is a lock stud having a 0.500 inch with 20 threads per inch. The lock stud is inserted in to 0.355 inch offset holes drilled 0.501±0.002 inches placed perpendicular to the center line of the adjuster holes. Upon insertion a lock washer 64 is fitted within a lock washer placement area 66 wherein lock nut 68, preferably a 12 point nut, 0.500 with 20 threads engages the threads 70 of the horizontally disposed bolt 58 thereby tightening of the lock nut 68 frictionally engages the cutout 60 formed from a 0.310 radius cut along the side surface 62 of the adjusting nut 52 securely fastening the components into a fixed position. The top view shown in FIG. 7 clearly sets forth the cutout 60 on the horizontally disposed bolt 58 and its offset location in regards to the upper adjusting bolt 52 for coupling to washer 64 and adjusting nut 68. FIG. 8 sets forth a top view of a stud lock 50 depicting the tops of each adjusting bolts 52 and the centrally disposed allen nut 56 with the offset horizontal attachment bolt 58 with lock nut 68 securely holding the components in a fixed position. In FIG. 8, the stud lock 50 is made from a solid piece of metal, such as aluminum or steel, with the aforementioned precision cut holes for engaging the side surface of each upper adjusting nut 52 coupled to the stud bolt of a conventional eight cylinder head. The locking block 50 is shown with its plurality of vertically disposed chambers, each said chamber sized approximately 0.002 inches larger than said sleeves of associated stud mounts. The block 50 is available for placement over stud mounts allowing at least a portion of said stud mounts to extent through the chambers. FIG. 9 sets forth yet another view of the stud lock 50 as viewed from the side so as to further illustrate the side surface 62 of each upper adjusting bolt and its relation to the horizontal securement bolts 58 which are set beneath the washer and adjusting nut 68.
Now referring to FIG. 10 the installation of the stud lock 50 is shown on the left bank 51 and the right bank 53 of a conventional eight cylinder overhead valve engine 70 wherein the stud bolts are shown protruding through the upper surface of the stud lock 50 where they can be easily tightened. Similarly the horizontal securement bolts 68 are shown in their offset location for engaging of the upper adjusting nut. As apparent by the illustration, the stud lock 50 provides a fixed placement between all of the rocker arm mounting studs 10 eliminating movement of any independent stud by reinforcement of an adjoining stud bolt. As further described during reference to FIGS. 13 and 14, the rocker arm 120 of the instant invention is shown with its bevel roller 122.
Referring to FIG. 11 shown is a conventional rocker arm 100 having a roller tip 102 which is a flat surface 104 providing broad surface contact with the tip 106 of an intake or exhaust valve stem 108. FIG. 12 sets forth the same rocker arm 100 wherein the roller tip 102 is shown in a slight misalignment causing the surface 104 of the roller tip 102 to engage only an edge of the intake or exhaust stem 108. In this particular instance the misalignment would cause the stem to be forced to one side which could cause premature wearing of the oil seal leading to oil burning in the engine.
Now referring to FIG. 13 shown is the rocker arm 120 of the instant invention having a roller tip 122 with a curved surface 124 providing for a substantial contact over at least half of the roller tip with the end 126 of the intake or exhaust stem 128 during a normal and straight forward alignment setup. The improved roller tip comprises a roller 122 having an outer surface 124 and a width W 1 delineated by a first side 123 and a second side 125, the outer surface 124 has a larger diameter in the center or the surface 124 and a smaller diameter along each side 123 and 125 thereof. The roller 124 has a centrally disposed axis for insertion of a shaft 130 allowing rotation of the roller 124. Referring to FIG. 14 wherein a slight misalignment of the rocker arm 120 of the instant invention is shown wherein the roller tip 122 maintains at least one-half surface contact 124 on the tip 126 of the exhaust or intake stem 128. The curved roller tip 122 maintains sufficient surface area so as to provide controlled downward movement of the stem 128 without premature wear of the rocker arm, roller tip, or valve stem.
FIG. 15 sets forth an improved rocker arm body 150 having a means for mounting to a stud bolt for receipt of a push rod 152 and a roller tip 154 on either side of pivotable bearing location 156. The improvement consists of machining the upper surface 158 of said rocker arm to a parallel plane "B" in accordance with a datum line of motion "A" of said roller tip 154. The datum line of motion "A" is set at 90 degree angle to a valve, not shown, at mid-lift point of motion. The improved roller arm sets forth a standard to establish that the least amount of radial motion occurs at a 90 degree angle to the axis of rotation; that installation of the roller rocker arm must be placed upon the valve to accommodate a "pivot point" which provides the axis to be 90 degrees to the angle of axis rotation; and correct assurance of this geometrical point of installation must symmetrically divide this 90 degree point to the amount of radial motion. The rocker arm provides precision measuring rules as part of the design of the rocker body to facilitate the correct, precise and easy installation of the rocker arm body.
It is to be understood that while I have illustrated and described certain forms of my invention, it is not to be limited to the specific forms or arrangement of parts herein describe and shown. It will be apparent to those skilled in the art that various changes may be made without departing from the scope of the invention and the invention is not to be considered limited to what is shown in the drawings and described in the specification. | A rocker arm mounting stud assembly having a rocker arm mounting stud with adjustable rocker arm fixture mounting for use with a matching trunnion. Further provided is a radius roller tip rocker arm providing a third dimension principle by making the contact point of the diameter of the roller tip, a radius, lean on its pivoting access to control misalignment away from a two dimensional plane. A teaching of rocker arm geometry is provided for establishing precision measuring rules to facilitate the correct and precise installation of the rocker arm. Further provided is a one piece stud lock providing a direct pressure method of holding each rocker arm mounting stud with precise force providing overlapping components for retainment of each rocker arm mounting stud in a precision set predetermined position. | 5 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims priority to U.S. Provisional Patent Application No. 61/738,155, filed Dec. 17, 2012. The contents of U.S. Provisional Patent Application No. 61/738,155 are incorporated herein by reference in their entirety.
BACKGROUND
[0002] The present application relates generally to the field of rotary cutters. The present application relates more specifically to the field of apparatus and methods for replacing a blade on a rotary cutter.
[0003] Rotary blades can be difficult to handle because they are relatively thin, with a circular shape in which the entire outer edge is sharpened. The blades may be packaged with coating, such as a light rust-preventative lubricant. When sold in quantity, the blades may be stacked together, and can be difficult to separate because of the coating.
SUMMARY
[0004] One embodiment relates to an apparatus for presenting a replacement blade from a cartridge. The apparatus includes a body with a bottom side and a top side opposite the bottom side; a first position and a second position laterally spaced from the first position; and a trough aligned with the second position. The apparatus further includes a carrier slidably coupled to the body, the carrier movable between the first position and the second position. When the carrier is in the first position, the carrier couples to a blade if a blade is present in the first position. When the carrier is in the second position, the carrier decouples from the blade such that the blade is deposited in the trough, if a blade is coupled to the carrier. When the carrier moves from the first position to the second position, the carrier causes a blade to move from the first position to the second position.
[0005] Another embodiment relates to an apparatus for presenting a replacement blade from a cartridge. The apparatus includes a body with a bottom side and a top side opposite the bottom side; a first position and a second position laterally spaced from the first position; at least one finger proximate the first position; and a trough aligned with the second position. The apparatus further includes a cartridge coupled to the first side of the body. The cartridge has at least one rotary blade therein and a spring providing a biasing force against the at least on rotary blade. The apparatus further includes a carrier slidably coupled to the second side of the body and movable between the first position and the second position.
[0006] Yet another embodiment relates to a method for replacing a blade of a rotary cutting tool. The method includes providing a body comprising a first position and a second position laterally spaced from the first position, and a trough aligned with the second position; providing a carrier slidably coupled to the body, the carrier movable between the first position and the second position; and providing a blade proximate the first position. The method further includes coupling the carrier to the blade; moving the carrier from the first position to the second position; and depositing the blade in the trough.
[0007] The foregoing is a summary and thus by necessity contains simplifications, generalizations, and omissions of detail. Consequently, those skilled in the art will appreciate that the summary is illustrative only and is not intended to be in any way limiting. Other aspects, inventive features, and advantages of the devices and/or processes described herein, as defined solely by the claims, will become apparent in the detailed description set forth herein and taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] FIG. 1 is a top perspective view of a rotary blade replacement apparatus with the blade carrier in the second position, in accordance with an exemplary embodiment.
[0009] FIG. 2 is a top perspective view of the body of the rotary blade replacement apparatus of FIG. 1 .
[0010] FIG. 3 is a bottom perspective view of a blade carrier for the rotary blade replacement apparatus of FIG. 1 .
[0011] FIG. 4 is a top perspective view of the cartridge of the rotary blade replacement apparatus of FIG. 1 .
[0012] FIG. 5 is a cross-section view of the rotary blade replacement apparatus of FIG. 1 with the blade carrier in the first position, taken along line 5 - 5 .
[0013] FIGS. 6A-6D are sequential cross-section views showing the carrier moving a blade from the first position to the second position, taken along line 6 - 6 .
[0014] FIG. 7 is a detail cross section view of the rotary blade replacement apparatus of FIG. 1 with the carrier in a position intermediate between the first position and the second position, taken along line 7 - 7 .
[0015] FIGS. 8A-D are sequential cross-section views showing the carrier being moved from the second position to the first position, taken along line 8 - 8 .
[0016] FIGS. 9A-9L are sequential perspective views of a method of replacing a rotary blade in a device utilizing the rotary blade replacement apparatus of FIG. 1 .
DETAILED DESCRIPTION
[0017] Referring generally to the FIGURES, a rotary blade replacement apparatus and components thereof are shown according to an exemplary embodiment.
[0018] Before discussing further details of the rotary blade replacement apparatus and/or the components thereof, it should be noted that references to “front,” “back,” “rear,” “upward,” “downward,” “inner,” “outer,” “right,” and “left” in this description are merely used to identify the various elements as they are oriented in the FIGURES. These terms are not meant to limit the element which they describe, as the various elements may be oriented differently in various applications.
[0019] It should further be noted that for purposes of this disclosure, the term “coupled” means the joining of two members directly or indirectly to one another. Such joining may be stationary in nature or moveable in nature and/or such joining may allow for the flow of fluids, electricity, electrical signals, or other types of signals or communication between the two members. Such joining may be achieved with the two members or the two members and any additional intermediate members being integrally formed as a single unitary body with one another or with the two members or the two members and any additional intermediate members being attached to one another. Such joining may be permanent in nature or alternatively may be removable or releasable in nature.
[0020] Referring to FIG. 1 , a rotary blade replacement apparatus 20 is shown according to an exemplary embodiment. The apparatus 20 is configured to facilitate the removal and storage of old blades from a device (e.g., a rotary cutting device) and provide a new blade for the device. The apparatus 20 includes a main body 22 with a left end 23 (e.g., left side, left end portion, etc.) and a right end 25 (e.g., right side, right end portion, etc.), a bottom side 27 (e.g., bottom portion, bottom surface, etc.), and a top side 29 (e.g., top portion, top surface, etc.). A carrier 26 is slidably coupled to the body 22 and is utilized to engage and move a blade 30 of the type depicted in FIG. 4 from the left end 23 to the right end 25 . In an exemplary embodiment, and as represented in FIG. 4 , a stack of blades 30 may be provided in a cartridge 28 that is coupled to the left end 23 of the body 22 . The carrier 26 is configured to index a single new blade 30 from within the cartridge 28 to an installation location on the right end 25 of the body 22 . Once the blade 30 is moved to the right end 25 of the body 22 by the carrier 26 , the blade 30 may be disengaged from the carrier 26 and coupled to the device. The body 22 may further include a location for the storage for old blades removed from the device, as shown in FIG. 5 and discussed in more detail below.
[0021] Referring to FIG. 2 , the body 22 of the apparatus 20 is shown according to an exemplary embodiment. The left end 23 of the body 22 includes an opening 32 allowing blades to pass through the body 22 from the bottom side 27 to the top side 29 and a pair of blade stops 34 (e.g., members, fingers, arms, etc.) disposed over the opening. The blade stops 34 are flexible (e.g., resilient, deflectable, etc.) members that are configured to contact the top surface of the topmost blade 30 and control the position of the blade 30 relative to the body 22 and the carrier 26 . The blade stops 34 are coupled to the floor 36 of the body 22 at a first or proximal end and free on a second or distal end opposite the first end to allow the blade 30 to move from the left end 23 to the right end 25 . Each of the blade stops 34 includes a slot or groove 38 configured to receive a protrusion 56 on the carrier, as described in more detail below. The right end 25 of the body 22 includes a trough 40 (e.g., depression, hollow, recess, etc.) sized to receive a blade moved to the right end 25 by the carrier 26 . The trough 40 includes a central opening 42 . A recessed path 46 extends from the trough 40 to the opening to provide a clearance for a blade catch 52 of the carrier 26 .
[0022] Referring to FIG. 3 , a bottom perspective view of the carrier 26 is shown according to an exemplary embodiment. The edges of the carrier 26 engage a pair of longitudinal guides or rails 44 extending between the left end 23 and the right end 25 . The rails 44 couple the carrier 26 to the top of body 22 and allow the carrier 26 to slide relative to the body 22 . The underside of the carrier 26 includes one or more bosses 50 providing a contact surface for the top surface of the blade 30 . The carrier 26 further includes a blade catch 52 that extends from the underside farther than the bosses 50 and is configured to engage or catch the blade 30 when it is received in the central opening or blade aperture 31 of the blade 30 . The blade catch 52 is coupled to a flexible arm 54 , allowing the blade catch 52 to be deflected relative to the main body of the carrier 26 . According to an exemplary embodiment, the blade apertures 31 are circular and the blade catch 52 is a cylindrical body configured to be received in the circular aperture 31 . According to other exemplary embodiments, the blade catch 52 may be shaped to fit other blade aperture shapes (e.g., square, hexagonal, etc.). The carrier 26 further includes one or more protrusions 56 . The protrusions 56 align with the corresponding grooves 38 in the blade stops 34 . When contacting the blade stops 34 , the protrusions 56 bias the blade stops 34 downward, away from the carrier 26 . When the protrusions 56 are received in the grooves 38 , the blade stops 34 are allowed to move towards the underside of the carrier 26 and return to a rest position.
[0023] As shown in FIG. 5 , the carrier 26 may include a handle 58 (e.g., a ridge, protrusion, grip, etc.) that may be grasped or otherwise engaged by a user to move the carrier 26 relative to the body 22 . In other embodiments, the carrier 26 may have a surface texture (e.g., knurling) to allow a user to engage the carrier 26 . The travel of the carrier 26 relative to the body is limited by fingers 59 , which extend radially outward from the carrier 26 . The fingers 59 are captured by the rails 44 and prevent the carrier 26 from sliding off the body 22 .
[0024] Referring to FIG. 4 , the cartridge 28 is shown according to an exemplary embodiment. The cartridge 28 is configured to hold one or more blades 30 and is coupled (e.g., via snap, bayonet, threaded fastener, etc.) to the bottom of the left end 23 of the body 22 such that the blades 30 are aligned with the opening 32 in the left end 23 of the body 22 . According to one embodiment, the cartridge 28 may be pre-loaded with five blades 30 in a stack. The cartridge 28 includes a recess 60 configured to receive the one or more blades 30 and a post 62 extending upward in the recess 60 . The post 62 is received in the blade apertures 31 and aligns the blades 30 with each other and the other components of the apparatus 20 (e.g., the carrier 26 ) when the cartridge 28 is coupled to the body 22 . The post 62 limits or constrains the lateral movement of the blades 30 , keeping the blades 30 generally centered within the cartridge 28 such that the sharpened edges of the blades 30 do not become dulled by contact with the side wall of the cartridge 28 . According to an exemplary embodiment, the post 62 comprises a cylindrical body configured for use with a blade 30 with a circular blade aperture 31 . According to other exemplary embodiments, the post 62 may be shaped to fit other blade aperture shapes (e.g., square, hexagonal, etc.). The cartridge 28 further includes one or more biasing features, shown as spring arms 64 in FIG. 4 , that bias the stack of blades 30 towards the body 22 and against a stop face (for example, the blade stops 34 , the contact surfaces of the bosses 50 on the carrier 26 , etc.).
[0025] Referring to FIG. 5 , the body 22 may further include a storage area 66 for receiving and retaining old blades. The old blade storage area 66 allows for storage of old blades. The entire apparatus 20 can be disposed of (e.g., recycled) to safely dispose of the stored old blades. In other exemplary embodiments, the blades 30 or the entire storage area 66 may be configured to be removed from the apparatus 20 and disposed. According to another embodiment, the apparatus 20 may be configured such that a user can safely remove the blades 30 from the storage area 66 for disposal of the blades 30 . The body 22 includes retaining features 68 that hold the old blades in the storage area 66 . The storage area 66 is configured to allow for the blades to be added into the storage area 66 directly from the rotary cutting device without a user having to touch the blades. The storage area 66 may be configured to hold any number of blades, which may be chosen to be multiples of the number of blades pre-loaded in the cartridge 28 .
[0026] FIGS. 6A-6D show the apparatus 20 with the carrier 26 being moved from a first position to a second position, moving a blade from the left end 23 of the body 22 to the right end 25 of the body 22 . According to the exemplary embodiment described, the replacement apparatus 20 transfers the new blade 30 from the cartridge 28 to the trough 40 without touching a sharpened edge of the blade 30 . As shown in FIG. 6A , when the carrier 26 is in the first position and is aligned with the opening 32 in the body 22 and the blades 30 in the cartridge 28 , the blade catch 52 is received in the blade aperture 31 and makes contact with inner walls of the blade aperture 31 . The blade catch 52 extends beyond the bosses 50 by a distance approximately equal to the thickness of the blade 30 to ensure that the blade catch 52 only contacts the inner wall of the blade aperture 31 of the topmost blade 30 (e.g., the blade 30 directly against the bottom face of the blade stops 34 and the bosses 50 ). As shown in FIG. 6B , the carrier 26 moves the top blade 30 away from the stack of blades 30 held in the cartridge 28 via the engagement of the blade aperture 31 by the blade catch 52 as the carrier 26 is moved away from the first position towards the second position.
[0027] As shown in FIG. 6C and FIG. 7 , the top blade 30 is supported by multiple surfaces. The bottom of the blade 30 may contact a portion of the floor 36 of the body 22 , while the top of the blade 30 may contact the contact surfaces of the bosses 50 extending from the underside of the carrier 26 and the blade stops 34 . As the blade clearance protrusions 56 exit the grooves 38 in the blade stops 34 , the blade clearance protrusions 56 pass over the distal end of the blade stop 34 . The contact between the blade 30 and the floor 36 of the body 22 inhibits downward movement of the blade to decouple the blade 30 from the blade catch 52 of the carrier 26 . In addition, the blade 30 is sufficiently resilient to allow enough distortion (flex) to allow downward deflection of the stops 34 without preventing linear travel of the carrier 26 from the left 23 to the right 25 . As shown in FIG. 7 , the features integral to the body 22 and carrier 26 ensure contact between the blade aperture and the blade catch 52 until the blade 30 is sufficiently above the installation location formed by the trough 40 at the right end 25 of the body 22 , at which time the blade 30 is allowed to fall away from the blade catch 52 , into the trough 40 . In other exemplary embodiments, the carrier may include a deflectable member or portion that can be actuated by a user to push the blade 30 off the blade carrier 52 into the trough 40 .
[0028] FIGS. 8A-8E show the apparatus with the carrier being moved from the second position to the first position after depositing a blade 30 in the trough 40 at the right end 25 of the body 22 , as shown in FIG. 8A . Referring to FIG. 8B , returning from the second position to the first position, the protrusions 56 engage the distal ends of the blade stops 34 , causing the blade stops 34 to deflect downward from a first or un-deflected state to a second or deflected state. The deflection of the blade stops 34 pushes any blades 30 in the cartridge 28 downward, deflecting the spring arms 64 . The blade catch 52 extends downward farther than the bosses 50 . This downward movement of the blade stops 34 and blades 30 is sufficient to create a clearance for the blade catch 52 , allowing the blade catch 52 to translate over and past the sharpened edges of the blades 30 without being damaged by catching the edge of the blades 30 . Referring to FIG. 8C , as the carrier 26 is further advanced, the protrusions 56 enter the grooves 38 , allowing the blade stops 34 to return to the first or un-deflected state. The blades 30 are then biased upward by the spring arms 64 and contact the bottom surface of the blade catch 52 . When the carrier 26 is in the first position (shown in FIG. 8D ), located directly above the cartridge 28 , the blade catch 52 drops into the blade aperture 31 to engage the topmost blade 30 in the stack. The length of the blade catch 52 and the difference in heights between the blade catch 52 and the bosses 50 is such that the blade catch 52 engages only the top cutting blade 30 and not the lower cutting blades 30 in the stack.
[0029] Referring ,to FIGS. 9A-9L , a user may use the replacement apparatus 20 to replace the blade 30 on a rotary cutting tool 70 . Preferably, the replacement apparatus 20 enables a user to replace the blade 30 on a rotary cutting tool 70 without needing to touch the blade 30 . The user may remove or actuate a retaining feature (e.g., nut, clips, etc.) from the rotary cutter 70 (see FIG. 9A ) and orient the cutting tool 70 such that the blade 30 desired to be remove d (e.g., the old blade) decouples from the cutting tool 70 (decouples from the axle or post of the cutting tool) (see FIG. 9B ).
[0030] According to one embodiment, when the cutter is in a first position, the old blade decouples from the rotary cutter by the force of gravity. According to the embodiment shown, a portion of the cutting tool 70 may be removed with the blade 30 . In this embodiment, the cutting tool 70 (e.g., the removable portion of the cutting tool 70 ) includes a magnet to retain the blade. The replacement apparatus 20 may be turned upside down to access the old blade storage area (see FIG. 9C ), and the blade 30 and any removable portion of the cutting tool 70 to which the blade 30 is coupled to may be aligned with the storage area (see FIG. 9D ). The blade 30 may be engaged by retaining features and held in the storage area while the removable portion of the cutting tool 70 is removed (see FIG. 9E ). In this embodiment, the retaining features are stronger than the magnet incorporated in the cutting tool 70 , and the retaining features cause the decoupling between the cutting tool 70 and the blade 30 . The replacement apparatus 20 may then be turned over (see FIG. 9F ) and actuated as described above to index a new blade from a first side of the apparatus 20 to the second side (see FIGS. 9F-9H ). The removable portion of the cutting tool 70 may then be positioned such that the axle passes through the hole in the blade 30 in the trough of the replacement apparatus 20 (see FIG. 91 ). According to the embodiment shown, the magnet of the removable portion attracts and retains the blade 30 to the removable portion. According to another embodiment, the cutting tool 70 and the replacement apparatus 20 may be reoriented (e.g., inverted) such that the new blade 30 exits the trough and is supported on the axle of the cutting tool 70 by gravity. The replacement apparatus 20 may then be decoupled and/or removed from the cutting tool 70 (see FIG. 9J ). According to the embodiment shown, the removable portion of the cutting tool 70 may be re-coupled to the cutting tool 70 , and the retaining feature on the cutting tool 70 may be actuated or re-attached (see FIG. 9K ). The cutting tool 70 may then be utilized with a new blade 30 (see FIG. 9L )
[0031] The applicant notes that elements in the figures may be shown inaccurately due to limitations in the CAD software used to create the drawings. For example, the spring arms 64 are shown in an uncompressed or undeflected state in the cross-section views such that they pass through the blades 30 . However, those skilled in the art will understand from the figures and the description herein that the spring arms 64 press against the underside of the bottommost blade held within the cartridge 28 and are deflected downward into the cavity 60 by the blades 30 .
[0032] The construction and arrangement of the elements of the rotary blade replacement apparatus as shown in the exemplary embodiments are illustrative only. Although only a few embodiments of the present disclosure have been described in detail, those skilled in the art who review this disclosure will readily appreciate that many modifications are possible (e.g., variations in sizes, dimensions, structures, shapes and proportions of the various elements, values of parameters, mounting arrangements, use of materials, colors, orientations, etc.) without materially departing from the novel teachings and advantages of the subject matter recited. For example, elements shown as integrally formed may be constructed of multiple parts or elements. The elements and assemblies may be constructed from any of a wide variety of materials that provide sufficient strength or durability, in any of a wide variety of colors, textures, and combinations. Additionally, in the subject description, the word “exemplary” is used to mean serving as an example, instance, or illustration. Any embodiment or design described herein as “exemplary” is not necessarily to be construed as preferred or advantageous over other embodiments or designs. Rather, use of the word “exemplary” is intended to present concepts in a concrete manner. Accordingly, all such modifications are intended to be included within the scope of the present disclosure. Other substitutions, modifications, changes, and omissions may be made in the design, operating conditions, and arrangement of the preferred and other exemplary embodiments without departing from the scope of the appended claims.
[0033] The order or sequence of any process or method steps may be varied or re-sequenced according to alternative embodiments. Any means-plus-function clause is intended to cover the structures described herein as performing the recited function and not only structural equivalents but also equivalent structures. Other substitutions, modifications, changes and omissions may be made in the design, operating configuration, and arrangement of the preferred and other exemplary embodiments without departing from the scope of the appended claims. | An apparatus for presenting a replacement blade from a cartridge includes a body and a carrier. The body includes a first side and a second side opposite the first side, a first position and a second position laterally spaced from the first position, and a trough aligned with the second position. The carrier is slidably coupled to the body and movable between the first position and the second position. When the carrier is in the first position, the carrier couples to a blade if a blade is present in the first position. When the carrier is in the second position, the carrier decouples from the blade such that the blade is deposited in the trough, if a blade is coupled to the carrier. When the carrier moves from the first position to the second position, the carrier causes a blade to move from the first position to the second position. | 8 |
CROSS-REFERENCE TO RELATED APPLICATION
This non-provisional application claims the benefit of U.S. Provisional Application Ser. No. 61/351,338 filed Jun. 4, 2010.
FIELD OF THE INVENTION
The present invention relates to novel compounds useful against HIV, and more particularly, to compounds derived from betulinic acid and other structurally related compounds which are useful as HIV maturation inhibitors, and to pharmaceutical compositions containing same, as well as to methods for their preparation and use.
BACKGROUND OF THE INVENTION
HIV-1 (human immunodeficiency virus-1) infection remains a major medical problem, with an estimated 45 million people infected worldwide at the end of 2007. The number of cases of HIV and AIDS (acquired immunodeficiency syndrome) has risen rapidly. In 2005, approximately 5.0 million new infections were reported, and 3.1 million people died from AIDS. Currently available drugs for the treatment of HIV include nucleoside reverse transcriptase (RT) inhibitors or approved single pill combinations: zidovudine (or AZT or RETROVIR®), didanosine (or VIDEX®), stavudine (or ZERIT®), lamivudine (or 3TC or EPIVIR®), zalcitabine (or DDC or HIVID®), abacavir succinate (or ZIAGEN®), Tenofovir disoproxil fumarate salt (or VIREAD®, emtricitabine (or FTC-EMTRIVA®), COMBIVIR® (contains -3TC plus AZT), TRIZIVIR® (contains abacavir, lamivudine, and zidovudine), EPZICOM® (contains abacavir and lamivudine), TRUVADA® (contains VIREAD® and EMTRIVA®); non-nucleoside reverse transcriptase inhibitors: nevirapine (or VIRAMUNE®, delavirdine (or RESCRIPTOR®) and efavirenz (or SUSTIVA®, ATRIPLA® (TRUVADA®+SUSTIVA®), and etravirine, and peptidomimetic protease inhibitors or approved formulations: saquinavir, indinavir, ritonavir, nelfinavir, amprenavir, lopinavir, KALETRA® (lopinavir and Ritonavir), darunavir, atazanavir (REYATAZ®) and tipranavir (APTIVUS®), and integrase inhibitors such as raltegravir (ISENTRESS®), and entry inhibitors such as enfuvirtide (T-20) (FUZEON®) and maraviroc (SELZENTRY®).
Each of these drugs can only transiently restrain viral replication if used alone. However, when used in combination, these drugs have a profound effect on viremia and disease progression. In fact, significant reductions in death rates among AIDS patients have been recently documented as a consequence of the widespread application of combination therapy. However, despite these impressive results, 30 to 50% of patients may ultimately fail combination drug therapies. Insufficient drug potency, non-compliance, restricted tissue penetration and drug-specific limitations within certain cell types (e.g. most nucleoside analogs cannot be phosphorylated in resting cells) may account for the incomplete suppression of sensitive viruses. Furthermore, the high replication rate and rapid turnover of HIV-1 combined with the frequent incorporation of mutations, leads to the appearance of drug-resistant variants and treatment failures when sub-optimal drug concentrations are present. Therefore, novel anti-HIV agents exhibiting distinct resistance patterns, and favorable pharmacokinetic as well as safety profiles are needed to provide more treatment options. Improved HIV fusion inhibitors and HIV entry coreceptor antagonists are two examples of new classes of anti-HIV agents further being studied by a number of investigators.
HIV attachment inhibitors are a further subclass of antiviral compounds that bind to the HIV surface glycoprotein gp120, and interfere with the interaction between the surface protein gp120 and the host cell receptor CD4. Thus, they prevent HIV from attaching to the human CD4 T-cell, and block HIV replication in the first stage of the HIV life cycle. The properties of HIV attachment inhibitors have been improved in an effort to obtain compounds with maximized utility and efficacy as antiviral agents. In particular, U.S. Pat. No. 7,354,924 and US 2005/0209246 are illustrative of HIV attachment inhibitors.
Another emerging class of HIV treatment compounds are called HIV maturation inhibitors. Maturation is the last of as many as 10 or more steps in HIV replication or the HIV life cycle, in which HIV becomes infectious as a consequence of several HIV protease-mediated cleavage events in the gag protein that ultimately results in release of the caspid (CA) protein. Maturation inhibitors prevent the HIV capsid from properly assembling and maturing, from forming a protective outer coat, or from emerging from human cells. Instead, non-infectious viruses are produced, preventing subsequent cycles of HIV infection.
Certain derivatives of betulinic acid have now been shown to exhibit potent anti-HIV activity as HIV maturation inhibitors. For example, U.S. Pat. No. 7,365,221 discloses monoacylated betulin and dihydrobetuline derivatives, and their use as anti-HIV agents. As discussed in the '221 reference, esterification of betulinic acid (1) with certain substituted acyl groups, such as 3′,3′-dimethylglutaryl and 3′,3′-dimethylsuccinyl groups produced derivatives having enhanced activity (Kashiwada, Y., et al., J. Med. Chem. 39:1016-1017 (1996)). Acylated betulinic acid and dihydrobetulinic acid derivatives that are potent anti-HIV agents are also described in U.S. Pat. No. 5,679,828. Esterification of the 3 carbon of betulin with succinic acid also produced a compound capable of inhibiting HIV-1 activity (Pokrovskii, A. G., et al., Gos. Nauchnyi Tsentr Virusol. Biotekhnol. “Vector” 9:485-491 (2001)).
Other references to the use of treating HIV infection with compounds derived from betulinic acid include US 2005/0239748 and US 2008/0207573.
One HIV maturation compound that has been in development has been identified as Bevirimat or PA-457, with the chemical formula of C 36 H 56 O 6 and the IUPAC name of 3β-(3-carboxy-3-methyl-butanoyloxy) 1up-20(29)-en-28-oic acid.
Reference is also made herein to the provisional application by Bristol-Myers Squibb entitled “C-28 AMIDES OF MODIFIED C-3 BETULINIC ACID DERIVATIVES AS HIV MATURATION INHIBITORS,” filed on Jun. 4, 2010 and assigned U.S. Ser. No. 61/351,332.
What is now needed in the art are new compounds which are useful as HIV maturation inhibitors, as well as new pharmaceutical compositions containing these compounds.
SUMMARY OF THE INVENTION
The present invention provides compounds of Formula I, II and III below, including pharmaceutically acceptable salts thereof, their pharmaceutical formulations, and their use in patients suffering from or susceptible to a virus such as HIV. The compounds of Formula I-III are effective antiviral agents, particularly as inhibitors of HIV. They are useful for the treatment of HIV and AIDS.
One embodiment of the present invention is directed to a compound, including pharmaceutically acceptable salts thereof, which is selected from the group of:
a compound of formula I
a compound of formula II
a compound of formula III
wherein R 1 is isopropenyl or isopropyl;
J and E are —H or —CH 3 ;
E is absent when the double bond is present;
X is a phenyl or heteroaryl ring substituted with A, wherein A is at least one member selected from the group of —H, -halo, -hydroxyl, —C 1-6 alkyl, —C 1-6 alkoxy, —C 1-6 haloalkyl, —NR 2 R 2 , —COOR 2 , —C(O)NR 2 R 2 , —C(O)NR 2 SO 2 R 3 , —SO 2 NR 2 R 2 , —NR 2 SO 2 R 2 , —SO 2 NR 2 R 2 , —C 1-6 cycloalkyl-COOR 2 , —C 1-6 alkenyl-COOR 2 , —C 1-6 alkynyl-COOR 2 , —C 1-6 alkyl-COOR 2 , —NHC(O)(CH 2 ) n —COOR 2 , —SO 2 NR 2 C(O)R 2 , -tetrazole, and -bicyclic heteroaryl-COOR 2 , wherein R 2 is H, —C 1-6 alkyl, or substituted —C 1-6 alkyl and wherein R 3 is C 1-6 alkyl and further wherein n=1-6;
Y is selected from the group of —COOR 2 , —C(O)NR 2 R 2 , —C(O)NR 2 SO 2 R 3 , —C(O)NR 2 SO 2 NR 2 R 2 , —NR 2 SO 2 R 2 , —SO 2 NR 2 R 2 , —C 1-6 cycloalkyl-COOR 2 , —C 1-6 alkenyl-COOR 2 , —C 1-6 alkynyl-COOR 2 , —C 1-6 alkyl-COOR 2 , —NHC(O)(CH 2 ) n —COOR 2 , —SO 2 NR 2 C(O)R 2 , -tetrazole, —CONHOH, -bicyclic heteroaryl-COOR 2 , and —B(OH) 2 , wherein n=1-6; and
Z is selected from the group of —COOH, —COOR 4 and —CH 2 OH, wherein R 4 is C 1-6 alkyl or C 1-6 alkylphenyl.
In a further embodiment, there is provided a method for treating mammals infected with a virus, especially wherein said virus is HIV, comprising administering to said mammal an antiviral effective amount of a compound which is selected from the group of compounds of Formulas I, II, III above, and one or more pharmaceutically acceptable carriers, excipients or diluents. Optionally, the compound of Formulas I, II and/or III can be administered in combination with an antiviral effective amount of another AIDS treatment agent selected from the group consisting of: (a) an AIDS antiviral agent; (b) an anti-infective agent; (c) an immunomodulator; and (d) other HIV entry inhibitors.
Another embodiment of the present invention is a pharmaceutical composition comprising an antiviral effective amount of a compound which is selected from the group of compounds of Formulas I, II and III, and one or more pharmaceutically acceptable carriers, excipients, and diluents; and optionally in combination with an antiviral effective amount of an AIDS treatment agent selected from the group consisting of: (a) an AIDS antiviral agent; (b) an anti-infective agent; (c) an immunomodulator; and (d) other HIV entry inhibitors.
In another embodiment of the invention there is provided one or more methods for making the compounds of Formulas I, II and III.
The present invention is directed to these, as well as other important ends, hereinafter described.
DETAILED DESCRIPTION OF THE EMBODIMENTS
Since the compounds of the present invention may possess asymmetric centers and therefore occur as mixtures of diastereomers and enantiomers, the present disclosure includes the individual diastereoisomeric and enantiomeric forms of the compounds of Formulas I, II, III in addition to the mixtures thereof.
The terms “C-3” and “C-28” refer to certain positions of a triterpene core as numbered in accordance with IUPAC rules (positions depicted below with respect to an illustrative triterpene: betulin):
The same numbering is maintained when referring to the compound series in schemes and general description of methods.
DEFINITIONS
Unless otherwise specifically set forth elsewhere in the application, one or more of the following terms may be used herein, and shall have the following meanings:
“H” refers to hydrogen, including its isotopes, such as deuterium.
The term “C 1-6 alkyl” as used herein and in the claims (unless specified otherwise) mean straight or branched chain alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, amyl, hexyl and the like.
“C 1 -C 4 -fluoroalkyl” refers to F-substituted C 1 -C 4 alkyl wherein at least one H atom is substituted with F atom, and each H atom can be independently substituted by F atom;
“Halogen” refers to chlorine, bromine, iodine or fluorine.
An “aryl” or “Ar” group refers to an all carbon monocyclic or fused-ring polycyclic (i.e., rings which share adjacent pairs of carbon atoms) groups having a completely conjugated pi-electron system. Examples, without limitation, of aryl groups are phenyl, napthalenyl and anthracenyl. The aryl group may be substituted or unsubstituted. When substituted the substituted group(s) is preferably one or more selected from alkyl, cycloalkyl, aryl, heteroaryl, heteroalicyclic, hydroxy, alkoxy, aryloxy, heteroaryloxy, heteroalicycloxy, thiohydroxy, thioaryloxy, thioheteroaryloxy, thioheteroalicycloxy, cyano, halogen, nitro, carbonyl, O-carbamyl, N-carbamyl, C-amido, N-amido, C-carboxy, O-carboxy, sulfinyl, sulfonyl, sulfonamido, trihalomethyl, ureido, amino and —NR x R y , wherein R x and R y are independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, carbonyl, C-carboxy, sulfonyl, trihalomethyl, and, combined, a five- or six-member heteroalicyclic ring.
As used herein, a “heteroaryl” group refers to a monocyclic or fused ring (i.e., rings which share an adjacent pair of atoms) group having in the ring(s) one or more atoms selected from the group consisting of nitrogen, oxygen and sulfur and, in addition, having a completely conjugated pi-electron system. Unless otherwise indicated, the heteroaryl group may be attached at either a carbon or nitrogen atom within the heteroaryl group. It should be noted that the term heteroaryl is intended to encompass an N-oxide of the parent heteroaryl if such an N-oxide is chemically feasible as is known in the art. Examples, without limitation, of heteroaryl groups are furyl, thienyl, benzothienyl, thiazolyl, imidazolyl, oxazolyl, oxadiazolyl, thiadiazolyl, benzothiazolyl, triazolyl, tetrazolyl, isoxazolyl, isothiazolyl, pyrrolyl, pyranyl, tetrahydropyranyl, pyrazolyl, pyridyl, pyrimidinyl, quinolinyl, isoquinolinyl, purinyl, carbazolyl, benzoxazolyl, benzimidazolyl, indolyl, isoindolyl, pyrazinyl. diazinyl, pyrazine, triazinyl, tetrazinyl, and tetrazolyl. When substituted the substituted group(s) is preferably one or more selected from alkyl, cycloalkyl, aryl, heteroaryl, heteroalicyclic, hydroxy, alkoxy, aryloxy, heteroaryloxy, heteroalicycloxy, thioalkoxy, thiohydroxy, thioaryloxy, thioheteroaryloxy, thioheteroalicycloxy, cyano, halogen, nitro, carbonyl, O-carbamyl, N-carbamyl, C-amido, N-amido, C-carboxy, O-carboxy, sulfinyl, sulfonyl, sulfonamido, trihalomethyl, ureido, amino, and —NR x R y , wherein R x and R y are as defined above.
As used herein, a “heteroalicyclic” group refers to a monocyclic or fused ring group having in the ring(s) one or more atoms selected from the group consisting of nitrogen, oxygen and sulfur. Rings are selected from those which provide stable arrangements of bonds and are not intended to encompass systems which would not exist. The rings may also have one or more double bonds. However, the rings do not have a completely conjugated pi-electron system. Examples, without limitation, of heteroalicyclic groups are azetidinyl, piperidyl, piperazinyl, imidazolinyl, thiazolidinyl, 3-pyrrolidin-1-yl, morpholinyl, thiomorpholinyl and tetrahydropyranyl. When substituted the substituted group(s) is preferably one or more selected from alkyl, cycloalkyl, aryl, heteroaryl, heteroalicyclic, hydroxy, alkoxy, aryloxy, heteroaryloxy, heteroalicycloxy, thiohydroxy, thioalkoxy, thioaryloxy, thioheteroaryloxy, thioheteroalicycloxy, cyano, halogen, nitro, carbonyl, thiocarbonyl, O-carbamyl, N-carbamyl, O-thiocarbamyl, N-thiocarbamyl, C-amido, C-thioamido, N-amido, C-carboxy, O-carboxy, sulfinyl, sulfonyl, sulfonamido, trihalomethanesulfonamido, trihalomethanesulfonyl, silyl, guanyl, guanidino, ureido, phosphonyl, amino and —NR x R y , wherein R x and R y are as defined above.
An “alkyl” group refers to a saturated aliphatic hydrocarbon including straight chain and branched chain groups. Preferably, the alkyl group has 1 to 20 carbon atoms (whenever a numerical range; e.g., “1-20”, is stated herein, it means that the group, in this case the alkyl group may contain 1 carbon atom, 2 carbon atoms, 3 carbon atoms, etc. up to and including 20 carbon atoms). More preferably, it is a medium size alkyl having 1 to 10 carbon atoms. Most preferably, it is a lower alkyl having 1 to 4 carbon atoms. The alkyl group may be substituted or unsubstituted. When substituted, the substituent group(s) is preferably one or more individually selected from trihaloalkyl, cycloalkyl, aryl, heteroaryl, heteroalicyclic, hydroxy, alkoxy, aryloxy, heteroaryloxy, heteroalicycloxy, thiohydroxy, thioalkoxy, thioaryloxy, thioheteroaryloxy, thioheteroalicycloxy, cyano, halo, nitro, carbonyl, thiocarbonyl, O-carbamyl, N-carbamyl, O-thiocarbamyl, N-thiocarbamyl, C-amido, C-thioamido, N-amido, C-carboxy, O-carboxy, sulfinyl, sulfonyl, sulfonamido, trihalomethanesulfonamido, trihalomethanesulfonyl, and combined, a five- or six-member heteroalicyclic ring.
A “cycloalkyl” group refers to an all-carbon monocyclic or fused ring (i.e., rings which share and adjacent pair of carbon atoms) group wherein one or more rings does not have a completely conjugated pi-electron system. Examples, without limitation, of cycloalkyl groups are cyclopropane, cyclobutane, cyclopentane, cyclopentene, cyclohexane, cyclohexene, cycloheptane, cycloheptene and adamantane. A cycloalkyl group may be substituted or unsubstituted. When substituted, the substituent group(s) is preferably one or more individually selected from alkyl, aryl, heteroaryl, heteroalicyclic, hydroxy, alkoxy, aryloxy, heteroaryloxy, heteroalicycloxy, thiohydroxy, thioalkoxy, thioaryloxy, thioheteroaryloxy, thioheteroalicycloxy, cyano, halo, nitro, carbonyl, thiocarbonyl, O-carbamyl, N-carbamyl, O-thiocarbamyl, N-thiocarbamyl, C-amido, C-thioamido, N-amido, C-carboxy, O-carboxy, sulfinyl, sulfonyl, sulfonamido, trihalomethanesulfonamido, trihalomethanesulfonyl, silyl, amidino, guanidino, ureido, phosphonyl, amino and —NR x R y with R x and R y as defined above.
An “alkenyl” group refers to an alkyl group, as defined herein, having at least two carbon atoms and at least one carbon-carbon double bond.
An “alkynyl” group refers to an alkyl group, as defined herein, having at least two carbon atoms and at least one carbon-carbon triple bond.
A “hydroxy” group refers to an —OH group.
An “alkoxy” group refers to both an —O-alkyl and an —O-cycloalkyl group as defined herein.
An “aryloxy” group refers to both an —O-aryl and an —O-heteroaryl group, as defined herein.
A “heteroaryloxy” group refers to a heteroaryl-O— group with heteroaryl as defined herein.
A “heteroalicycloxy” group refers to a heteroalicyclic-O— group with heteroalicyclic as defined herein.
A “thiohydroxy” group refers to an —SH group.
A “thioalkoxy” group refers to both an S-alkyl and an —S-cycloalkyl group, as defined herein.
A “thioaryloxy” group refers to both an —S-aryl and an —S-heteroaryl group, as defined herein.
A “thioheteroaryloxy” group refers to a heteroaryl-S— group with heteroaryl as defined herein.
A “thioheteroalicycloxy” group refers to a heteroalicyclic-S— group with heteroalicyclic as defined herein.
A “carbonyl” group refers to a —C(═O)—R″ group, where R″ is selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heteroaryl (bonded through a ring carbon) and heteroalicyclic (bonded through a ring carbon), as each is defined herein.
An “aldehyde” group refers to a carbonyl group where R″ is hydrogen.
A “thiocarbonyl” group refers to a —C(═S)—R″ group, with R″ as defined herein.
A “Keto” group refers to a —CC(═O)C— group wherein the carbon on either or both sides of the C═O may be alkyl, cycloalkyl, aryl or a carbon of a heteroaryl or heteroalicyclic group.
A “trihalomethanecarbonyl” group refers to a Z 3 CC(═O)— group with said Z being a halogen.
A “C-carboxy” group refers to a —C(═O)O—R″ groups, with R″ as defined herein.
An “O-carboxy” group refers to a R″C(—O)O-group, with R″ as defined herein.
A “carboxylic acid” group refers to a C-carboxy group in which R″ is hydrogen.
A “trihalomethyl” group refers to a —CZ 3 , group wherein Z is a halogen group as defined herein.
A “trihalomethanesulfonyl” group refers to an Z 3 CS(═O) 2 — groups with Z as defined above.
A “trihalomethanesulfonamido” group refers to a Z 3 CS(═O) 2 NR x — group with Z as defined above and R x being H or (C 1-6 )alkyl.
A “sulfinyl” group refers to a —S(═O)—R″ group, with R″ being (C 1-6 )alkyl.
A “sulfonyl” group refers to a —S(═O) 2 R″ group with R″ being (C 1-6 )alkyl.
A “S-sulfonamido” group refers to a —S(═O) 2 NR X R Y , with R X and R Y independently being H or (C 1-6 )alkyl.
A “N-Sulfonamido” group refers to a R″S(═O) 2 NR x — group, with R x being H or (C 1-6 )alkyl.
A “O-carbamyl” group refers to a —OC(═O)NR x R y group, with R X and R Y independently being H or (C 1-6 )alkyl.
A “N-carbamyl” group refers to a R x OC(═O)NR y group, with R X and R Y independently being H or (C 1-6 )alkyl.
A “O-thiocarbamyl” group refers to a —OC(═S)NR x R y group, with R x and R y independently being H or (C 1-6 )alkyl.
A “N-thiocarbamyl” group refers to a R x OC(═S)NR y — group, with R x and R y independently being H or (C 1-6 )alkyl.
An “amino” group refers to an —NH 2 group.
A “C-amido” group refers to a —C(═O)NR x R y group, with R x and R y independently being H or (C 1-6 )alkyl.
A “C-thioamido” group refers to a —C(═S)NR x R y group, with R x and R y independently being H or (C 1-6 )alkyl.
A “N-amido” group refers to a R x C(═O)NR y — group, with R x and R y independently being H or (C 1-6 )alkyl.
An “ureido” group refers to a —NR x C(═O)NR y R y2 group, with R x , R y , and R y2 independently being H or (C 1-6 )alkyl.
A “guanidino” group refers to a —R x NC(═N)NR y R y2 group, with R x , R y , and R y2 independently being H or (C 1-6 )alkyl.
A “amidino” group refers to a R x R y NC(═N)— group, with R x and R y independently being H or (C 1-6 )alkyl.
A “cyano” group refers to a —CN group.
A “silyl” group refers to a —Si(R″) 3 , with R″ being (C 1-6 )alkyl or phenyl.
A “phosphonyl” group refers to a P(═O)(OR x ) 2 with R x being (C 1-6 )alkyl.
A “hydrazino” group refers to a —NR x NR y R y2 group, with R x , R y , and R y2 independently being H or (C 1-6 )alkyl.
A “4, 5, or 6 membered ring cyclic N-lactam” group refers to
Any two adjacent R groups may combine to form an additional aryl, cycloalkyl, heteroaryl or heterocyclic ring fused to the ring initially bearing those R groups.
It is known in the art that nitrogen atoms in heteroaryl systems can be “participating in a heteroaryl ring double bond”, and this refers to the form of double bonds in the two tautomeric structures which comprise five-member ring heteroaryl groups. This dictates whether nitrogens can be substituted as well understood by chemists in the art. The disclosure and claims of the present disclosure are based on the known general principles of chemical bonding. It is understood that the claims do not encompass structures known to be unstable or not able to exist based on the literature.
Pharmaceutically acceptable salts and prodrugs of compounds disclosed herein are within the scope of the invention. The term “pharmaceutically acceptable salt” as used herein and in the claims is intended to include nontoxic base addition salts. Suitable salts include those derived from organic and inorganic acids such as, without limitation, hydrochloric acid, hydrobromic acid, phosphoric acid, sulfuric acid, methanesulfonic acid, acetic acid, tartaric acid, lactic acid, sulfinic acid, citric acid, maleic acid, fumaric acid, sorbic acid, aconitic acid, salicylic acid, phthalic acid, and the like. The term “pharmaceutically acceptable salt” as used herein is also intended to include salts of acidic groups, such as a carboxylate, with such counterions as ammonium, alkali metal salts, particularly sodium or potassium, alkaline earth metal salts, particularly calcium or magnesium, and salts with suitable organic bases such as lower alkylamines (methylamine, ethylamine, cyclohexylamine, and the like) or with substituted lower alkylamines (e.g. hydroxyl-substituted alkylamines such as diethanolamine, triethanolamine or tris(hydroxymethyl)-aminomethane), or with bases such as piperidine or morpholine.
As stated above, the compounds of the invention also include “prodrugs”. The term “prodrug” as used herein encompasses both the term “prodrug esters” and the term “prodrug ethers”. The term “prodrug esters” as employed herein includes esters and carbonates formed by reacting one or more hydroxyls of compounds of Formula I with either alkyl, alkoxy, or aryl substituted acylating agents or phosphorylating agent employing procedures known to those skilled in the art to generate acetates, pivalates, methylcarbonates, benzoates, amino acid esters, phosphates, half acid esters such as malonates, succinates or glutarates, and the like. In certain embodiments, amino acid esters may be especially preferred.
Examples of such prodrug esters include
The term “prodrug ethers” include both phosphate acetals and O-glucosides. Representative examples of such prodrug ethers include
As set forth above, the invention is directed to a compound, including pharmaceutically acceptable salts thereof, which is selected from the group of:
a compound of formula I
a compound of formula II
a compound of formula III
wherein R 1 is isopropenyl or isopropyl;
J and E are —H or —CH 3 ;
E is absent when the double bond is present;
X is a phenyl or heteroaryl ring substituted with A, wherein A is at least one member selected from the group of —H, -halo, -hydroxyl, —C 1-6 alkyl, —C 1-6 alkoxy, —C 1-6 haloalkyl, —NR 2 R 2 , —COOR 2 , —C(O)NR 2 R 2 , —C(O)NR 2 SO 2 R 3 , —SO 2 NR 2 R 2 , —NR 2 SO 2 R 2 , —SO 2 NR 2 R 2 , —C 1-6 cycloalkyl-COOR 2 , —C 1-6 alkenyl-COOR 2 , —C 1-6 alkynyl-COOR 2 , —C 1-6 alkyl-COOR 2 , —NHC(O)(CH 2 ) n —COOR 2 , —SO 2 NR 2 C(O)R 2 , -tetrazole, and -bicyclic heteroaryl-COOR 2 , wherein R 2 is H, —C 1-6 alkyl, or substituted —C 1-6 alkyl and wherein R 3 is C 1-6 alkyl and further wherein n=1-6;
Y is selected from the group of —COOR 2 , —C(O)NR 2 R 2 , —C(O)NR 2 SO 2 R 3 , —C(O)NR 2 SO 2 NR 2 R 2 , —NR 2 SO 2 R 2 , —SO 2 NR 2 R 2 , —C 1-6 cycloalkyl-COOR 2 , —C 1-6 alkenyl-COOR 2 , —C 1-6 alkynyl-COOR 2 , —C 1-6 alkyl-COOR 2 , —NHC(O)(CH 2 ) n —COOR 2 , —SO 2 NR 2 C(O)R 2 , -tetrazole, —CONHOH, -bicyclic heteroaryl-COOR 2 , and —B(OH) 2 , wherein n=1-6; and
Z is selected from the group of —COOH, —COOR 4 and —CH 2 OH, wherein R 4 is C 1-6 alkyl or C 1-6 alkylphenyl.
More preferred compounds include those which are encompassed by Formula I. Of these, those wherein X is a phenyl ring are even more preferred. Also preferred are compounds of Formula I wherein A is at least one member selected from the group of —H, —OH, -halo, —C 1-3 alkyl, and —C 1-3 alkoxy, wherein -halo is selected from the group of —Cl, —F and —Br. Also preferred are compounds of Formula I wherein Y is —COOH.
In another preferred embodiment there is provided a compound of Formula Ia below wherein X is a phenyl ring and Y is —COOH in the para position:
In this embodiment, it is also preferred that A is at least one member selected from the group of —H, -halo, —OH, —C 1-3 alkyl and —C 1-3 alkoxy. It is particularly preferred that A is at least one member selected from the group of —H, -fluoro, -chloro, —OH, methyl and methoxy.
Other compounds derived from Formula I which are preferred as part of the invention include,
Of the foregoing, the following compounds are particularly preferred:
Also preferred as part of the invention are the compounds of Formula I wherein X is 5 or 6-membered heteroaryl ring. In particular, the compounds of Formula I wherein X is a 5-membered heteroaryl ring having the following structure are particularly preferred:
wherein each of U, V and W is selected from the group consisting of C, N, O and S, with the proviso that at least one of U, V and W is other than C. Of these, the compounds wherein X is selected from the group of thiophene, pyrazole, isoxaxole, and oxadiazole groups are particularly preferred. Also preferred are the compounds of Formula I wherein X is a 6-membered heteroaryl ring selected from the group of pyridyl and pyrimidine rings.
Other compounds derived from Formula I (wherein X is a 5 or 6-membered heteroaryl ring) which are preferred as part of the invention include the following:
Other preferred compounds of the invention include those which are encompassed by Formula II as set forth above. Of these, the compounds wherein X is a phenyl group and Y is —COOH in the para position (and A is as previously set forth) according to Formula IIa below are particularly preferred:
Other preferred compounds of Formula II include the following:
The compounds of the present invention, according to all the various embodiments described above, may be administered orally, parenterally (including subcutaneous injections, intravenous, intramuscular, intrasternal injection or infusion techniques), by inhalation spray, or rectally, and by other means, in dosage unit formulations containing non-toxic pharmaceutically acceptable carriers, excipients and diluents available to the skilled artisan. One or more adjuvants may also be included.
Thus, in accordance with the present invention, there is further provided a method of treatment, and a pharmaceutical composition, for treating viral infections such as HIV infection and AIDS. The treatment involves administering to a patient in need of such treatment a pharmaceutical composition which contains an antiviral effective amount of one or more of the compounds of Formulas I, II and/or III, together with one or more pharmaceutically acceptable carriers, excipients or diluents. As used herein, the term “antiviral effective amount” means the total amount of each active component of the composition and method that is sufficient to show a meaningful patient benefit, i.e., inhibiting, ameliorating, or healing of acute conditions characterized by inhibition of the HIV infection. When applied to an individual active ingredient, administered alone, the term refers to that ingredient alone. When applied to a combination, the term refers to combined amounts of the active ingredients that result in the therapeutic effect, whether administered in combination, serially or simultaneously. The terms “treat, treating, treatment” as used herein and in the claims means preventing, ameliorating or healing diseases associated with HIV infection.
The pharmaceutical compositions of the invention may be in the form of orally administrable suspensions or tablets; as well as nasal sprays, sterile injectable preparations, for example, as sterile injectable aqueous or oleaginous suspensions or suppositories. Pharmaceutically acceptable carriers, excipients or diluents may be utilized in the pharmaceutical compositions, and are those utilized in the art of pharmaceutical preparations.
When administered orally as a suspension, these compositions are prepared according to techniques typically known in the art of pharmaceutical formulation and may contain microcrystalline cellulose for imparting bulk, alginic acid or sodium alginate as a suspending agent, methylcellulose as a viscosity enhancer, and sweeteners/flavoring agents known in the art. As immediate release tablets, these compositions may contain microcrystalline cellulose, dicalcium phosphate, starch, magnesium stearate and lactose and/or other excipients, binders, extenders, disintegrants, diluents, and lubricants known in the art.
The injectable solutions or suspensions may be formulated according to known art, using suitable non-toxic, parenterally acceptable diluents or solvents, such as mannitol, 1,3-butanediol, water, Ringer's solution or isotonic sodium chloride solution, or suitable dispersing or wetting and suspending agents, such as sterile, bland, fixed oils, including synthetic mono- or diglycerides, and fatty acids, including oleic acid.
The compounds herein set forth can be administered orally to humans in a dosage range of about 1 to 100 mg/kg body weight in divided doses, usually over an extended period, such as days, weeks, months, or even years. One preferred dosage range is about 1 to 10 mg/kg body weight orally in divided doses. Another preferred dosage range is about 1 to 20 mg/kg body weight in divided doses. It will be understood, however, that the specific dose level and frequency of dosage for any particular patient may be varied and will depend upon a variety of factors including the activity of the specific compound employed, the metabolic stability and length of action of that compound, the age, body weight, general health, sex, diet, mode and time of administration, rate of excretion, drug combination, the severity of the particular condition, and the host undergoing therapy.
Also contemplated herein are combinations of the compounds of Formulas I, II and/or III herein set forth, together with one or more other agents useful in the treatment of AIDS. For example, the compounds of this disclosure may be effectively administered, whether at periods of pre-exposure and/or post-exposure, in combination with effective amounts of the AIDS antivirals, immunomodulators, antiinfectives, or vaccines, such as those in the following non-limiting table:
Drug Name
Manufacturer
Indication
ANTIVIRALS
097
Hoechst/Bayer
HIV infection,
AIDS, ARC
(non-nucleoside
reverse trans-
criptase (RT)
inhibitor)
Amprenavir
Glaxo Wellcome
HIV infection,
141 W94
AIDS, ARC
GW 141
(protease inhibitor)
Abacavir (1592U89)
Glaxo Wellcome
HIV infection,
GW 1592
AIDS, ARC
(RT inhibitor)
Acemannan
Carrington Labs
ARC
(Irving, TX)
Acyclovir
Burroughs Wellcome
HIV infection, AIDS,
ARC
AD-439
Tanox Biosystems
HIV infection, AIDS,
ARC
AD-519
Tanox Biosystems
HIV infection, AIDS,
ARC
Adefovir dipivoxil
Gilead Sciences
HIV infection
AL-721
Ethigen
ARC, PGL
(Los Angeles, CA)
HIV positive, AIDS
Alpha Interferon
Glaxo Wellcome
Kaposi′s sarcoma,
HIV in combination
w/Retrovir
Ansamycin
Adria Laboratories
ARC
LM 427
(Dublin, OH)
Erbamont
(Stamford, CT)
Antibody which
Advanced Biotherapy
AIDS, ARC
Neutralizes pH
Concepts
Labile alpha aberrant
(Rockville, MD)
Interferon
AR177
Aronex Pharm
HIV infection, AIDS,
ARC
Beta-fluoro-ddA
Nat′l Cancer Institute
AIDS-associated
diseases
BMS-234475
Bristol-Myers Squibb/
HIV infection,
(CGP-61755)
Novartis
AIDS, ARC
(protease inhibitor)
CI-1012
Warner-Lambert
HIV-1 infection
Cidofovir
Gilead Science
CMV retinitis,
herpes, papillomavirus
Curdlan sulfate
AJI Pharma USA
HIV infection
Cytomegalovirus
MedImmune
CMV retinitis
Immune globin
Cytovene
Syntex
Sight threatening
Ganciclovir
CMV
peripheral CMV
retinitis
Darunavir
Tibotec- J & J
HIV infection, AIDS, ARC
(protease inhibitor)
Delaviridine
Pharmacia-Upjohn
HIV infection,
AIDS, ARC
(RT inhibitor)
Dextran Sulfate
Ueno Fine Chem.
AIDS, ARC, HIV
Ind. Ltd. (Osaka,
positive
Japan)
asymptomatic
ddC
Hoffman-La Roche
HIV infection, AIDS,
Dideoxycytidine
ARC
ddI
Bristol-Myers Squibb
HIV infection, AIDS,
Dideoxyinosine
ARC; combination
with AZT/d4T
DMP-450
AVID
HIV infection,
(Camden, NJ)
AIDS, ARC
(protease inhibitor)
Efavirenz
Bristol Myers Squibb
HIV infection,
(DMP 266, Sustiva ®)
AIDS, ARC
(-)6-Chloro-4-(S)-
(non-nucleoside RT
cyclopropylethynyl-
inhibitor)
4(S)-trifluoro-
methyl-1,4-dihydro-
2H-3,1-benzoxazin-
2-one, STOCRINE
EL10
Elan Corp, PLC
HIV infection
(Gainesville, GA)
Etravirine
Tibotec/J & J
HIV infection, AIDS, ARC
(non-nucleoside
reverse transcriptase
inhibitor)
Famciclovir
Smith Kline
herpes zoster,
herpes simplex
GS 840
Gilead
HIV infection,
AIDS, ARC
(reverse transcriptase
inhibitor)
HBY097
Hoechst Marion
HIV infection,
Roussel
AIDS, ARC
(non-nucleoside
reverse transcriptase
inhibitor)
Hypericin
VIMRx Pharm.
HIV infection, AIDS,
ARC
Recombinant Human
Triton Biosciences
AIDS, Kaposi′s
Interferon Beta
(Almeda, CA)
sarcoma, ARC
Interferon alfa-n3
Interferon Sciences
ARC, AIDS
Indinavir
Merck
HIV infection, AIDS,
ARC, asymptomatic
HIV positive, also in
combination with
AZT/ddI/ddC
ISIS 2922
ISIS Pharmaceuticals
CMV retinitis
KNI-272
Nat′l Cancer Institute
HIV-assoc. diseases
Lamivudine, 3TC
Glaxo Wellcome
HIV infection,
AIDS, ARC
(reverse
transcriptase
inhibitor); also
with AZT
Lobucavir
Bristol-Myers Squibb
CMV infection
Nelfinavir
Agouron
HIV infection,
Pharmaceuticals
AIDS, ARC
(protease inhibitor)
Nevirapine
Boeheringer
HIV infection,
Ingleheim
AIDS, ARC
(RT inhibitor)
Novapren
Novaferon Labs, Inc.
HIV inhibitor
(Akron, OH)
Peptide T
Peninsula Labs
AIDS
Octapeptide
(Belmont, CA)
Sequence
Trisodium
Astra Pharm.
CMV retinitis, HIV
Phosphonoformate
Products, Inc.
infection, other CMV
infections
PNU-140690
Pharmacia Upjohn
HIV infection,
AIDS, ARC
(protease inhibitor)
Probucol
Vyrex
HIV infection, AIDS
RBC-CD4
Sheffield Med.
HIV infection,
Tech (Houston, TX)
AIDS, ARC
Ritonavir
Abbott
HIV infection,
AIDS, ARC
(protease inhibitor)
Saquinavir
Hoffmann-
HIV infection,
LaRoche
AIDS, ARC
(protease inhibitor)
Stavudine; d4T
Bristol-Myers Squibb
HIV infection, AIDS,
Didehydrodeoxy-
ARC
Thymidine
Tipranavir
Boehringer Ingelheim
HIV infection, AIDS, ARC
(protease inhibitor)
Valaciclovir
Glaxo Wellcome
Genital HSV & CMV
infections
Virazole
Viratek/ICN
asymptomatic HIV
Ribavirin
(Costa Mesa, CA)
positive, LAS, ARC
VX-478
Vertex
HIV infection, AIDS,
ARC
Zalcitabine
Hoffmann-LaRoche
HIV infection, AIDS,
ARC, with AZT
Zidovudine; AZT
Glaxo Wellcome
HIV infection, AIDS,
ARC, Kaposi′s
sarcoma, in combination
with other therapies
Tenofovir disoproxil,
Gilead
HIV infection,
fumarate salt
AIDS,
(VIREAD ®)
(reverse transcriptase
inhibitor)
EMTRIVA ®
Gilead
HIV infection,
(Emtricitabine)
AIDS,
(FTC)
(reverse transcriptase
inhibitor)
COMBIVIR ®
GSK
HIV infection,
AIDS,
(reverse transcriptase
inhibitor)
Abacavir succinate
GSK
HIV infection,
(or ZIAGEN ®)
AIDS,
(reverse transcriptase
inhibitor)
REYATAZ ®
Bristol-Myers Squibb
HIV infection
(or atazanavir)
AIDs, protease
inhibitor
FUZEON ®
Roche/Trimeris
HIV infection
(Enfuvirtide or T-20)
AIDs, viral Fusion
inhibitor
LEXIVA ®
GSK/Vertex
HIV infection
(or Fosamprenavir calcium)
AIDs, viral protease
inhibitor
Maraviroc
Pfizer
HIV infection
SELZENTRY ®;
AIDs, (CCR5 antagonist, in
(UK 427857)
development)
TRIZIVIR ®
GSK
HIV infection
AIDs,
(three drug combination)
Sch-417690 (vicriviroc)
Schering-Plough
HIV infection
AIDs, (CCR5 antagonist, in
development)
TAK-652
Takeda
HIV infection
AIDs, (CCR5 antagonist, in
development)
GSK 873140
GSK/ONO
HIV infection
(ONO-4128)
AIDs, (CCR5 antagonist,
in development)
Integrase Inhibitor
Merck
HIV infection
MK-0518
AIDs
Raltegravir
TRUVADA ®
Gilead
Combination of Tenofovir
disoproxil fumarate salt
(VIREAD ®)) and
EMTRIVA ®
(Emtricitabine)
Integrase Inhibitor
Gilead/Japan Tobacco
HIV Infection
GS917/JTK-303
AIDs
Elvitegravir
in development
Triple drug combination
Gilead/Bristol-Myers Squibb
Combination of Tenofovir
ATRIPLA ®
disoproxil fumarate salt
(VIREAD ®)), EMTRIVA ®
(Emtricitabine), and
SUSTIVA ® (Efavirenz)
4′-ethynyl-d4T
Bristol-Myers Squibb
HIV infection
AIDs
in development
CMX-157
Chimerix
HIV infection
Lipid conjugate of
AIDs
nucleotide tenofovir
GSK1349572
GSK
HIV infection
Integrase inhibitor
AIDs
IMMUNOMODULATORS
AS-101
Wyeth-Ayerst
AIDS
Bropirimine
Pharmacia Upjohn
Advanced AIDS
Acemannan
Carrington Labs, Inc.
AIDS, ARC
(Irving, TX)
CL246,738
Wyeth
AIDS, Kaposi′s
Lederle Labs
sarcoma
FP-21399
Fuki ImmunoPharm
Blocks HIV fusion
with CD4+ cells
Gamma Interferon
Genentech
ARC, in combination
w/TNF (tumor
necrosis factor)
Granulocyte
Genetics Institute
AIDS
Macrophage Colony
Sandoz
Stimulating Factor
Granulocyte
Hoechst-Roussel
AIDS
Macrophage Colony
Immunex
Stimulating Factor
Granulocyte
Schering-Plough
AIDS,
Macrophage Colony
combination
Stimulating Factor
w/AZT
HIV Core Particle
Rorer
Seropositive HIV
Immunostimulant
IL-2
Cetus
AIDS, in combination
Interleukin-2
w/AZT
IL-2
Hoffman-LaRoche
AIDS, ARC, HIV, in
Interleukin-2
Immunex
combination w/AZT
IL-2
Chiron
AIDS, increase in
Interleukin-2
CD4 cell counts
(aldeslukin)
Immune Globulin
Cutter Biological
Pediatric AIDS, in
Intravenous
(Berkeley, CA)
combination w/AZT
(human)
IMREG-1
Imreg
AIDS, Kaposi′s
(New Orleans, LA)
sarcoma, ARC, PGL
IMREG-2
Imreg
AIDS, Kaposi′s
(New Orleans, LA)
sarcoma, ARC, PGL
Imuthiol Diethyl
Merieux Institute
AIDS, ARC
Dithio Carbamate
Alpha-2
Schering Plough
Kaposi′s sarcoma
Interferon
w/AZT, AIDS
Methionine-
TNI Pharmaceutical
AIDS, ARC
Enkephalin
(Chicago, IL)
MTP-PE
Ciba-Geigy Corp.
Kaposi′s sarcoma
Muramyl-Tripeptide
Granulocyte
Amgen
AIDS, in combination
Colony Stimulating
w/AZT
Factor
Remune
Immune Response
Immunotherapeutic
Corp.
rCD4
Genentech
AIDS, ARC
Recombinant
Soluble Human CD4
rCD4-IgG
AIDS, ARC
hybrids
Recombinant
Biogen
AIDS, ARC
Soluble Human CD4
Interferon
Hoffman-La Roche
Kaposi′s sarcoma
Alfa 2a
AIDS, ARC,
in combination w/AZT
SK&F106528
Smith Kline
HIV infection
Soluble T4
Thymopentin
Immunobiology
HIV infection
Research Institute
(Annandale, NJ)
Tumor Necrosis
Genentech
ARC, in combination
Factor; TNF
w/gamma Interferon
ANTI-INFECTIVES
Clindamycin with
Pharmacia Upjohn
PCP
Primaquine
Fluconazole
Pfizer
Cryptococcal
meningitis,
candidiasis
Pastille
Squibb Corp.
Prevention of
Nystatin Pastille
oral candidiasis
Ornidyl
Merrell Dow
PCP
Eflornithine
Pentamidine
LyphoMed
PCP treatment
Isethionate (IM & IV)
(Rosemont, IL)
Trimethoprim
Antibacterial
Trimethoprim/sulfa
Antibacterial
Piritrexim
Burroughs Wellcome
PCP treatment
Pentamidine
Fisons Corporation
PCP prophylaxis
Isethionate for
Inhalation
Spiramycin
Rhone-Poulenc
Cryptosporidial
diarrhea
Intraconazole-
Janssen-Pharm.
Histoplasmosis;
R51211
cryptococcal
meningitis
Trimetrexate
Warner-Lambert
PCP
Daunorubicin
NeXstar, Sequus
Kaposi′s sarcoma
Recombinant Human
Ortho Pharm. Corp.
Severe anemia
Erythropoietin
assoc. with AZT
therapy
Recombinant Human
Serono
AIDS-related
Growth Hormone
wasting, cachexia
Megestrol Acetate
Bristol-Myers Squibb
Treatment of
anorexia assoc.
W/AIDS
Testosterone
Alza, Smith Kline
AIDS-related wasting
Total Enteral
Norwich Eaton
Diarrhea and
Nutrition
Pharmaceuticals
malabsorption
related to AIDS
Additionally, the compounds of the disclosure herein set forth may be used in combination with HIV entry inhibitors. Examples of such HIV entry inhibitors are discussed in DRUGS OF THE FUTURE 1999, 24(12), pp. 1355-1362; CELL, Vol. 9, pp. 243-246, Oct. 29, 1999; and DRUG DISCOVERY TODAY, Vol. 5, No. 5, May 2000, pp. 183-194 and Inhibitors of the entry of HIV into host cells . Meanwell, Nicholas A.; Kadow, John F. Current Opinion in Drug Discovery & Development (2003), 6(4), 451-461. Specifically the compounds can be utilized in combination with attachment inhibitors, fusion inhibitors, and chemokine receptor antagonists aimed at either the CCR5 or CXCR4 coreceptor. HIV attachment inhibitors are also set forth in U.S. Pat. No. 7,354,924 and US 2005/0209246.
It will be understood that the scope of combinations of the compounds of this disclosure with AIDS antivirals, immunomodulators, anti-infectives, HIV entry inhibitors or vaccines is not limited to the list in the above Table but includes, in principle, any combination with any pharmaceutical composition useful for the treatment of AIDS.
Preferred combinations are simultaneous or alternating treatments with a compound of the present disclosure and an inhibitor of HIV protease and/or a non-nucleoside inhibitor of HIV reverse transcriptase. An optional fourth component in the combination is a nucleoside inhibitor of HIV reverse transcriptase, such as AZT, 3TC, ddC or ddI. A preferred inhibitor of HIV protease is REYATAZ® (active ingredient Atazanavir). Typically a dose of 300 to 600 mg is administered once a day. This may be co-administered with a low dose of Ritonavir (50 to 500 mgs). Another preferred inhibitor of HIV protease is KALETRA®. Another useful inhibitor of HIV protease is indinavir, which is the sulfate salt of N-(2(R)-hydroxy-1-(S)-indanyl)-2(R)-phenylmethyl-4-(S)-hydroxy-5-(1-(4-(3-pyridyl-methyl)-2(S)—N′-(t-butylcarboxamido)-piperazinyl))-pentaneamide ethanolate, and is synthesized according to U.S. Pat. No. 5,413,999. Indinavir is generally administered at a dosage of 800 mg three times a day. Other preferred protease inhibitors are nelfinavir and ritonavir. Another preferred inhibitor of HIV protease is saquinavir which is administered in a dosage of 600 or 1200 mg tid. Preferred non-nucleoside inhibitors of HIV reverse transcriptase include efavirenz. These combinations may have unexpected effects on limiting the spread and degree of infection of HIV. Preferred combinations include those with the following (1) indinavir with efavirenz, and, optionally, AZT and/or 3TC and/or ddI and/or ddC; (2) indinavir, and any of AZT and/or ddI and/or ddC and/or 3TC, in particular, indinavir and AZT and 3TC; (3) stavudine and 3TC and/or zidovudine; (4) tenofovir disoproxil fumarate salt and emtricitabine.
In such combinations the compound of the present invention and other active agents may be administered separately or in conjunction. In addition, the administration of one element may be prior to, concurrent to, or subsequent to the administration of other agent(s).
General Chemistry
Methods of Synthesis
The present invention comprises compounds of Formulas I, II and III, their pharmaceutical formulations, and their use in patients suffering from or susceptible to HIV infection. The compounds of Formulas I, II and III include pharmaceutically acceptable salts thereof. General procedures to construct compounds of Formulas I, II and III and intermediates useful for their synthesis are described in the following Schemes (after the Abbreviations).
ABBREVIATIONS
One or more of the following abbreviations, most of which are conventional abbreviations well known to those skilled in the art, may be used throughout the description of the disclosure and the examples:
h=hour(s)
min=minute(s)
rt=room temperature
mol=mole(s)
mmol=millimole(s)
g=gram(s)
mg=milligram(s)
mL=milliliter(s)
TFA=trifluoroacetic Acid
DCE=1,2-Dichloroethane
DMAP=4-dimethylaminopyridine
DMF=N,N-dimethylformamide
KHMDS=potassium hexamethyldisilazide
TMS=trimethylsilyl
DCM=dichloromethane
MeOH=methanol
THF=tetrahydrofuran
EtOAc=ethyl acetate
DME=dimethoxyethane
TLC=thin layer chromatography
DMSO=dimethylsulfoxide
PCC=pyridinium chlorochromate
ATM=atmosphere(s)
HOAc=acidic acid
TBAF=tetrabutylammonium fluoride
TBDPSCl=tertbutyldiphenylchlorosilane
Hex=hexane(s)
Preparation of Compounds of Formulas I, II and III General Chemistry Schemes:
Compounds of Formula I and II can be prepared from commercially available (Aldrich, others) betulinic acid and/or betulin, by chemistry described in the following schemes.
General reaction schemes are set forth as follows:
The carboxylic acid in the C-28 position can be protected with a suitable protective group. Standard oxidation (i.e. PCC, Dess-Martin, Swern) produces the C-3 ketone which is then converted into the triflate using methods available to those skilled in the art. Palladium catalyzed cross coupling with boronic acid or stannanes (standard Suzuki or Stille couplings) followed by deprotection of the carboxylic acid affords the C-3 modified betulinic acid derivatives. Compounds of Formula II derived from betulinic acid can be prepared by taking compounds of formula I with the C-28 acid and hydrogenating stepwise or in one single step the double bonds present in the molecule as shown in scheme 2.
Preparation of compounds of formula I where Z=—CH 2 OH can be done in a similar manner starting from betulin instead of betulinic acid as follows: the hydroxyl group in C-28 position of betulin can be protected with a suitable hydroxyl-protective group. Standard oxidation (i.e. PCC, Dess-Martin) produces the C-3 ketone which is then converted into the triflate using methods available to those skilled in the art. Palladium catalyzed cross coupling with boronic acid or stannanes (standard Suzuki or Stille couplings) followed by deprotection of the carboxylic acid affords the C-3 modified betulin derivatives. Compounds of Formula II derived from betulin can be prepared by taking compounds of formula I with the C-28 hydroxyl group and hydrogenating stepwise or in one single step the double bonds present in the molecule as shown in scheme 4.
Some compounds of Formula I containing a carboxylic acid in the substituent in the C-3 position of the core can be further derivatized by converting the carboxylic acid in an acid chloride followed by addition of an amine. Deprotection of the C-28 acid or carboxylic acid produces the final compounds.
The same synthetic methods can be applied to prepare compounds of Formula III using ursolic acid, oleanoic acid or moronic acid (oxidation is not necessary in this case, since the C-3 ketone is already present) as starting material instead of betulinic acid or betulin as shown, for example, in the following scheme:
EXAMPLES
The following examples illustrate typical syntheses of the compounds of Formulas I, II and III as described generally above. These examples are illustrative only and are not intended to limit the disclosure in any way. The reagents and starting materials are readily available to one of ordinary skill in the art.
Chemistry
Typical Procedures and Characterization of Selected Examples:
Unless otherwise stated, solvents and reagents were used directly as obtained from commercial sources, and reactions were performed under a nitrogen atmosphere. Flash chromatography was conducted on Silica gel 60 (0.040-0.063 particle size; EM Science supply). 1 H NMR spectra were recorded on Bruker DRX-500f at 500 MHz (or Bruker AV 400 MHz, Bruker DPX-300B or Varian Gemini 300 at 300 MHz as stated). The chemical shifts were reported in ppm on the δ scale relative to δTMS=0. The following internal references were used for the residual protons in the following solvents: CDCl 3 (δ H 7.26), CD 3 OD (δ H 3.30), Acetic-d 4 (Acetic Acid d 4 ) (δ H 11.6, 2.07), DMSOmix or DMSO-D6_CDCl 3 (( H 2.50 and 8.25) (ratio 75%:25%), and DMSO-D6 (δ H 2.50). Standard acronyms were employed to describe the multiplicity patterns: s (singlet), br. s (broad singlet), d (doublet), t (triplet), q (quartet), m (multiplet), b (broad), app (apparent). The coupling constant (J) is in Hertz. All Liquid Chromatography (LC) data were recorded on a Shimadzu LC-10AS liquid chromatograph using a SPD-10AV UV-Vis detector with Mass Spectrometry (MS) data determined using a Micromass Platform for LC in electrospray mode.
LC/MS Methods
Method 1
Start % B=0, Final % B=100 over 2 minute gradient
Flow Rate=4 mL/Min
Solvent A=95% Water/5% Acetonitrile/10 mM Ammonium Acetate
Solvent B=5% Water/95% Acetonitrile/10 mM Ammonium Acetate
Column ═PHENOMENEX-LUNA 3.0×50 mm S10
Method 2
Start % B=30, Final % B=95 over 5 minute gradient
Flow Rate=2 mL/Min
Solvent A=100% Water/10 mM Ammonium Acetate
Solvent B=100% Acetonitrile/10 mM Ammonium Acetate
Column=Supelco Acentis 4.6×50 mm 2.7 um C18
Method 3
Start % B=30, Final % B=95 over 6 minute gradient
Flow Rate=1.5 mL/Min
Solvent A=100% Water/10 mM Ammonium Acetate
Solvent B=100% Acetonitrile/10 mM Ammonium Acetate
Column=Supelco Acentis 4.6×50 mm 2.7 um C18
Method 4
Start % B=30, Final % B=95 over 6 minute gradient
Flow Rate=2 mL/Min
Solvent A=100% Water/10 mM Ammonium Acetate
Solvent B=100% Acetonitrile/10 mM Ammonium Acetate
Column=Supelco Acentis 4.6×50 mm 2.7 um C18
Method 5
Start % B=0, Final % B=100 over 4 minute gradient
Flow Rate=4 mL/Min
Solvent A=95% Water/5% Acetonitrile/10 mM Ammonium Acetate
Solvent B=5% Water/95% Acetonitrile/10 mM Ammonium Acetate
Column=LUNA 3.0×50 mm S10
Method 6
Start % B=10, Final % B=95 over 7 minute gradient
Flow Rate=2 mL/Min
Solvent A=100% Water/10 mM Ammonium Acetate
Solvent B=100% Acetonitrile
Column=Ascentis C-18, 4.6×50 mm 2.7 um
Method 7
Start % B=0, Final % B=100 over 2 minute gradient
Flow Rate=4 mL/Min
Solvent A=95% Water/5% Methanol/10 mM Ammonium Acetate
Solvent B=5% Water/95% Methanol/10 mM Ammonium Acetate
Column=PHENOMENEX-LUNA 3.0×50 mm S10
Method 8
Start % B=20, Final % B=95 over 12 minute gradient
Flow Rate=1 mL/Min
Solvent A=100% Water/10 mM Ammonium Acetate
Solvent B=100% Methanol/10 mM Ammonium Acetate
Column=PHENOMENEX-LUNA 4.6×150 mm 5 um C5
Method 9
Start % B=70, Final % B=95 over 5 minute gradient
Flow Rate=1.2 mL/Min
Solvent A=100% Water/10 mM Ammonium Acetate
Solvent B=100% Methanol/10 mM Ammonium Acetate
Column=Waters Xbridge 4.6×50 mm 5 um C18
Preparation of Compounds
Preparation of (1R,3aS,5aR,5bR,7aR,9S,11aR,13aR,13bR)-methyl 9-hydroxy-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)icosahydro-1H-cyclopenta[a]chrysene-3a-carboxylate
To a solution of (1R,3aS,5aR,5bR,7aR,9S,11aR,13aR,13bR)-9-hydroxy-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)icosahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid (1 g, 2.190 mmol) in MeOH (5 mL) and toluene (5.00 mL) was added (diazomethyl)trimethylsilane (1.642 mL, 3.28 mmol). The reaction mixture was stirred for 3 hours at room temperature. TLC indicated starting material was consumed and a new product was formed. The reaction mixture was concentrated under reduced pressure to give the desired product (1R,3aS,5aR,5bR,7aR,9S,11aR,13aR,13bR)-methyl 9-hydroxy-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)icosahydro-1H-cyclopenta[a]chrysene-3a-carboxylate as a white solid (1 g, 97%). 1 H NMR (500 MHz, DMSO-D6) δ ppm 0.65 (s, 3H), 0.76 (s, 3H), 0.87 (d, J=12.67 Hz, 6H), 0.94 (s, 3H), 0.96-1.63 (m, 18H), 1.65 (s, 3H), 1.72-1.87 (m, 2H), 2.03-2.16 (m, 2H), 2.85-3.09 (m, 3H), 3.60 (s, 3H), 4.26 (d, J=4.58 Hz, 1H), 4.58 (s, 1H), 4.70 (d, J=1.83 Hz, 1H).
Preparation of (1R,3aS,5aR,5bR,7aR,11aR,13aR,13bR)-methyl 5a,5b,8,8,11a-pentamethyl-9-oxo-1-(prop-1-en-2-yl)icosahydro-1H-cyclopenta[a]chrysene-3a-carboxylate
To a solution of (1R,3aS,5aR,5bR,7aR,9S,11aR,13aR,13bR)-methyl 9-hydroxy-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)icosahydro-1H-cyclopenta[a]chrysene-3a-carboxylate (4 g, 8.50 mmol) in CH 2 Cl 2 (100 mL) was added PCC (5.50 g, 25.5 mmol). The reaction mixture was stirred for 15 hours at room temperature. TLC indicated starting material was consumed and a new compound was generated. The reaction mixture was concentrated under reduced pressure and the residue was purified by biotage using ethyl acetate/hexanes (0-20%) to give the desired product (1R,3aS,5aR,5bR,7aR,11aR,13aR,13bR)-methyl 5a,5b,8,8,11a-pentamethyl-9-oxo-1-(prop-1-en-2-yl)icosahydro-1H-cyclopenta[a]chrysene-3a-carboxylate as a white solid (4 g, 100%). 1 H NMR (500 MHz, DMSO-D6) δ ppm 0.85 (s, 3H), 0.88 (s, 3H), 0.93 (s, 3H), 0.95 (s, 3H), 0.98 (s, 3H), 1.00-1.64 (m, 17H), 1.65 (s, 3H), 1.73-1.84 (m, 3H), 2.07-2.23 (m, 2H), 2.28-2.39 (m, 1H), 2.39-2.48 (m, 1H), 2.86-3.00 (m, 1H), 3.56-3.63 (s, 3H), 4.58 (s, 1H), 4.71 (d, J=1.83 Hz, 1H).
Preparation of (1R,3aS,5aR,5bR,7aR,11aR,13aR,13bR)-methyl 5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-9-(trifluoromethylsulfonyloxy)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylate
To a solution of (1R,3aS,5aR,5bR,7aR,11aR,13aR,13bR)-methyl 5a,5b,8,8,11a-pentamethyl-9-oxo-1-(prop-1-en-2-yl)icosahydro-1H-cyclopenta[a]chrysene-3a-carboxylate (2 g, 4.27 mmol) and 1,1,1-trifluoro-N-phenyl-N-(trifluoromethylsulfonyl)methanesulfonamide (3.05 g, 8.53 mmol) in THF (30 mL) at −78° C. was slowly added KHMDS (0.5 M in Toluene) (17.07 mL, 8.53 mmol). The reaction mixture was stirred for 1 hour at −78° C. TLC indicated starting material was consumed and one new compound was generated. The reaction mixture was quenched with brine, and extracted with diethyl ether. The combined organic layer was dried over Na 2 SO 4 , filtered and concentrated under reduced pressure. The residue was dissolved in toluene and purified by biotage using ethyl acetate/hexanes (0-5%) to provide (1R,3aS,5aR,5bR,7aR,11aR,13aR,13bR)-methyl 5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-9-(trifluoromethylsulfonyloxy)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylate as a white solid (1.8 g, 70%). 1 H NMR (400 MHz, CHLOROFORM-D) δ ppm 0.92 (s, 3H), 0.97 (d, J=7.78 Hz, 3H), 1.01-1.05 (m, 6H), 1.13 (s, 3H), 1.15-1.67 (m, 15H), 1.68-1.82 (m, 5H), 1.84-1.98 (m, 2H), 2.17 (dd, J=17.07, 6.78 Hz, 1H), 2.22-2.34 (m, 2H), 2.88-3.12 (m, 1H), 3.69 (s, 3H), 4.62 (s, 1H), 4.75 (s, 1H), 5.57 (dd, J=6.78, 1.76 Hz, 1H).
General Procedure for Preparation of Examples 1a-b
Example 1a
Preparation of 3-((1R,3aS,5aR,5bR,7aR,11aS,13aR,13bR)-3a-(methoxycarbonyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)benzoic acid
A mixture of (1R,3aS,5aR,5bR,7aR,11aR,13aR,13bR)-methyl 5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-9-(trifluoromethylsulfonyloxy)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylate (240 mg, 0.399 mmol), 3-boronobenzoic acid (133 mg, 0.799 mmol), sodium carbonate (212 mg, 1.997 mmol) and Pd(Ph 3 P) 4 (46.2 mg, 0.040 mmol) in DME (2.000 ml) and water (2 ml) was heated to 100° C. for 3 hours. TLC and LCMS indicated starting material was consumed, and the desired product was formed. The reaction mixture was cooled to room temperature, neutralized with 1N HCl, extracted with ethyl acetate, dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by biotage using ethyl acetate/hexanes (0-100%) ethyl acetate/hexanes to give the desired product 3-((1R,3aS,5aR,5bR,7aR,11aS,13aR,13bR)-3a-(methoxycarbonyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)benzoic acid as a white solid (120 mg, 50%). LCMS: m/e 571.47 (M−H) − , 3.91 min (method 5). 1 H NMR (500 MHz, DMSO-D6) δ ppm 0.88 (d, J=5.19 Hz, 6H), 0.92 (s, 3H), 0.95 (s, 3H), 0.98 (s, 3H), 1.00-1.56 (m, 15H), 1.57-1.73 (m, 5H), 1.73-1.86 (m, 2H), 2.07 (dd, J=17.24, 6.26 Hz, 1H), 2.11-2.17 (m, 1H), 2.18-2.28 (m, 1H), 2.85-3.03 (m, 1H), 3.61 (s, 3H), 4.59 (s, 1H), 4.72 (d, J=1.83 Hz, 1H), 5.25 (d, J=4.58 Hz, 1H), 7.33 (d, J=7.32 Hz, 1H), 7.40 (t, J=7.63 Hz, 1H), 7.65 (s, 1H), 7.82 (d, J=7.93 Hz, 1H).
Example 1b
Preparation of 4-((1R,3aS,5aR,5bR,7aR,11aS,13aR,13bR)-3a-(methoxycarbonyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)benzoic acid
The title compound was prepared following the method described above for compound 3-((1R,3aS,5aR,5bR,7aR,11aS,13aR,13bR)-3a-(methoxycarbonyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)benzoic acid (example 1a) using 4-boronobenzoic acid as the reactant boronic acid. The product was isolated as a white solid (60 mg, 26%). LCMS: m/e 571.47 (M−H) − , 8.27 min (method 6). 1 H NMR (500 MHz, DMSO-d 6 ) δ ppm 0.89 (s, 6H), 0.92 (s, 3H), 0.94 (s, 3H), 0.98 (s, 3H), 1.00-1.72 (m, 17H), 1.67 (s, 3H), 1.74-1.86 (m, 2H), 2.03-2.11 (m, 1H), 2.11-2.17 (m, 1H), 2.17-2.28 (m, 1H), 2.89-3.02 (m, 1H), 3.61 (s, 3H), 4.59 (s, 1H), 4.72 (d, J=2.14 Hz, 1H), 5.24 (dd, J=6.10, 1.53 Hz, 1H), 7.21 (d, J=8.24 Hz, 2H), 7.86 (d, J=8.55 Hz, 2H).
General Procedure for Preparation of Example 2a-b
Example 2a
Preparation of (1R,3aS,5aR,5bR,7aR,11aS,13aR,13bR)-9-(3-carboxyphenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid
A mixture of 3-((1R,3aS,5aR,5bR,7aR,11aS,13aR,13bR)-3a-(methoxycarbonyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)benzoic acid (140 mg, 0.244 mmol) and lithium bromide (425 mg, 4.89 mmol) in DMF (2 mL) was heated to 100° C. for 2 days. TLC indicated starting material was consumed and desired product was observed. The reaction mixture was filtered and the clear solution was purified by HPLC to provide the desired product (1R,3aS,5aR,5bR,7aR,11aS,13aR,13bR)-9-(3-carboxyphenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid as a white solid (25 mg, 17%). LCMS: m/e 557.48 (M−H) − , 5.67 min (method 6). 1 H NMR (400 MHz, DMSO-d 6 ) δ ppm 0.89 (s, 3H), 0.91 (s, 3H), 0.96 (s, 3H), 0.98 (s, 3H), 1.00 (s, 3H), 1.01-1.76 (m, 17H), 1.68 (s, 3H), 1.79-1.89 (m, 2H), 2.04-2.19 (m, 2H), 2.27-2.32 (m, 1H), 2.93-3.05 (m, 1H), 4.59 (s, 1H), 4.73 (d, J=2.01 Hz, 1H), 5.26 (d, J=4.77 Hz, 1H), 7.29-7.35 (m, 1H), 7.40 (t, J=7.65 Hz, 1H), 7.66 (s, 1H), 7.83 (d, J=7.53 Hz, 1H).
Example 2b
Preparation of (1R,3aS,5aR,5bR,7aR,11aS,13aR,13bR)-9-(4-carboxyphenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid
The title compound was prepared following the method described above for compound (1R,3aS,5aR,5bR,7aR,11aS,13aR,13bR)-9-(3-carboxyphenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid (example 2a). The product was isolated as a white solid (40 mg, 19%). LCMS: m/e 557.46 (M−H) − , 5.44 min (method 6). 1 H NMR (500 MHz, DMSO-d 6 ) δ ppm 0.88 (s, 3H), 0.89 (s, 3H), 0.94 (s, 6H), 0.98 (s, 3H), 0.99-1.72 (m, 17H), 1.66 (s, 3H), 1.77-1.88 (m, 2H), 2.01-2.17 (m, 2H), 2.24-2.34 (m, 1H), 2.92-3.04 (m, 1H), 4.58 (s, 1H), 4.71 (d, J=2.14 Hz, 1H), 5.22 (d, J=4.58 Hz, 1H), 7.13 (d, J=7.93 Hz, 2H), 7.81 (d, J=8.24 Hz, 2H).
General Procedure for Preparation of Examples 3a-b
Example 3a
Preparation of (3aS,5aR,5bR,7aS,9S,11aS,13aR,13bR)-9-(3-carboxyphenyl)-1-isopropyl-5a,5b,8,8,11a-pentamethylicosahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid
To a solution of (1R,3aS,5aR,5bR,7aR,11aS,13aR,13bR)-9-(3-carboxyphenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid (20 mg, 0.036 mmol) in EtOAc (3 mL) was added 10% Pd/C (4 mg, 0.0036 mmol). The reaction mixture was stirred at room temperature under 1 ATM of H 2 for 36 h. LCMS indicated the reaction was complete and the desired product was formed. The reaction mixture was filtered through a celite pad which was washed with ethyl acetate. The filtrate was concentrated under reduced pressure to provide (3aS,5aR,5bR,7aS,9S,11aS,13aR,13bR)-9-(3-carboxyphenyl)-1-isopropyl-5a,5b,8,8,11a-pentamethylicosahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid as a white solid (8 mg, 38%). LCMS: m/e 561.45 (M−H) − , 3.53 min (method 5). 1 H NMR (500 MHz, DMSO-d 6 ) δ ppm 0.64 (s, 3H), 0.71 (s, 3H), 0.74 (d, J=6.71 Hz, 3H), 0.80-0.86 (m, 3H), 0.92 (s, 3H), 0.93 (s, 3H), 0.95-0.98 (m, 3H), 0.98-1.66 (m, 18H), 1.68-1.82 (m, 3H), 2.07-2.22 (m, 3H), 2.23-2.34 (m, 1H), 2.42 (dd, J=13.12, 2.75 Hz, 1H), 7.36 (t, J=7.48 Hz, 1H), 7.39-7.46 (m, 1H), 7.70-7.80 (m, 2H).
Example 3b
Preparation of (1S,3aS,5aR,5bR,7aS,9S,11aS,11bR,13aR,13bR)-9-(4-carboxyphenyl)-1-isopropyl-5a,5b,8,8,11a-pentamethylicosahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid
The title compound was prepared following the method described above for compound (3aS,5aR,5bR,7aS,9S,11aS,13aR,13bR)-9-(3-carboxyphenyl)-1-isopropyl-5a,5b,8,8,11a-pentamethylicosahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid (example 3a). The product was isolated as a white solid (2.2 mg, 9%). LCMS: m/e 561.59 (M−H) − , 5.60 min (method 2). 1 H NMR (599 MHz, DMSO_CDCl 3 ) δ ppm 0.71 (s, 3H), 0.77 (s, 3H), 0.79 (d, J=7.03 Hz, 3H), 0.88 (d, J=6.44 Hz, 3H), 0.97 (s, 3H), 0.98 (s, 3H), 1.01 (s, 3H), 1.02-1.87 (m, 21H), 2.11-2.26 (m, 3H), 2.29-2.39 (m, 1H), 2.42-2.50 (m, 1H), 7.31 (d, J=7.62 Hz, 2H), 7.87 (d, J=7.62 Hz, 2H).
Intermediate 1: Preparation of (1R,3aS,5aR,5bR,7aR,9S,11aR,11bR,13aR,13bR)-benzyl 9-hydroxy-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)icosahydro-1H-cyclopenta[a]chrysene-3a-carboxylate
To a suspension of betulinic acid (12 g, 26.3 mmol) and potassium carbonate (7.26 g, 52.6 mmol) in DMF (150 mL) was added benzyl bromide (3.28 mL, 27.6 mmol). The mixture was heated to 60° C. for 3.5 h, and was cooled to rt. Solids started to precipitate upon cooling. The mixture was diluted with 200 mL of water and the solids that formed were collected by filtration to give (1R,3aS,5aR,5bR,7aR,9S,11aR,11bR, 13aR,13bR)-benzyl 9-hydroxy-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)icosahydro-1H-cyclopenta[a]chrysene-3a-carboxylate (13.92 g, 25.5 mmol, 97% yield) as a white solid. 1 H NMR (500 MHz, CHLOROFORM-d) δ ppm 0.74 (s, 3H), 0.75 (s, 3H), 0.79 (s, 3H), 0.82-1.71 (m, 20H), 0.93 (s, 3H), 0.95 (s, 3H), 1.67 (s, 3H), 1.81-1.93 (m, 2H), 2.13-2.21 (m, 1H), 2.27 (ddd, J=12.36, 3.20, 3.05 Hz, 1H), 3.01 (td, J=10.99, 4.88 Hz, 1H), 3.17 (ddd, J=11.44, 5.65, 5.49 Hz, 1H), 4.59 (s, 1H), 4.71 (d, J=1.83 Hz, 1H), 5.06-5.16 (m, 2H), 7.28-7.39 (m, 5H).
Intermediate 2: Preparation of (1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-benzyl 5a,5b,8,8,11a-pentamethyl-9-oxo-1-(prop-1-en-2-yl)icosahydro-1H-cyclopenta[a]chrysene-3a-carboxylate
To a solution of (1R,3aS,5aR,5bR,7aR,9S,11aR,11bR,13aR,13bR)-benzyl 9-hydroxy-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)icosahydro-1H-cyclopenta[a]chrysene-3a-carboxylate (7.1 g, 12.98 mmol) in DCM (100 mL) was added PCC (4.20 g, 19.48 mmol). After stirring for five minutes, the mixture turned a deep crimson color. The mixture was further stirred for 5.5 h. The mixture was filtered through a pad of celite and silica gel which was washed with dichloromethane and then a 1:1 mixture of ethyl acetate:hexanes. The filtrate was concentrated under reduced pressure to give (1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-benzyl 5a,5b,8,8,11a-pentamethyl-9-oxo-1-(prop-1-en-2-yl)icosahydro-1H-cyclopenta[a]chrysene-3a-carboxylate (6.92 g, 12.7 mmol, 98% yield) as a white foam. 1 H NMR (500 MHz, CHLOROFORM-d) δ ppm 0.78 (s, 3H), 0.89 (s, 3H), 0.94 (s, 3H), 0.95-1.73 (m, 17H), 1.01 (s, 3H), 1.05 (s, 3H), 1.67 (s, 3H), 1.82-1.94 (m, 3H), 2.21 (td, J=12.28, 3.51 Hz, 1H), 2.28 (dt, J=12.59, 3.17 Hz, 1H), 2.34-2.42 (m, 1H), 2.43-2.51 (m, 1H), 3.01 (td, J=10.99, 4.88 Hz, 1H), 4.59 (s, 1H), 4.72 (d, J=1.83 Hz, 1H), 5.06-5.17 (m, 2H), 7.28-7.38 (m, 5H).
Intermediate 3: Preparation of (1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-benzyl 5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-9-(trifluoromethylsulfonyloxy)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylate
To a solution of (1R,3aS,5aR,5bR,7aR,11aR,13aR,13bR)-benzyl 5a,5b,8,8,11a-pentamethyl-9-oxo-1-(prop-1-en-2-yl)icosahydro-1H-cyclopenta[a]chrysene-3a-carboxylate (6.9 g, 12.67 mmol) and 1,1,1-trifluoro-N-phenyl-N-(trifluoromethylsulfonyl)methanesulfonamide (9.05 g, 25.3 mmol) in THF (200 mL) at −78° C. was added KHMDS (50.7 mL, 25.3 mmol) slowly. The reaction mixture was stirred for 1 hour at −78° C. TLC indicated starting material was consumed and desired product was formed. The reaction mixture was quenched with brine, extracted with diethyl ether. The extracts were dried over Na 2 SO 4 , filtered and concentrated under reduced pressure. The residue was dissolved in toluene and purified by biotage 2-10% toluene/hexanes and 5-10% ethyl acetate/hexanes to provide the desired product. 1 H NMR (500 MHz, CHLOROFORM-d) δ ppm 0.77 (s, 3H), 0.88 (s, 3H), 0.91-1.77 (m, 17H), 0.94 (s, 3H), 1.00 (s, 3H), 1.10 (s, 3H), 1.67 (s, 3H), 1.81-1.96 (m, 2H), 2.14 (dd, J=17.09, 6.71 Hz, 1H), 2.22 (td, J=12.21, 3.36 Hz, 1H), 2.25-2.31 (m, 1H), 3.02 (td, J=10.99, 4.58 Hz, 1H), 4.59 (s, 1H), 4.72 (d, J=1.53 Hz, 1H), 5.05-5.12 (m, 1H), 5.13-5.18 (m, 1H), 5.54 (dd, J=6.71, 1.53 Hz, 1H), 7.29-7.41 (m, 5H).
General Method for the Preparation of Examples 4a-o
Example 4a
Step 1
Suzuki Coupling
Preparation of 3-(4-((1R,3aS,5aR,5bR,7aR,11aS,13aR,13bR)-3a-(benzyloxycarbonyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)phenyl)propanoic acid
A mixture of (1R,3aS,5aR,5bR,7aR,11aR,13aR,13bR)-benzyl 5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-9-(trifluoromethylsulfonyloxy)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylate (100 mg, 0.148 mmol), 3-(4-boronophenyl)propanoic acid (43.0 mg, 0.222 mmol), Pd(Ph 3 P) 4 (17.07 mg, 0.015 mmol) and sodium carbonate (78 mg, 0.739 mmol) in DME (1 mL) and Water (1 mL) was heated to 100° C. for 1.5 hours. LCMS indicated desired product was formed. The reaction mixture was cooled to the room temperature and neutralized to pH=4-5 using 1N HCl. The reaction mixture was extracted with ethyl acetate. The extracts were dried over Na 2 SO 4 , filtered through a celite pad and concentrated under reduced pressure. The residue was purified by 80-100% ethyl acetate/hexanes to give the desired product, 3-(4-((1R,3aS,5aR,5bR,7aR,11aS,13aR,13bR)-3a-(benzyloxycarbonyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)phenyl)propanoic acid, as colorless oil (60 mg, 55%). LCMS: m/e 675.63 (M−H) − , 4.78 min (method 5). 1 H NMR (500 MHz, CHLOROFORM-d) d ppm 0.82 (s, 3H), 0.89 (s, 3H), 0.90 (s, 3H), 0.95 (s, 3H), 0.97 (s, 3H), 0.99-1.73 (m, 17H), 1.69 (s, 3H), 1.80-1.97 (m, 2H), 2.04-2.11 (m, 1H), 2.19-2.37 (m, 2H), 2.62-2.73 (m, 2H), 2.93 (t, J=7.78 Hz, 2H), 3.04 (td, J=10.91, 4.73 Hz, 1H), 4.60 (s, 1H), 4.73 (d, J=2.14 Hz, 1H), 5.05-5.20 (m, 2H), 5.21-5.29 (m, 1H), 6.92-7.00 (m, 2H), 7.06 (d, J=7.63 Hz, 1H), 7.17 (t, J=7.48 Hz, 1H), 7.28-7.41 (m, 5H).
Step 2
Deprotection of Benzyl Ester (Method A)
Preparation of (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-9-(4-(2-carboxyethyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid
A mixture of 3-(4-((1R,3aS,5aR,5bR,7aR,11aS,13aR,13bR)-3a-(benzyloxycarbonyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)phenyl)propanoic acid (60 mg, 0.089 mmol) and 10% Pd/C (28.3 mg, 0.027 mmol) in Ethyl acetate (2 mL) was stirred under 1 ATM of H 2 for 24 hours. LCMS indicated the completion of the reaction. The reaction mixture was filtered and the white solid was collected. The solid was purified by Prep. HPLC to provide the desired product, (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-9-(4-(2-carboxyethyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid, as white solid (10.32 mg, 30%). LCMS: m/e 585.59 (M−H) − , 4.38 min (method 2). 1 H NMR (599 MHz, DMSO-D6_CDCl 3 ) δ ppm 0.91 (s, 3H), 0.93 (s, 3H), 1.00 (s, 6H), 1.02 (s, 3H), 1.05-1.72 (m, 17H), 1.71 (s, 3H), 1.84-1.95 (m, 2H), 2.10 (dd, J=17.58, 6.44 Hz, 1H), 2.20 (d, J=11.72 Hz, 1H), 2.30-2.39 (m, 1H), 2.60 (s, 2H), 2.85 (t, J=7.62 Hz, 2H), 3.02 (td, J=10.25, 5.27 Hz, 1H), 4.61 (br. s, 1H), 4.74 (s, 1H), 5.23 (d, J=5.27 Hz, 1H), 6.94 (d, J=7.62 Hz, 1H), 6.98 (s, 1H), 7.12 (d, J=8.20 Hz, 1H), 7.20 (t, J=7.62 Hz, 1H).
Example 4b
Preparation of (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-9-(4-(3-carboxypropanamido)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid
The title compound was prepared following the methods described above for (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-9-(4-(2-carboxyethyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid (example 4a) using 4-(4-boronophenylamino)-4-oxobutanoic acid as the reactant boronic acid. The product was isolated as a white solid (2.98 mg, 9%). LCMS: m/e 628.63 (M−H) − , 3.71 min (method 2). 1 H NMR (599 MHz, DMSO-D6_CDCl 3 ) δ ppm 0.91 (s, 3H), 0.93 (s, 3H), 0.98 (s, 3H), 0.99 (s, 3H), 1.02 (s, 3H), 1.03-1.71 (m, 17H), 1.71 (s, 3H), 1.84-1.93 (m, 2H), 2.09 (dd, J=17.87, 5.57 Hz, 1H), 2.20 (d, J=12.30 Hz, 1H), 2.29-2.39 (m, 1H), 2.59-2.62 (m, 2H), 2.97-3.10 (m, 1H), 3.30-3.33 (m, 2H), 4.61 (br. s, 1H), 4.74 (s, 1H), 5.24 (d, J=5.27 Hz, 1H), 7.03 (d, J=8.79 Hz, 2H), 7.51 (d, J=8.20 Hz, 2H).
Example 4c
Preparation of (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-9-(4-(1-carboxycyclopropyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid
The title compound was prepared following the methods described above for compound (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-9-(4-(2-carboxyethyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid (example 4a) using 1-(4-boronophenyl)cyclopropanecarboxylic acid as the reactant boronic acid. The product was isolated as a white solid (1.76 mg, 5%). LCMS: m/e 597.64 (M−H) − , 4.43 min (method 2). 1 H NMR (599 MHz, DMSO-D6_CDCl 3 ) δ ppm 0.92 (s, 3H), 0.94 (s, 3H), 0.99 (d, J=3.52 Hz, 6H), 1.02 (s, 3H), 1.03-1.71 (m, 21H), 1.71 (s, 3H), 1.82-1.95 (m, 2H), 2.10 (dd, J=17.28, 6.15 Hz, 1H), 2.20 (d, J=12.30 Hz, 1H), 2.30-2.39 (m, 1H), 2.97-3.09 (m, 1H), 4.61 (br. s, 1H), 4.74 (s, 1H), 5.25 (d, J=4.69 Hz, 1H), 7.04 (d, J=7.62 Hz, 2H), 7.25 (d, J=7.62 Hz, 2H).
Example 4d
Preparation of (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-9-(4-carboxy-3-fluorophenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid
The title compound was prepared following the method described above for compound (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-9-(4-(2-carboxyethyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid (example 4a) using 4-borono-2-fluorobenzoic acid as the reactant boronic acid. The product was isolated as a white solid (6.46 mg, 19%). LCMS: m/e 575.54 (M−H) − , 3.88 min (method 2). 1 H NMR (599 MHz, DMSO-D6_CDCl 3 ) δ ppm 0.95 (s, 6H), 0.98 (s, 3H), 1.00 (s, 3H), 1.02 (s, 3H), 1.04-1.76 (m, 17H), 1.71 (s, 3H), 1.88 (d, J=7.03 Hz, 2H), 2.13 (dd, J=17.58, 6.44 Hz, 1H), 2.20 (d, J=12.30 Hz, 1H), 2.29-2.39 (m, 1H), 2.98-3.07 (m, 1H), 4.61 (s, 1H), 4.74 (s, 1H), 5.33 (d, J=5.27 Hz, 1H), 6.96 (d, J=11.13 Hz, 1H), 7.02 (d, J=8.20 Hz, 1H), 7.79 (t, J=7.62 Hz, 1H).
Example 4e
Preparation of (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-5a,5b,8,8,11a-pentamethyl-9-(3-(N-methylsulfamoyl)phenyl)-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid
The title compound was prepared following the method described above for compound (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-9-(4-(2-carboxyethyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid (example 4a) using 3-(N-methylsulfamoyl)phenylboronic acid as the reactant boronic acid. The product was isolated as a white solid (32.47 mg, 62%). LCMS: m/e 606.58 (M−H) − , 4.47 min (method 2). 1 H NMR (599 MHz, DMSO-D6_CDCl 3 ) δ ppm 0.94 (s, 3H), 0.95 (s., 3H), 1.00 (br. s., 6H), 1.03 (s, 3H), 1.04-1.78 (m, 17H), 1.71 (s, 3H), 1.88 (t, J=7.03 Hz, 2H), 2.14 (dd, J=17.28, 6.15 Hz, 1H), 2.20 (d, J=12.30 Hz, 1H), 2.31-2.39 (m, 1H), 2.46 (d, J=4.69 Hz, 3H), 2.99-3.08 (m, 1H), 4.61 (s., 1H), 4.74 (s, 1H), 5.34 (d, J=5.86 Hz, 1H), 7.39 (d, J=8.20 Hz, 1H), 7.46 (q, J=5.27 Hz, 1H), 7.51-7.58 (m, 2H), 7.71 (d, J=7.62 Hz, 1H).
Example 4f
Preparation of (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-9-(4-hydroxyphenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a, 11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid
The title compound was prepared following the method described above for compound (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-9-(4-(2-carboxyethyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid (example 4a) using 4-hydroxyphenylboronic acid as the reactant boronic acid. The product was isolated as a white solid (1.25 mg, 4%). LCMS: m/e 529.55 (M−H) − , 4.34 min (method 2).
Example 4g
Preparation of (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-5a,5b,8,8,11a-pentamethyl-9-(3-(methylsulfonamido)phenyl)-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid
The title compound was prepared following the method described above for compound (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-9-(4-(2-carboxyethyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid (example 4a) using 3-(methylsulfonamido)phenylboronic acid as the reactant boronic acid. The product was isolated as a white solid (46.41 mg, 90%). LCMS: m/e 606.58 (M−H) − , 4.37 min (method 2). 1 H NMR (599 MHz, DMSO-D6_CDCl 3 ) δ ppm 0.93 (s, 6H), 0.99 (s, 3H), 1.00 (s, 3H), 1.02 (s, 3H), 1.03-1.74 (m, 17H), 1.71 (s, 3H), 1.84-1.96 (m, 2H), 2.11 (dd, J=16.99, 5.86 Hz, 1H), 2.20 (d, J=12.30 Hz, 1H), 2.30-2.39 (m, 1H), 2.96 (s, 3H), 2.99-3.07 (m, 1H), 4.61 (s., 1H), 4.74 (s, 1H), 5.28 (d, J=4.69 Hz, 1H), 6.87 (d, J=7.62 Hz, 1H), 7.03 (s, 1H), 7.14 (d, J=8.20 Hz, 1H), 7.25 (t, J=7.62 Hz, 1H).
Example 4h
Preparation of (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-9-(4-((E)-2-carboxyvinyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid
The title compound was prepared following the method described above for compound (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-9-(4-(2-carboxyethyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid (example 4a) using (E)-3-(4-boronophenyl)acrylic acid as the reactant boronic acid. The product was isolated as a white solid (3.65 mg, 11%). LCMS: m/e 583.60 (M−H) − , 5.03 min (method 2). 1 H NMR (599 MHz, DMSO-D6_CDCl 3 ) δ ppm 0.94 (d, J=3.52 Hz, 6H), 1.00 (s, 6H), 1.02 (s, 3H), 1.03-1.76 (m, 17H), 1.71 (s, 3H), 1.88 (d, J=7.03 Hz, 2H), 2.08-2.16 (m, 1H), 2.20 (d, J=12.30 Hz, 1H), 2.30-2.40 (m, 1H), 3.02 (d, J=5.27 Hz, 1H), 4.61 (s., 1H), 4.74 (s, 1H), 5.28 (d, J=4.69 Hz, 1H), 6.49 (d, J=15.82 Hz, 1H), 7.17 (d, J=8.20 Hz, 2H), 7.54-7.71 (m, 3H).
Example 41
Preparation of (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-9-(3-(2H-tetrazol-5-yl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid
The title compound was prepared following the method described above for compound (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-9-(4-(2-carboxyethyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid (example 4a) using 3-(2H-tetrazol-5-yl)phenylboronic acid as the reactant boronic acid. The product was isolated as a white solid (4.56 mg, 26%). LCMS: m/e 581.53 (M−H) − , 4.12 min (method 3). 1 H NMR (400 MHz, <DMSOmix>) δ ppm 0.95 (d, J=4.10 Hz, 6H), 0.99 (s, 3H), 1.01 (s, 6H), 1.03-1.76 (m, 17H), 1.69 (s, 3H), 1.81-1.93 (m, 2H), 2.07-2.23 (m, 2H), 2.34 (dd, J=13.47, 2.34 Hz, 1H), 2.95-3.06 (m, 1H), 4.58 (s, 1H), 4.72 (s, 1H), 5.32 (d, J=4.39 Hz, 1H), 7.22 (d, J=6.44 Hz, 1H), 7.38-7.51 (m, 1H), 7.81 (s, 1H), 7.92 (d, J=7.32 Hz, 1H).
Example 4j
Preparation of (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-5a,5b,8,8,11a-pentamethyl-9-(4-(methylsulfonyl)phenyl)-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid
The title compound was prepared following the method described above for compound (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-9-(4-(2-carboxyethyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid (example 4a) using 4-(methylsulfonyl)phenylboronic acid as the reactant boronic acid. The product was isolated as a white solid (3.5 mg, 20%). LCMS: m/e 591.61 (M−H) − , 6.74 min (method 3). 1 H NMR (400 MHz, <DMSOmix>) δ ppm 0.92 (s, 6H), 0.98 (s, 6H), 1.00 (s, 3H), 1.02-1.77 (m, 17H), 1.68 (s, 3H), 1.79-1.97 (m, 2H), 2.05-2.23 (m, 2H), 2.32 (t, J=13.47 Hz, 1H), 2.90-3.06 (m, 1H), 3.19 (s, 3H), 4.58 (s, 1H), 4.71 (s, 1H), 5.29 (d, J=5.57 Hz, 1H), 7.36 (d, J=6.44 Hz, 2H), 7.85 (d, J=8.20 Hz, 2H).
Example 4k
Preparation of (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-9-(3-(2-carboxyethyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid
The title compound was prepared following the method described above for compound (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-9-(4-(2-carboxyethyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid (example 4a) using (E)-3-(3-boronophenyl)acrylic acid as the reactant boronic acid. The product was isolated as a white solid (34.4 mg, 80%). LCMS: m/e 585.63 (M−H) − , 6.47 min (method 3). 1 H NMR (400 MHz, <DMSOmix>) δ ppm 0.89 (d, 6H), 0.97 (s, 6H), 1.00 (s, 3H), 1.01-1.66 (m, 17H), 1.68 (s, 3H), 1.80-1.94 (m, 2H), 2.02-2.12 (m, 1H), 2.13-2.22 (m, 1H), 2.26-2.39 (m, 1H), 2.55-2.60 (m, 2H), 2.83 (t, J=7.62 Hz, 2H), 2.94-3.07 (m, 1H), 4.58 (br. s., 1H), 4.71 (s, 1H), 5.20 (d, J=4.10 Hz, 1H), 6.88-6.98 (m, 2H), 7.08 (d, J=6.44 Hz, 1H), 7.13-7.22 (m, 1H).
Compound 41: Preparation of (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-9-(2-(2-carboxyethyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid
The title compound was prepared following the method described above for compound (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-9-(4-(2-carboxyethyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid (example 4a) using (E)-3-(2-boronophenyl)acrylic acid as the reactant boronic acid. The product was isolated as a white solid (37.4 mg, 86%). LCMS: m/e 585.58 (M−H) − , 6.84 min (method 3). 1 H NMR (400 MHz, <DMSOmix>) δ ppm 0.80 (d, 3H), 0.98 (s, 6H), 1.00 (s, 6H), 1.04-1.73 (m, 17H), 1.68 (s, 3H), 1.79-1.96 (m, 2H), 2.00-2.23 (m, 2H), 2.27-2.37 (m, 1H), 2.71-2.83 (m, 2H), 2.84-2.95 (m, 2H), 2.96-3.05 (m, 1H), 4.59 (s, 1H), 4.72 (s, 1H), 5.24 (d, J=4.98 Hz, 1H), 6.97-7.06 (m, 1H), 7.06-7.14 (m, 1H), 7.14-7.30 (m, 2H).
Compound 4m: Preparation of 3-(4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-carboxy-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)phenyl)quinoline-4-carboxylic acid
The title compound was prepared following the method described above for compound (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-9-(4-(2-carboxyethyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid (example 4a) using 2-(4-boronophenyl)quinoline-4-carboxylic acid as the reactant boronic acid. The product was isolated as a white solid (4.7 mg, 27%). LCMS: m/e 684.65 (M−H) − , 5.11 min (method 3). 1 H NMR (400 MHz, <DMSOmix>) δ ppm 0.95-1.00 (m, 9H), 1.01 (s, 6H), 1.05-1.77 (m, 17H), 1.69 (s, 3H), 1.80-1.94 (m, 2H), 2.07-2.23 (m, 2H), 2.31-2.38 (m, 1H), 2.94-3.06 (m, 1H), 4.59 (s, 1H), 4.72 (s, 1H), 5.33 (d, J=6.15 Hz, 1H), 7.30 (d, J=7.32 Hz, 2H), 7.59-7.67 (m, 1H), 7.74-7.84 (m, 1H), 8.08-8.14 (m, 1H), 8.18 (d, J=8.79 Hz, 2H), 8.32-8.42 (m, 1H), 8.72 (d, J=6.15 Hz, 1H).
Example 4n
Preparation of 5-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-carboxy-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)thiophene-2-carboxylic acid
The title compound was prepared following the method described above for compound (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-9-(4-(2-carboxyethyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid (example 4a) using 5-boronothiophene-2-carboxylic acid as the reactant boronic acid. The product was isolated as a white solid (4.15 mg, 23%). LCMS: m/e 563.53 (M−H) − , 2.94 min (method 4). 1 H NMR (400 MHz, <DMSOmix>) δ ppm 0.90 (br. s., 3H), 0.96 (s, 3H), 0.98 (s, 3H), 1.04 (s, 3H), 1.06 (s, 3H), 1.09-1.76 (m, 17H), 1.68 (s, 3H), 1.80-1.94 (m, 2H), 2.10-2.23 (m, 2H), 2.25-2.40 (m, 1H), 2.91-3.05 (m, 1H), 4.58 (br. s., 1H), 4.71 (br. s., 1H), 5.75 (d, J=5.86 Hz, 1H), 6.90 (d, J=3.22 Hz, 1H), 7.51 (br. s., 1H).
Compound 4o: Preparation of (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-9-(4-carboxy-3-chlorophenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid
The title compound was prepared following the method described above for compound (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-9-(4-(2-carboxyethyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid (example 4a) using 4-borono-2-chlorobenzoic acid as the reactant boronic acid. Purification of the product was accomplished by first using Biotage flash chromatography with a 0-50% ethyl acetate in hexanes gradient with 0.1% acetic acid added to the mixture. The compound was not sufficiently pure, so further purification by prep HPLC followed (acetonitrile/water mobile phase with TFA buffer on a C18 reverse phase column). After concentrating the desired fractions, the title compound was isolated as a white film (6.1 mg, 6.8% yield over two steps). LCMS: m/e 591.60 (M−H) − , 1.54 min (method 1). 1 H NMR (500 MHz, Pyr) δ ppm 0.92 (br. s., 6H), 0.96 (s, 3H), 1.10 (s, 3H), 1.11 (s, 3H), 1.18-1.84 (m, 15H), 1.83 (s, 3H), 1.89 (t, J=13.28 Hz, 1H), 1.99 (br. s., 1H), 2.09 (dd, J=17.09, 6.10 Hz, 1H), 2.24-2.33 (m, 2H), 2.66 (d, J=12.51 Hz, 1H), 2.81 (t, J=11.75 Hz, 1H), 3.54-3.63 (m, 1H), 4.82 (s, 1H), 5.00 (s, 1H), 5.37 (d, J=5.80 Hz, 1H), 7.24 (d, J=8.24 Hz, 1H), 7.51 (s, 1H), 8.21 (d, J=7.63 Hz, 1H).
Intermediate 4: Preparation of (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-benzyl 9-(4-(methoxycarbonyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylate
To a round bottom flask containing a solution of (1R,3aS,5aR,5bR,7aR,11aR,11bR,13bR)-benzyl 5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-9-(trifluoromethylsulfonyloxy)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylate (6.21 g, 9.18 mmol) in dioxane (25 mL) was added 2-propanol (25 mL) and water (15 mL) followed by sodium carbonate monohydrate (3.42 g, 27.5 mmol), 4-methoxycarbonylphenylboronic acid (2.478 g, 13.77 mmol), and tetrakis(triphenylphosphine)palladium(0) (0.318 g, 0.275 mmol). The flask was attached to a reflux condenser, was flushed with N 2 , and was heated to reflux overnight. After heating the mixture for 14.5 h, it was cooled to rt and was diluted with water (75 mL). The mixture was extracted with ethyl acetate (3×75 mL) and washed with brine. The combined organic layers were dried with MgSO 4 , filtered, and concentrated under reduced pressure. The residue was adsorbed to silica gel and was purified by Biotage flash chromatography using a 0-20% EtOAc in hexanes gradient. The fractions containing the expected product was combined and concentrated under reduced pressure. The expected product, (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR 13bR)-benzyl 9-(4-(methoxycarbonyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylate (4.16 g, 6.28 mmol, 68.4% yield), was isolated as a white foam. 1 H NMR (500 MHz, CHLOROFORM-d) δ ppm 0.82 (s, 3H), 0.87-1.75 (m, 17H), 0.91 (s, 3H), 0.92 (s, 3H), 0.95 (s, 3H), 0.97 (s, 3H), 1.69 (s, 3H), 1.82-1.95 (m, 2H), 2.09 (dd, J=17.24, 6.26 Hz, 1H), 2.20-2.32 (m, 2H), 3.04 (td, J=10.91, 4.73 Hz, 1H), 3.90 (s, 3H), 4.60 (s, 1H), 4.73 (d, J=1.83 Hz, 1H), 5.07-5.19 (m, 2H), 5.28 (dd, J=6.10, 1.83 Hz, 1H), 7.19 (d, J=8.24 Hz, 2H), 7.29-7.40 (m, 5H), 7.92 (d, J=8.24 Hz, 2H).
Deprotection of Benzyl Group (Method B).
Intermediate 5: Preparation of (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-tert-butyldimethylsilyl 9-(4-(methoxycarbonyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylate
To a solution of (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-benzyl 9-(4-(methoxycarbonyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylate (3.82 g, 5.76 mmol) in dichloroethane (100 mL) was added triethylamine (1.285 mL, 9.22 mmol), tert-butyldimethylsilane (1.912 mL, 11.52 mmol), and palladium(II) acetate (0.647 g, 2.88 mmol). The mixture was flushed with N 2 , then was heated to 60° C. After 2 h, the reaction was cooled to rt, was filtered through a pad of celite and silica gel to remove the solids which were washed with 25% EtOAc in hexanes. The filtrate was concentrated under reduced pressure and was treated with 20 mL of acetic acid, 10 mL of THF and 3 mL of water. After stirring for 1 h the solids that formed were collected by filtration and were washed with water to give (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-tert-butyldimethylsilyl 9-(4-(methoxycarbonyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylate (3.62 g, 5.27 mmol, 91% yield) as a white solid. 1 H NMR (400 MHz, CHLOROFORM-d) δ ppm 0.28-0.32 (m, 6H), 0.90-1.78 (m, 16H), 0.94 (s, 6H), 0.98 (s, 9H), 0.99 (br. s., 3H), 1.01 (s, 6H), 1.71 (s, 3H), 1.84-2.02 (m, 2H), 2.06-2.17 (m, 1H), 2.22-2.35 (m, 2H), 3.08 (td, J=10.92, 4.27 Hz, 1H), 3.92 (s, 4H), 4.62 (s, 1H), 4.75 (d, J=1.76 Hz, 1H), 5.30 (dd, J=6.15, 1.63 Hz, 1H), 7.21 (d, J=8.28 Hz, 2H), 7.94 (d, J=8.28 Hz, 2H).
Preparation of ((1R,3aS,5aR,5bR,7aR,9S,11aR,11bR,13aR,13bR)-9-hydroxy-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)icosahydro-1H-cyclopenta[a]chrysen-3a-yl)methyl benzoate
Betuline (2.5 g, 5.65 mmol), Benzoic anhydride (2.147 mL, 11.29 mmol) and DMAP (0.690 g, 5.65 mmol) were heated in pyridine (50 mL) for 3 h. TLC showed no starting material. The reaction was quenched with water and the mixture was concentrated in vacuo to remove most of the pyridine. Methylene chloride was added and the organic phase was separated and dried over Na 2 SO 4 . The drying agent was removed by filtration and the filtrate was concentrated under reduced pressure. The crude material containing ((1R,3aS,5aR,5bR,7aR,9S,11aR,11bR,13bR)-9-hydroxy-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)icosahydro-1H-cyclopenta[a]chrysen-3a-yl)methyl benzoate was taken to the next step without further purification.
Preparation of ((1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-5a,5b,8,8,11a-pentamethyl-9-oxo-1-(prop-1-en-2-yl)icosahydro-1H-cyclopenta[a]chrysen-3a-yl)methyl benzoate
The crude material containing ((1R,3aS,5aR,5bR,7aR,9S,11aR,11bR,13bR)-9-hydroxy-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)icosahydro-1H-cyclopenta[a]chrysen-3a-yl)methyl benzoate (2.98 g, 5.45 mmol) from page above was dissolved in CH 2 Cl 2 (50 ml) and treated with PCC (1.762 g, 8.18 mmol). The mixture was stirred at rt for 2 h. TLC showed no starting material and one less polar product. The mixture was filtered through celite and silica gel and the filtrate was concentrated in vacuo to afford the title compound as a white solid
Preparation of ((1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-9-(trifluoromethylsulfonyloxy)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-3a-yl)methyl benzoate
A mixture of ((1R,3aS,5aR,5bR,7aR,11aR,11bR,13bR)-5a,5b,8,8,11a-pentamethyl-9-oxo-1-(prop-1-en-2-yl)icosahydro-1H-cyclopenta[a]chrysen-3a-yl)methyl benzoate (2.97 g, 5.45 mmol), and N-Phenylbis(trifluoromethane)sulfonimide (3.89 g, 10.90 mmol) was stirred in THF (30 mL) at −78° C. KHMDS (0.5 in Toluene) (21.80 mL, 10.90 mmol) was slowly added and the reaction mixture and was kept at −78° C. for 1 h. TLC showed starting material and a less polar spot. KHMDS (1 eq, 5 ml) was added and the mixture was stirred at −78° C. for 1 h longer. Reaction was quenched with brine and warmed at rt. The organic layer was extracted with ether and dried over Na 2 SO 4 , filtered, concentrated and purified using silica gel (0-10% Toluene/Hexanes) to separate the excess triflate reagent from the product, ((1R,3aS,5aR,5bR,7aR,11aR,11bR,13bR)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-9-(trifluoromethylsulfonyloxy)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-3a-yl)methyl benzoate (2.22 g, 3.28 mmol, 60.2% yield for 3 steps), which was isolated as a white solid. 1 H NMR (400 MHz, CHLOROFORM-d) δ ppm 0.94 (s, 3H), 1.03 (s, 3H), 1.04 (s, 3H), 1.10-1.86 (m, 18H), 1.12 (s, 3H), 1.14 (s, 3H), 1.73 (s, 3H), 1.92-2.13 (m, 3H), 2.18 (dd, J=17.07, 6.78 Hz, 1H), 2.55 (td, J=11.11, 5.90 Hz, 1H), 4.12 (d, J=11.04 Hz, 1H), 4.55 (dd, J=11.04, 1.25 Hz, 1H), 4.64 (s, 1H), 4.75 (d, J=2.01 Hz, 1H), 5.58 (dd, J=6.65, 1.88 Hz, 1H), 7.43-7.49 (m, 2H), 7.55-7.60 (m, 1H), 8.05-8.09 (m, 2H).
General Method for the Preparation of Compounds 5a-u
Step 1: Suzuki Coupling
To a sealable vial containing ((1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-9-(trifluoromethylsulfonyloxy)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-3a-yl)methyl benzoate (0.074-0.322 mmol) was added the corresponding boronic acid (1.05-1.5 equiv.), base (either K 3 PO 4 (4 equiv.) or sodium carbonate monohydrate (3 equiv.)), and tetrakis(triphenylphosphine)palladium(0) (0.03-0.1 equiv.). The mixture was diluted with either 1,4-dioxane, a mixture of 1,4-dioxane:water (4:1), a mixture of 2-propanol:water (4:1), or a mixture of 1,4-dioxane:2-propanol:water (2:2:1) to a concentration of 0.059-0.074 M. The vial was flushed with N 2 , sealed, and heated to 85° C.-100° C. After 3-24 h of heating, the mixture was cooled to rt. The mixture was diluted with either sat. NH 4 Cl, 1N HCl, or water and was extracted with dichloromethane. The combined organic layers were dried with Na 2 SO 4 . The drying agent was removed by filtration and the filtrate was concentrated under reduced pressure. The residue was either used directly in the next step, or was purified by Biotage flash chromatography to afford the expected C-3 coupled product which was used in the next step.
Step 2: Deprotection of Alcohol
To a solution of the C-3 coupled product from the previous step (0.058-0.295 mmol) in dioxane:water (3:1 or 4:1) was added lithium hydroxide monohydrate (19-43 equiv.). The mixture was heated to 75° C. for 3-15 h, was cooled to rt, and was quenched with 1N HCl. The mixture was extracted with dichloromethane and the organic layers were combined and dried with Na 2 SO 4 . The drying agent was removed by filtration and the filtrate was concentrated under reduced pressure. The residue was purified by either Biotage flash chromatography, crystallization from dioxane and water, or prep HPLC to give the expected deprotected product.
Example 5a
Preparation of 2-chloro-4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13bR)-3a-(hydroxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)benzoic acid
The title compound was prepared by the general method described above using 4-carboxy-3-chlorophenylboronic acid as the reactant boronic acid. The product was purified by biotage flash chromatography using a 25-50% EtOAc in hexanes gradient with 0.1% HOAc added. Fractions containing the product were concentrated to give the title compound as a white solid (20.1 mg, 0.034 mmol, 11.5% yield over two steps). LCMS: m/e 577.6 (M−H) − , 1.60 min (method 1). 1 H NMR (500 MHz, CHLOROFORM-d) δ ppm 0.93 (s, 3H), 0.93 (s, 3H), 0.96 (s, 3H), 1.00-2.12 (m, 22H), 1.01 (s, 3H), 1.08 (s, 3H), 1.69 (s, 3H), 2.40 (td, J=10.99, 5.80 Hz, 1H), 3.36 (d, J=10.68 Hz, 1H), 3.84 (d, J=10.68 Hz, 1H), 4.59 (s, 1H), 4.69 (d, J=1.83 Hz, 1H), 5.31 (dd, J=6.10, 1.53 Hz, 1H), 7.10 (dd, J=7.93, 1.53 Hz, 1H), 7.25 (s, 1H), 7.89 (d, J=7.93 Hz, 1H).
Example 5b
Preparation of 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13bR)-3a-(hydroxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)benzoic acid
The title compound was prepared by the general method described above using 4-ethoxycarbonylphenylboronic acid as the reactant boronic acid. The product was purified by Biotage flash chromatography using a 0-5% MeOH in dichloromethane gradient followed by crystallization from dioxane and water. The product was isolated as a white solid (12 mg, 0.022 mmol, 29.5% yield over two steps). LCMS: m/e 543.6 (M−H) − , 1.82 min (method 1). 1 H NMR (400 MHz, Pyr) δ ppm 1.02 (s, 3H), 1.03 (s, 6H), 1.10 (s, 3H), 1.10 (s, 3H), 1.11-2.02 (m, 18H), 1.82 (s, 3H), 2.09-2.27 (m, 2H), 2.41-2.52 (m, 2H), 2.68 (td, J=10.92, 5.77 Hz, 1H), 3.71 (d, J=10.79 Hz, 1H), 4.14 (d, J=10.79 Hz, 1H), 4.80 (s, 1H), 4.94 (d, J=2.26 Hz, 1H), 5.42 (d, J=4.52 Hz, 1H), 7.42 (d, J=8.03 Hz, 2H), 8.47 (d, J=8.03 Hz, 2H).
Example 5c
Preparation of 5-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13bR)-3a-(hydroxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)thiophene-2-carboxylic acid
The title compound was prepared by the general method described above using 2-carboxythiophene-5-boronic acid as the reactant boronic acid. The product was purified by crystallization from dioxane and water. The title compound was isolated as an off-white solid (15 mg, 0.027 mmol, 36% yield over two steps). LCMS: m/e 549.5 (M−H) − , 1.63 min (method 1). 1 H NMR (400 MHz, Pyr) δ ppm 0.92 (s, 3H), 1.00-2.00 (m, 18H), 1.06 (s, 3H), 1.09 (s, 3H), 1.14 (s, 3H), 1.17 (s, 3H), 1.81 (s, 3H), 2.09-2.27 (m, 2H), 2.40-2.52 (m, 2H), 2.67 (td, J=10.92, 5.77 Hz, 1H), 3.71 (d, J=10.79 Hz, 1H), 4.13 (d, J=10.54 Hz, 1H), 4.80 (s, 1H), 4.94 (d, J=2.26 Hz, 1H), 5.90 (dd, J=6.27, 2.01 Hz, 1H), 7.07 (d, J=3.76 Hz, 1H), 8.05 (d, J=3.76 Hz, 1H).
Example 5d
Preparation of 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13bR)-3a-(hydroxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)thiophene-2-carboxylic acid
The title compound was prepared by the general method described above using 4-boronothiophene-2-carboxylic acid as the reactant boronic acid. The product was purified by crystallization from dioxane and water followed by Biotage flash chromatography using 0-10% MeOH in dichloromethane with 0.1% HOAc added. The title compound was isolated as a white solid (10 mg, 0.017 mmol, 23% yield over two steps). LCMS: m/e 549.3 (M−H) − , 1.55 min (method 1). 1 H NMR (400 MHz, CHLOROFORM-d) δ ppm 0.81-1.79 (m, 24H), 1.03 (s, 3H), 1.10 (br. s., 3H), 1.27 (s, 3H), 1.71 (s, 3H), 1.84-2.15 (m, 4H), 2.37-2.47 (m, 1H), 3.38 (d, J=10.79 Hz, 1H), 3.84 (d, J=10.54 Hz, 1H), 4.61 (s, 1H), 4.71 (s, 1H), 5.44 (br. s., 1H), 7.18 (br. s., 1H), 7.65 (br. s., 1H).
Example 5e
Preparation of 5-((1R,3aS,5aR,5bR,7aR,11aS,13aR,13bR)-3a-(hydroxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)pyridin-2-ol
The title compound was prepared following the method described above using 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-2-ol as the reactant boronic acid. The product was isolated as a white solid (5.46 mg, 33%). LCMS: m/e 518.38 (M+H) + , 5.38 min (method 9). 1 H NMR (600 MHz, DMSO-D6_CDCl 3 ) ppm 0.88 (s, 3H), 0.91 (s, 3H), 0.93 (s, 3H), 0.99 (s, 3H), 1.07 (s, 3H) 1.00-1.78 (m, 17H), 1.68 (s, 3H), 1.85-1.99 (m, 3H), 2.05 (dd, J=17.28, 6.15 Hz, 1H), 2.35-2.47 (m, 1H), 3.14 (dd, J=10.25, 4.98 Hz, 1H), 3.22 (d, J=5.27 Hz, 1H), 3.53-3.64 (m, 1H), 4.19 (br. s., 1H), 4.56 (br. s., 1H), 4.68 (br. s., 1H), 5.32 (d, J=4.69 Hz, 1H), 6.26 (d, J=9.37 Hz, 1H), 6.96 (br. s., 1H), 7.15-7.30 (m, 1H), 11.46 (br. s., 1H).
Example 5f
Preparation of 2-fluoro-4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(hydroxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)phenol
The title compound was prepared following the method described above using 2-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol as the reactant boronic acid. The product was isolated as a white solid (12.9 mg, 77%). LCMS: m/e 535.46 (M+H) + , 6.27 min (method 9). 1 H NMR (600 MHz, DMSO-D6_CDCl 3 ) δ ppm 0.89 (s, 3H), 0.91 (s, 3H), 0.94 (s, 3H), 0.99 (s, 3H), 1.07 (s, 3H), 1.01-1.78 (m, 17H), 1.67 (s, 3H), 1.86-1.99 (m, 3H), 2.05 (dd, J=16.99, 6.44 Hz, 1H), 2.38-2.48 (m, 1H), 3.14 (dd, J=9.96, 5.27 Hz, 1H), 3.22 (d, J=5.27 Hz, 1H), 3.59 (dd, J=9.67, 5.57 Hz, 1H), 4.16-4.27 (m, 1H), 4.56 (br. s., 1H), 4.69 (br. s., 1H), 5.24 (d, J=4.69 Hz, 1H), 6.69 (d, J=8.20 Hz, 1H), 6.78 (d, J=12.30 Hz, 1H), 6.84 (t, J=8.79 Hz, 1H), 9.54 (br. s., 1H).
Compound 5g: Preparation of 2-chloro-4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(hydroxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)phenol
The title compound was prepared following the method described above using 2-chloro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol as the reactant boronic acid. The product was isolated as a white solid (7.56 mg, 45%). LCMS: m/e 551.47 (M−H) − , 6.53 min (method 9). 1 H NMR (600 MHz, DMSO-D6_CDCl 3 ) δ ppm 0.89 (s, 3H), 0.91 (s, 3H), 0.94 (s, 3H), 0.99 (s, 3H), 1.02-1.78 (m, 17H), 1.08 (s, 3H), 1.68 (s, 3H), 1.86-1.99 (m, 3H), 2.06 (dd, J=16.99, 5.86 Hz, 1H), 2.34-2.47 (m, 1H), 3.14 (dd, J=10.25, 4.98 Hz, 1H), 3.22 (d, J=5.27 Hz, 1H), 3.59 (dd, J=10.25, 4.98 Hz, 1H), 4.19 (br. s., 1H), 4.56 (br. s., 1H), 4.69 (br. s., 1H), 5.23 (d, J=5.27 Hz, 1H), 6.82-6.91 (m, 2H), 6.99 (s, 1H), 9.86 (br. s., 1H).
Compound 5h: Preparation of 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(hydroxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)-3-methylphenol
The title compound was prepared following the method described above using 3-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol as the reactant boronic acid. The product was isolated as a white solid (10.42 mg, 62%). LCMS: m/e 531.46 (M+H) + , 6.37 min (method 9). 1 H NMR (600 MHz, DMSO-D6_CDCl 3 ) δ ppm 1.00 (s, 9H), 1.08 (s, 6H), 1.04-1.81 (m, 17H), 1.68 (s, 3H), 1.86-2.00 (m, 3H), 2.02-2.10 (m, 1H), 2.14 (s, 3H), 2.42 (d, J=6.44 Hz, 1H), 3.14 (dd, J=10.55, 5.27 Hz, 1H), 3.22 (d, J=5.27 Hz, 1H), 3.53-3.66 (m, 1H), 4.19 (br. s., 1H), 4.56 (br. s., 1H), 4.69 (s, 1H), 5.15 (d, J=5.27 Hz, 1H), 6.49 (d, J=8.20 Hz, 1H), 6.57 (br. s., 1H), 6.79 (d, J=7.03 Hz, 1H), 8.98 (br. s., 1H).
Example 5i
Preparation of N-(4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(hydroxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)phenyl)methanesulfonamide
The title compound was prepared following the method described above using 4-(methylsulfonamido)phenylboronic acid as the reactant boronic acid. The product was isolated as a white solid (3.97 mg, 23%). LCMS: m/e 592.78 (M−H) − , 5.76 min (method 9). 1 H NMR (600 MHz, DMSO-D6_CDCl 3 ) δ ppm 0.90 (s., 3H), 0.91 (s., 3H), 0.96 (s, 3H), 1.00 (s, 3H), 1.08 (s, 3H), 0.97-1.78 (m, 17H), 1.68 (s, 3H), 1.85-2.00 (m, 3H), 2.07 (dd, J=16.70, 6.15 Hz, 1H), 2.37-2.47 (m, 1H), 2.97 (s, 3H), 3.14 (dd, J=10.55, 5.27 Hz, 1H), 3.22 (d, J=5.27 Hz, 1H), 3.55-3.64 (m, 1H), 4.19 (br. s., 1H), 4.56 (br. s., 1H), 4.69 (br. s., 1H), 5.23 (d, J=4.69 Hz, 1H), 7.05 (d, J=8.79 Hz, 2H), 7.13 (d, J=8.79 Hz, 2H), 9.61 (br. s., 1H).
Compound 5j: Preparation of 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(hydroxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)benzenesulfonamide
The title compound was prepared following the method described above using 4-(N-cyclopropylsulfamoyl)phenylboronic acid as the reactant boronic acid. White solid (1.87 mg, 12%). LCMS: m/e 578.75 (M−H) − , 5.19 min (method 9). 1 H NMR (600 MHz, DMSO-D6_CDCl 3 ) δ ppm 0.92 (br. s., 6H), 0.98 (s, 3H), 1.00 (s, 3H), 1.09 (s, 3H), 1.01-1.77 (m, 17H), 1.68 (s, 3H), 1.86-2.01 (m, 3H), 2.10 (dd, J=16.70, 6.15 Hz, 1H), 2.37-2.46 (m, 1H), 3.09-3.18 (m, 1H), 3.22 (d, J=5.27 Hz, 1H), 3.53-3.64 (m, 1H), 4.20 (br. s., 1H), 4.56 (br. s., 1H), 4.69 (br. s., 1H), 5.27 (d, J=4.69 Hz, 1H), 7.24-7.33 (m, 4H), 7.77 (d, J=7.62 Hz, 2H).
Example 5k
Preparation of 3-fluoro-4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(hydroxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)benzoic acid
The title compound was prepared following the method described above using 4-(ethoxycarbonyl)-2-fluorophenylboronic acid as the reactant boronic acid. The product was isolated as a white solid (10.57 mg, 25%). LCMS: m/e 563.45 (M+H) + , 14.26 min (method 8). 1 H NMR (600 MHz, DMSO-D6_CDCl 3 ) δ ppm 0.88 (s, 3H), 0.94 (s, 3H), 0.99 (s, 3H), 1.01 (s, 3H), 1.09 (s, 3H), 1.01-1.79 (m, 17H), 1.68 (s, 3H), 1.84-2.02 (m, 3H), 2.11 (dd, J=17.28, 6.74 Hz, 1H), 2.36-2.47 (m, 1H), 3.14 (d, J=9.37 Hz, 1H), 3.22-3.26 (m, 1H), 3.59 (d, J=10.55 Hz, 1H), 4.18 (br. s., 1H), 4.56 (br. s., 1H), 4.69 (s, 1H), 5.33 (d, J=5.27 Hz, 1H), 7.22 (t, J=7.62 Hz, 1H), 7.61 (d, J=8.79 Hz, 1H), 7.71 (d, J=7.62 Hz, 1H).
Example 5l
Preparation of ((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-9-(4-(2H-tetrazol-5-yl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-3a-yl)methanol
The title compound was prepared following the method described above using 4-(2H-tetrazol-5-yl)phenylboronic acid as the reactant boronic acid. The product was isolated as a white solid (0.66 mg, 1.6%). LCMS: m/e 569.51 (M+H) + , 14.28 min (method 8).
Example 5m
Preparation of 2-fluoro-4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(hydroxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)benzoic acid
The title compound was prepared following the method described above using 4-borono-2-fluorobenzoic acid as the reactant boronic acid. The product was isolated as a white solid (0.9 mg, 2%). LCMS: m/e 563.35 (M+H) + , 14.19 min (method 8).
Example 5n
Preparation of 3-chloro-4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(hydroxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)benzoic acid
The title compound was prepared following the method described above using 4-borono-3-chlorobenzoic acid as the reactant boronic acid. The product was isolated as a white solid (10.37 mg, 24%). LCMS: m/e 579.67 (M+H) + , 14.44 min (method 8). 1 H NMR (600 MHz, DMSO-D6_CDCl 3 ) δ ppm 0.92-0.98 (m, 3H), 0.99-1.04 (m, 6H), 1.03-1.08 (m, 3H), 1.09 (s, 3H), 1.11-1.81 (m, 17H), 1.68 (s, 3H), 1.85-2.02 (m, 3H), 2.14 (dd, J=16.70, 5.57 Hz, 1H), 2.38-2.47 (m, 1H), 3.14 (d, J=6.44 Hz, 1H), 3.23-3.27 (m, 1H), 3.59 (d, J=9.96 Hz, 1H), 4.18 (br. s., 1H), 4.56 (s., 1H), 4.69 (s., 1H), 5.31 (d, J=5.27 Hz, 1H), 7.32 (d, J=6.45 Hz, 1H), 7.82 (d, J=8.20 Hz, 1H), 7.94 (s, 1H).
Example 5o
Preparation of 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(hydroxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)-2-methoxybenzoic acid
The title compound was prepared following the method described above using 4-borono-2-methoxybenzoic acid as the reactant boronic acid. The product was isolated as a white solid (0.9 mg, 2%). LCMS: m/e 575.50 (M+H) + , 14.29 min (method 8).
Example 5p
Preparation of 2-hydroxy-4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(hydroxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)benzoic acid
The title compound was prepared following the method described above using 3-hydroxy-4-(methoxycarbonyl)phenylboronic acid as the reactant boronic acid. The product was isolated as a white solid (17.6 mg, 42%). LCMS: m/e 561.39 (M+H) + , 14.15 min (method 8). 1 H NMR (600 MHz, DMSO-D6_CDCl 3 ) δ ppm 0.94 (s, 6H), 0.96 (s, 3H), 1.00 (s, 3H), 1.08 (s, 3H), 1.02-1.79 (m, 17H), 1.68 (s, 3H), 1.85-2.02 (m, 3H), 2.09 (dd, J=15.82, 4.69 Hz, 1H), 2.38-2.46 (m, 1H), 3.11-3.18 (m, 1H), 3.20-3.22 (m, 1H), 3.59 (d, J=7.62 Hz, 1H), 4.18 (br. s., 1H), 4.56 (br. s., 1H), 4.69 (br. s., 1H), 5.27 (br. s., 1H), 6.63 (br. s., 2H), 7.68 (d, J=7.03 Hz, 1H).
Example 5q
Preparation of 5-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(hydroxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)pyrimidine-2-carboxylic acid
The title compound was prepared following the method described above using 2-cyanopyrimidin-5-ylboronic acid as the reactant boronic acid. The product was isolated as a white solid (1.13 mg, 3%). LCMS: m/e 547.38 (M+H) + , 13.57 min (method 8).
Example 5r
Preparation of 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(hydroxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)-3-methylbenzoic acid
The title compound was prepared following the method described above using 4-(methoxycarbonyl)-2-methylphenylboronic acid as the reactant boronic acid. The product was isolated as a white solid (13 mg, 20%). LCMS: m/e 557.64 (M−H) − , 2.22 min (method 7). 1 H NMR (500 MHz, CHLOROFORM-d) δ ppm 0.99 (s, 3H), 1.02 (s, 6H), 1.06 (d, J=5.49 Hz, 3H), 1.09 (s, 3H), 1.11-1.78 (m, 15H), 1.69 (s, 3H), 1.83-1.90 (m, 2H), 1.90-2.02 (m, 3H), 2.11 (dd, J=17.24, 5.65 Hz, 1H), 2.31 (s, 3H), 2.36-2.46 (m, 1H), 3.35 (d, J=10.68 Hz, 1H), 3.66-3.68 (m, 1H), 3.83 (d, J=11.60 Hz, 1H), 4.59 (s., 1H), 4.69 (d, J=1.83 Hz, 1H), 5.24 (d, J=4.58 Hz, 1H), 7.14 (d, J=8.24 Hz, 1H), 7.79 (d, J=7.63 Hz, 1H), 7.91 (s., 1H).
Example 5s
Preparation of 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(hydroxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)-2-(trifluoromethyl)benzoic acid
The title compound was prepared following the method described above using 4-borono-2-(trifluoromethyl)benzoic acid as the reactant boronic acid. The product was isolated as a white solid (28 mg, 89%). LCMS: m/e 611.39 (M−H) − , 2.2 min (method 7). 1 H NMR (500 MHz, DMSO-d 6 ) δ 7.32 (d, J=7.9 Hz, 1H), 7.23 (s, 1H), 7.17 (s, 1H), 5.24 (d, J=4.6 Hz, 1H), 4.68 (d, J=2.4 Hz, 1H), 4.55 (s, 1H), 3.55 (d, J=10.7 Hz, 1H), 3.10 (d, J=10.7 Hz, 1H), 2.46-2.36 (m, 1H), 2.06 (dd, J=17.2, 6.3 Hz, 1H), 1.95-1.01 (m, 21H), 1.65 (s, 3H), 1.05 (s, 3H), 0.98 (s, 4H), 0.94 (s, 3H), 0.89 (s, 3H), 0.87 (s, 3H).
Example 5t
Preparation of 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(hydroxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)phthalic acid
The title compound was prepared following the method described above using 4-boronophthalic acid
as the reactant boronic acid. The product was isolated as a white solid (3 mg, 42%). LCMS: m/e 587.4 (M−H) − , 2.25 min (method 7). 1 H NMR (500 MHz, DMSO-d 6 ) δ 8.08 (d, J=8.2 Hz, 1H), 7.92 (d, J=2.1 Hz, 1H), 7.22 (dd, J=8.1, 2.0 Hz, 1H), 5.24 (d, J=4.9 Hz, 1H), 4.69 (d, J=2.7 Hz, 1H), 4.55 (s, 1H), 3.56 (d, J=10.4 Hz, 1H), 3.10 (d, J=11.3 Hz, 1H), 2.48-2.39 (m, 1H), 2.15-2.03 (m, 1H), 1.96-0.92 (m, 21H), 1.65 (s, 3H), 1.06 (s, 3H), 0.98 (s, 3H), 0.95 (s, 3H), 0.89 (s, 6H).
Example 5u
Preparation of 6-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(hydroxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)nicotinic acid
The title compound was prepared following the method described above using 5-(methoxycarbonyl)pyridin-2-ylboronic acid as the reactant boronic acid. The product was isolated as a white solid (2.1 mg, 59%). LCMS: m/e 544.32 (M−H) − , 2.11 min (method 7). 1 H NMR (500 MHz, DMSO-d 6 ) δ 8.87 (d, J=1.2 Hz, 1H), 8.04 (dd, J=7.9, 1.8 Hz, 1H), 7.20 (d, J=7.9 Hz, 1H), 5.57 (d, J=4.3 Hz, 1H), 4.69 (d, J=2.1 Hz, 1H), 4.55 (s, 1H), 3.55 (d, J=11.0 Hz, 1H), 3.10 (d, J=10.7 Hz, 1H), 2.46-2.34 (m, 1H), 2.13 (dd, J=17.4, 6.1 Hz, 1H), 1.92-1.07 (m, 21H), 1.65 (s, 3H), 1.13 (s, 3H), 1.05 (s, 3H), 0.98 (d, J=2.1 Hz, 6H), 0.90 (s., 3H).
Preparation of (1R,3aS,5aR,5bR,7aR,11aS,13aR,13bR)-benzyl 9-(4-(chlorocarbonyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylate
A mixture of (1R,3aS,5aR,5bR,7aR,11aR,13aR,13bR)-benzyl 5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-9-(trifluoromethylsulfonyloxy)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylate (300 mg, 0.443 mmol), 4-boronobenzoic acid (88 mg, 0.532 mmol), Pd(Ph 3 P) 4 (15.36 mg, 0.013 mmol) and Na 2 CO 3 (141 mg, 1.330 mmol) in Water (1 mL) and DME (1 mL) was heated up at 100° C. for 2 hours. LCMS indicated the formation of the precursor of the desired product. The reaction mixture was quenched with distilled water (5 mL) and extracted with ethyl acetate (3×5 mL). The extracts were combined and dried over Na 2 SO 4 . The organic solution was filtered and concentrated under reduced pressure to provide the crude precursor of the desired product. LCMS: m/e 647.59 (M−H) − , 2.44 min (method 7). The residue was dissolved in CH 2 Cl 2 (1.000 mL), then SOCl 2 (0.647 mL, 8.86 mmol) was added. The reaction mixture was refluxed for 17 hours and concentrated under reduced pressure. The residue was dried under vacuum for 3 hours to provide the desired product (1R,3aS,5aR,5bR,7aR,11aS,13aR,13bR)-benzyl 9-(4-(chlorocarbonyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylate as yellow oil (120 mg, 41%). The compound was quenched with methanol to form a methyl ester. LCMS: m/e 663.57 (M+H) + , 2.92 min (method 7).
Example 6a
Preparation of (1R,3aS,5aR,5bR,7aR,11aS,13aR,13bR)-9-(4-(isopropylsulfonylcarbamoyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid
To a mixture of propane-2-sulfonamide (18.46 mg, 0.150 mmol), DMAP (0.915 mg, 7.49 μmol) and Hunig's Base (0.065 mL, 0.375 mmol) in DME (2 mL) was added (1R,3aS,5aR,5bR,7aR,11aS,13aR,13bR)-benzyl 9-(4-(chlorocarbonyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylate (50 mg, 0.075 mmol). The reaction mixture was stirred for 16 hours. LCMS indicated the formation of the desired product. The reaction mixture was quenched with distilled water, extracted with ethyl acetate and concentrated under reduced pressure to give crude intermediate (1R,3aS,5aR,5bR,7aR,11aS,13aR,13bR)-benzyl 9-(4-(isopropylsulfonylcarbamoyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylate as a yellow solid. LCMS: m/e 754.60 (M+H) + , 2.36 min (method 7). To this intermediate (50 mg, 0.066 mmol) in EtOAc (2 mL) and MeOH (2.00 mL) was added 10% Pd/C (21.17 mg, 0.020 mmol). The reaction mixture was hydrogentated using a Parr shaker at 40 Psi for 17 hours. LCMS indicated the reaction was completed. The reaction mixture was filtered through a pad of celite and concentrated under reduced. The residue was purified by prep HPLC to provide the desired product, (1R,3aS,5aR,5bR,7aR,11aS,13aR,13bR)-9-(4-(isopropylsulfonylcarbamoyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid, as a white solid (12 mg, 26%). LCMS: m/e 664.48 (M+H) + , 2.18 min (method 7). 1 H NMR (500 MHz, CHLOROFORM-d) δ ppm 0.91 (s, 6H), 0.96 (s, 3H), 1.00 (d, J=4.27 Hz, 6H), 1.18-1.27 (m, 8H), 1.35-1.55 (m, 13H), 1.60-1.75 (m, 5H), 1.94-2.03 (m, 2H), 2.07-2.14 (m, 1H), 2.22-2.31 (m, 2H), 2.97-3.07 (m, 1H), 3.98-4.08 (m, 1H), 4.61 (s, 1H), 4.74 (s, 1H), 5.28 (d, J=4.88 Hz, 1H), 7.23-7.25 (m, 2H), 7.74 (d, J=8.24 Hz, 2H).
Example 6b
Preparation of (1R,3aS,5aR,5bR,7aR,11aS,13aR,13bR)-5a,5b,8,8,11a-pentamethyl-9-(4-(methylsulfonylcarbamoyl)phenyl)-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid
The title compound was prepared from the procedure described above for (1R,3aS,5aR,5bR,7aR,11aS,13aR,13bR)-benzyl 9-(4-(chlorocarbonyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylate using methanesulfonamide as the reactant sulfonamide. The title compound was isolated as a white solid (3.2 mg, 7%). LCMS: m/e 636.51 (M+H) + , 2.13 min (method 7). 1 H NMR (500 MHz, DMSO-D6) δ ppm 0.88 (d, J=3.05 Hz, 6H), 0.94 (s, 6H), 0.98 (s, 3H), 1.11-1.62 (m, 15H), 1.63-1.72 (m, 5H), 1.77-1.88 (m, 2H), 2.03-2.17 (m, 2H), 2.24-2.35 (m, 1H), 2.97 (d, J=4.58 Hz, 1H), 3.57 (s, 3H), 4.58 (s, 1H), 4.71 (d, J=1.83 Hz, 1H), 5.23 (d, J=4.58 Hz, 1H), 7.17 (d, J=8.24 Hz, 2H), 7.86 (d, J=8.24 Hz, 2H), 12.03 (s, 1H), 12.10 (br. s., 1H).
Example 7
Preparation of (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-9-(4-(methoxycarbonyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid
To solution of (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-tert-butyldimethylsilyl 9-(4-(methoxycarbonyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylate (3.12 g, 4.54 mmol) in Dioxane (25 mL) was added TBAF (75% wt in water) (2.375 g, 6.81 mmol). The mixture was stirred at rt for 4 h then was diluted with 1N HCl (25 mL) and water (5 mL) and extracted with dichloromethane (3×100 mL). The combined organic layers were dried with Na 2 SO 4 , filtered, and partially concentrated under reduced pressure to a volume of 10 mL. To the partially concentrated mixture was added 1N HCl (50 mL). The solids that formed were collected by filtration and were washed with water. The expected product, (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-9-(4-(methoxycarbonyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid (2.58 g, 4.50 mmol, 99% yield), was isolated as a white solid. LCMS: m/e 571.47 (M−H) − , 3.60 min (method 7). 1 H NMR (500 MHz, CHLOROFORM-d) δ ppm 0.89-1.79 (m, 17H), 0.91 (s, 6H), 0.98 (s, 3H), 1.00 (br. s., 3H), 1.01 (br. s., 3H), 1.70 (s, 3H), 1.94-2.06 (m, 2H), 2.10 (dd, J=17.09, 6.10 Hz, 1H), 2.21-2.33 (m, 2H), 2.99-3.07 (m, 1H), 3.90 (s, 3H), 4.62 (br. s., 1H), 4.75 (s, 1H), 5.26-5.32 (m, 1H), 7.18 (d, J=8.24 Hz, 2H), 7.92 (d, J=8.24 Hz, 2H), 9.80 (br. s., 1H).
Preparation of ethyl 3-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(benzoyloxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)-1H-pyrazole-5-carboxylate
To a sealable vial containing ethyl 3-(tributylstannyl)-1H-pyrazole-5-carboxylate (0.052 g, 0.122 mmol) was added ((1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-9-(trifluoromethylsulfonyloxy)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-3a-yl)methyl benzoate (0.075 g, 0.111 mmol), lithium chloride (0.014 g, 0.332 mmol), and tetrakis(triphenylphosphine)palladium(0) (6.40 mg, 5.54 μmol). The mixture was diluted with 1,4-Dioxane (2 mL) and was flushed with N 2 . The vial was sealed and heated to 85° C. for 15.5 h. The mixture was cooled to rt, was diluted with water (4 mL) and was extracted with dichloromethane (3×4 mL). The combined organic layers were dried with Na 2 SO 4 . The drying agent was removed by filtration and the filtrate was concentrated under reduced pressure. The residue purified by Biotage flash chromatography using a 0-25% EtOAc in hexanes gradient. The fractions containing the expected product were combined and concentrated under reduced pressure to give ethyl 3-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(benzoyloxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)-1H-pyrazole-5-carboxylate (0.070 g, 0.105 mmol, 95% yield) as a white solid. LCMS: m/e 665.66 (M−H) − , 2.74 min (method 1). 1 H NMR (500 MHz, CHLOROFORM-d) δ ppm 0.85-1.84 (m, 21H), 0.91 (s, 3H), 1.02 (s, 3H), 1.03 (br. s., 3H), 1.05 (s, 3H), 1.10 (s, 3H), 1.71 (s, 3H), 1.89-2.07 (m, 3H), 2.15 (dd, J=17.70, 6.41 Hz, 1H), 2.53 (td, J=11.06, 5.95 Hz, 1H), 4.11 (d, J=10.99 Hz, 1H), 4.38 (q, J=7.02 Hz, 2H), 4.52 (d, J=10.07 Hz, 1H), 4.61 (s, 1H), 4.72 (d, J=1.53 Hz, 1H), 5.75 (d, J=4.58 Hz, 1H), 6.73 (s, 1H), 7.44 (t, J=7.78 Hz, 2H), 7.55 (t, J=7.32 Hz, 1H), 8.05 (d, J=7.02 Hz, 2H).
Example 8
Preparation of 3-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(hydroxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)-1H-pyrazole-5-carboxylic acid
To a solution of ethyl 3-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(benzoyloxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)-1H-pyrazole-5-carboxylate (0.07 g, 0.105 mmol) in 1,4-Dioxane (4 mL) was added Water (1 mL) and lithium hydroxide monohydrate (0.085 g, 2.026 mmol). The mixture was heated to 75° C. for 18.25 h, was cooled to rt, and was quenched with 1N HCl (7 mL). The mixture was extracted with dichloromethane (4×7 mL) and the combined organic layers were dried with Na 2 SO 4 . The drying agent was removed by filtration and the filtrate was concentrated under reduced pressure. Purification was accomplished by crystallization from dioxane and water to give 3-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(hydroxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)-1H-pyrazole-5-carboxylic acid (0.03 g, 0.052 mmol, 49.2% yield) as a white solid. LCMS: m/e 533.60 (M−H) − , 1.24 min (method 1). 1 H NMR (500 MHz, Pyr) δ ppm 0.86 (t, J=7.48 Hz, 3H), 0.95 (s, 3H), 1.06 (s, 6H), 1.06-1.99 (m, 22H), 1.80 (s, 3H), 2.14-2.24 (m, 2H), 2.40-2.51 (m, 2H), 2.65 (dt, J=10.99, 5.49 Hz, 1H), 3.69 (d, J=10.68 Hz, 1H), 4.12 (d, J=10.68 Hz, 1H), 4.79 (s, 1H), 4.93 (d, J=2.14 Hz, 1H), 6.13 (br. s., 1H), 7.33 (s, 1H).
Preparation of ethyl 5-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(benzoyloxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)isoxazole-3-carboxylate
To a sealable vial containing ethyl 5-(tributylstannyl)isoxazole-3-carboxylate (0.052 g, 0.122 mmol) was added ((1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-9-(trifluoromethylsulfonyloxy)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-3a-yl)methyl benzoate (0.075 g, 0.111 mmol), lithium chloride (0.014 g, 0.332 mmol), and tetrakis(triphenylphosphine)palladium(0) (6.40 mg, 5.54 μmol). The mixture was diluted with 1,4-Dioxane (2 mL) and was flushed with N 2 . The vial was sealed and heated to 85° C. After 15.5 h of heating, the mixture was cooled to rt, was diluted with water (4 mL), and was extracted with dichloromethane (3×4 mL). The combined organic layers were dried over Na 2 SO 4 . The drying agent was removed by filtration and the filtrate was concentrated under reduced pressure. The residue was purified by Biotage flash chromatography using a 0-10% EtOAc in hexanes gradient. The fractions containing the expected product were combined and concentrated under reduced pressure. Ethyl 5-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(benzoyloxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)isoxazole-3-carboxylate was isolated as an off-white foam (0.015 g total mass, 0.022 mmol, 20.3% yield). LCMS: m/e 668.53 (M+H) + , 3.11 min (method 1).
Example 9
Preparation of 5-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(hydroxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)isoxazole-3-carboxylic acid
To a solution of ethyl 5-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(benzoyloxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)isoxazole-3-carboxylate (0.015 g, 0.022 mmol) in 1,4-Dioxane (2 mL) was added Water (0.5 mL) and Lithium hydroxide monohydrate (0.17 g, 4.05 mmol). The mixture was heated to 75° C. After 3.5 h the mixture was cooled to rt and was diluted with 1N HCl (7 mL) then was extracted with dichloromethane (4×7 mL). The combined organic layers were dried with Na 2 SO 4 . The drying agent was removed by filtration and the filtrate was concentrated under reduced pressure. The residue was purified by crystallization using dioxane, water, and methanol. The expected product, 5-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(hydroxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)isoxazole-3-carboxylic acid (4 mg, 7.17 mmol, 31.9% yield), was isolated as a white solid. LCMS: m/e 536.35 (M+H) + , 2.03 min (method 7). 1 H NMR (500 MHz, Pyr) δ ppm 0.87 (s, 3H), 0.96-1.88 (m, 20H), 1.04 (s, 3H), 1.05 (s, 3H), 1.17 (s, 3H), 1.21 (s, 3H), 1.81 (s, 3H), 2.14-2.27 (m, 1H), 2.39-2.53 (m, 1H), 2.59-2.74 (m, 1H), 3.70 (d, J=10.99 Hz, 1H), 4.12 (d, J=10.99 Hz, 1H), 4.80 (br. s., 1H), 4.94 (s, 1H), 6.40 (d, J=6.41 Hz, 1H), 7.08 (s, 1H).
Example 10
Preparation of 4-((1S,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(hydroxymethyl)-1-isopropyl-5a,5b,8,8,11a-pentamethyl-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)benzoic acid
A mixture of 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(hydroxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a, 8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)benzoic acid (50 mg, 0.092 mmol) and a catalytic amount of Pd/C (9.77 mg, 0.092 mmol) was dissolved in a mixture of methanol (1 mL) and ethyl acetate (1 mL) and stirred under 1 ATM of H 2 for 24 hours. LCMS indicated the completion of the reaction. The reaction mixture was filtered to remove the catalyst. The solution was concentrated in vacuo and the residue was purified using reverse phase prep HPLC to afford the title compound as a white solid. LCMS: m/e 529.29 (M+H−H 2 O) + , 0.15 min (method 1). 1 H NMR (500 MHz, CHLOROFORM-d) δ ppm 1 H NMR (500 MHz, CHLOROFORM-d) δ ppm 0.80 (d, 3H), 0.88 (d, J=6.71 Hz, 3H), 0.97 (s, 6H), 1.02 (s, 6H), 1.12 (s, 3H), 1.18-2.23 (m, 24H), 3.36 (d, J=10.99 Hz, 1H), 3.84 (d, J=10.68 Hz, 1H), 5.27-5.42 (m, 1H), 7.26 (d, J=7.93 Hz, 2H), 8.01 (d, J=8.24 Hz, 2H).
Example 11
Preparation of methyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(hydroxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)benzoate
c
Step 1: Betuline (2 g, 4.52 mmol) was dissolved in DMF (13 ml) and treated with IMIDAZOLE (0.923 g, 13.55 mmol) and TBDPS-Cl (2.437 ml, 9.49 mmol) at 50° C. for 18 h. TLC showed the reaction was complete. The reaction mixture was cooled to rt and diluted with EtOAc and water. The organic layer was separated dried over sodium sulfate, filtered and concentrated in vacuo. The crude was purified using silica gel chromatography (0-20% EtOAc/Hex) to afford (1R,3aS,5aR,5bR,7aR,9S,11aR,11bR,13bR)-3a-((tert-butyldiphenylsilyloxy)methyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)icosahydro-1H-cyclopenta[a]chrysen-9-ol (2.75 g, 89% yield) as a white solid. 1 H NMR (500 MHz, CHLOROFORM-d) δ ppm 0.73 (s, 3H), 0.78 (s, 3H), 0.79 (s, 3H), 0.95 (s, 3H), 0.99 (s, 3H), 1.09 (s, 9H), 0.98-1.66 (m, 19H), 1.67 (s, 3H), 1.80-1.94 (m, 2H), 2.11-2.19 (m, 2H), 2.29 (td, J=11.06, 5.65 Hz, 1H), 3.16-3.24 (m, 1H), 3.35 (d, J=10.07 Hz, 1H), 3.71 (d, J=9.77 Hz, 1H), 3.75-3.81 (m, 1H), 4.55 (s, 1H), 4.62 (d, J=2.14 Hz, 1H), 7.37-7.49 (m, 6H), 7.66-7.75 (m, 4H).
Step 2: (1R,3aS,5aR,5bR,7aR,9S,11aR,11bR,13bR)-3a-((tert-butyldiphenylsilyloxy)methyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)icosahydro-1H-cyclopenta[a]chrysen-9-ol (2.75 g, 4.04 mmol) was dissolved in dichloromethane (50 mL) and treated with PCC (1.480 g, 6.86 mmol) at rt for 18 h. The reaction mixture was diluted with 500 mL of 50% EtOAc/Hexane and stirred at rt for 10 min then filtered through a silica gel and celite pad. The solution obtained was concentrated in vacuo and the residue was dissolved in methylene chloride and purified using silica gel (0-20% EtOAc/Hexanes) to afford: (1R,3aS,5aR,5bR,7aR,11aR,11bR,13bR)-3a-((tert-butyldiphenylsilyloxy)methyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)octadecahydro-1H-cyclopenta[a]chrysen-9(5bH)-one as a white solid (2.5 g, 91%). 1 H NMR (400 MHz, CHLOROFORM-d) δ ppm 0.77 (S, 3H), 0.89 (s, 3H), 0.97 (s, 3H), 1.05 (s, 3H), 1.09 (s, 12H), 1.13-1.52 (m, 18H), 1.67 (s, 3H), 1.80-1.96 (m, 2H), 2.11-2.22 (m, 2H), 2.29 (td, J=11.04, 5.77 Hz, 1H), 2.35-2.59 (m, 2H), 3.33-3.42 (m, 1H), 3.71 (d, J=9.79 Hz, 1H), 4.56 (s, 1H), 4.62 (d, J=2.01 Hz, 1H), 7.35-7.52 (m, 6H), 7.65-7.78 (m, 4H).
Step 3: (1R,3aS,5aR,5bR,7aR,11aR,11bR,13bR)-3a-((tert-butyldiphenylsilyloxy)methyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)octadecahydro-1H-cyclopenta[a]chrysen-9(5bH)-one (2.5 g, 3.68 mmol) was dissolved in THF (20 mL) and cooled to −78° C. A solution of KHMDS (14.73 mL, 7.36 mmol) in toluene was added and the mixture was stirred at this temperature for 30 min, then N-Phenylbis(trifluoromethane)sulfonimide (1.447 g, 4.05 mmol) was added and the stirring was continued for 3 h. The reaction was quenched with water and extracted with ethylacetate. The organic layers were combined and dried over sodium sulfate, filtered and concentrated. The residue was purified using silica gel (0-20% EtOAc/Hexanes) to afford (1R,3aS,5aR,5bR,7aR,11aR,11bR,13bR)-3a-((tert-butyldiphenylsilyloxy)methyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl trifluoromethanesulfonate (3.0 g, 3.70 mmol, 100% yield) as a white solid. This compound was taken to the next step without further purification. HPLC: rt=17.6 min (95% water, 5% MeOH, 10 mm Ammonium Acetate; column: Phenomenex Luna C5 4×6×150 mm 5 u; flow: 1 mL/min)
Step 4: A mixture of (1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-3a-((tert-butyldiphenylsilyloxy)methyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl trifluoromethanesulfonate (3 g, 3.70 mmol), 4-methoxycarbonylphenylboronic acid (0.998 g, 5.55 mmol), Na 2 CO 3 (1.176 g, 11.10 mmol) and TETRAKIS(TRIPHENYLPHOSPHINE)PALLADIUM(0) (0.128 g, 0.111 mmol) were refluxed in a mixture of Dioxane (8 mL), 2-Propanol (8.00 mL) and Water (5.00 mL) for 18 h. The reaction mixture was diluted with ethyl acetate and water and the organic layer was separated, dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified on silica gel to afford methyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-((tert-butyldiphenylsilyloxy)methyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)benzoate (1.5 g, 1.882 mmol, 50.9% yield) as a white solid. 1 H NMR (500 MHz, CHLOROFORM-d) δ ppm 0.81 (s, 3H), 0.95 (d, J=3.36 Hz, 9H), 1.00 (s, 3H), 1.09 (s, 9H), 1.12-1.66 (m, 18H), 1.69 (s, 3H), 1.81-1.95 (m, 1H), 2.08 (dd, J=17.24, 6.26 Hz, 1H), 2.14-2.23 (m, 2H), 2.31 (td, J=10.99, 5.80 Hz, 1H), 3.37 (d, J=10.07 Hz, 1H), 3.75 (d, J=9.46 Hz, 1H), 3.93 (s, 3H), 4.56 (s, 1H), 4.63 (d, J=1.83 Hz, 1H), 5.27-5.31 (m, 1H), 7.21 (d, J=8.24 Hz, 2H), 7.39-7.52 (m, 6H), 7.66-7.78 (m, 4H), 7.95 (d, J=8.24 Hz, 2H).
Step 5: A mixture of methyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-((tert-butyldiphenylsilyloxy)methyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)benzoate (1.5 g, 1.882 mmol) and tetrabutylammonium fluoride (0.492 g, 1.882 mmol) in THF (15 mL) was heated at 50° C. for 18 h. The reaction quenched with water and diluted with EtOAc. The organic layer was separated, dried over Na 2 SO 4 , filtered, concentrated in vacuo and purified on silica gel using 0-50%-EtOAc/Hex to afford methyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(hydroxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)benzoate (838 mg, 1.500 mmol, 80% yield) as a white solid. A portion of 20 mg was further purified using reverse phase prep HPLC for characterization. 1 H NMR (500 MHz, CHLOROFORM-d) δ ppm 0.95 (s, 3H), 1.03 (s, 3H), 1.04 (s, 3H), 1.12 (s, 6H), 0.95-2.63 (m, 26H), 3.38 (d, J=10.99 Hz, 1H), 3.80-3.89 (m, 1H), 3.98 (s, 3H), 4.57-4.65 (m, 1H), 4.72 (d, J=2.44 Hz, 1H), 5.25-5.43 (m, 1H), 7.22 (d, J=8.24 Hz, 2H), 7.95 (d, J=8.24 Hz, 2H).
Example 14
Preparation of (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-9-(4-boronophenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid
Step 1: To a solution of (1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-benzyl 5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-9-(((trifluoromethyl)sulfonyl)oxy)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylate (3.0 g, 4.43 mmol) in THF (100 mL) was added 1,4-benzenediboronic acid (1.469 g, 8.86 mmol) and tetrakis(triphenylphosphine)palladium(0) (0.259 g, 0.222 mmol). The resulting yellow mixture was purged with N 2 . Then, a solution of sodium carbonate (2.82 g, 26.6 mmol) in H 2 O (25.00 mL) was added and the reaction mixture was heated to reflux at 90° C. After 6 h, the reaction mixture was cooled to rt, diluted with EtOAc (50 mL) and washed with H 2 O (50 mL). The aqueous layer was extracted with EtOAc (2×50 mL). The combined organic layer was filtered through celite pad, washed with brine, dried over MgSO 4 , filtered and concentrated to afford a light brown solid. The crude material was absorbed onto silica gel (20 g), loaded onto a silica gel column and eluted with 3:1 hexanes:EtOAc to give (4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-((benzyloxy)carbonyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)phenyl)boronic acid (983 mg, 34.2%) as white solid. 1 H NMR (500 MHz, CHLOROFORM-d) δ 8.18-8.14 (m, 2H), 7.43-7.38 (m, 4H), 7.38-7.35 (m, 1H), 7.31-7.29 (m, 1H), 5.37-5.34 (m, 1H), 5.17 (t, J=1.0 Hz, 2H), 4.77 (d, J=1.5 Hz, 1H), 4.64 (s, 1H), 3.08 (td, J=10.8, 4.7 Hz, 1H), 2.35-2.30 (m, 1H), 2.30-2.25 (m, 1H), 2.15 (dd, J=17.1, 6.1 Hz, 1H), 1.98-1.89 (m, 2H), 1.73 (s, 3H), 1.69 (d, J=3.7 Hz, 1H), 1.67-1.64 (m, 1H), 1.56-1.37 (m, 10H), 1.37-1.23 (m, 3H), 1.19 (d, J=13.1 Hz, 1H), 1.07 (dd, J=13.1, 4.3 Hz, 1H), 1.02 (s, 6H), 0.99 (br. s., 3H), 0.99 (br. s., 3H), 0.96-0.93 (m, 1H), 0.87 (s, 3H). 13 C NMR (126 MHz, CHLOROFORM-d) δ 175.8, 150.6, 148.41-148.39 (m, 1C), 148.3, 146.8, 136.5, 134.6, 129.7, 128.5, 128.2, 128.1, 123.7, 109.6, 65.7, 56.6, 52.9, 49.6, 49.4, 46.9, 42.4, 41.8, 40.5, 38.4, 37.5, 37.0, 36.3, 33.6, 32.1, 30.6, 29.6, 29.5, 25.7, 21.3, 21.1, 19.8, 19.4, 16.5, 15.6, 14.7.
Step 2: A −78° C. solution of (4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-((benzyloxy)carbonyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)phenyl)boronic acid (0.200 g, 0.308 mmol) in DCM (3 mL) was purged with N 2 (g). Boron tribromide (1M solution in DCM) (1.079 mL, 1.079 mmol) was added dropwise. The resulting yellow reaction mixture was stirred at −78° C. for 1 h. The cold bath was removed and H 2 O (5 mL) was added to quench the reaction. The resulting white paste was filtered and washed with H 2 O. The crude material was dissolved in THF and DCM loaded onto a silica gel column and eluted with 1:1 hexanes:EtOAc. The fractions containing the desired product were reunited and concentrated in vacuo. The residue was further purified by reverse phase HPLC to give (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-9-(4-boronophenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid (45.2 mg, 24.15%) as a white solid. 1 H NMR (500 MHz, DMSO-d 6 ) δ 12.09 (br. s., 1H), 7.97 (br. s., 2H), 7.68 (d, J=7.9 Hz, 2H), 7.04 (d, J=7.9 Hz, 2H), 5.18 (d, J=4.6 Hz, 1H), 4.70 (s, 1H), 4.57 (s, 1H), 3.02-2.90 (m, 1H), 2.33-2.23 (m, 1H), 2.12 (d, J=6.4 Hz, 1H), 2.05 (dd, J=17.2, 6.3 Hz, 1H), 1.80 (d, J=7.3 Hz, 2H), 1.69-1.66 (m, 1H), 1.65 (s, 3H), 1.56 (t, J=11.3 Hz, 1H), 1.50 (br. s., 1H), 1.45-1.36 (m, 8H), 1.33-1.28 (m, 1H), 1.23 (br. s., 1H), 1.21-1.12 (m, 3H), 1.02-0.98 (m, 1H), 0.97 (s, 3H), 0.93 (s, 6H), 0.87 (s, 3H), 0.86 (s, 3H).
Preparation of Compounds of Formula III.
As previously stated, compounds of formula III can be prepared as described above for compounds of formula I and II, using ursolic acid, oleanolic acid and moronic acid as starting material instead of betulinic acid or betulin to give the corresponding E-ring modified final products. The following is a more specific version of the scheme 6 set forth above:
Preparation of Intermediates A1, and B1
Intermediate A1: (1S,2R,4aS,6aS,6bR,8aR,10S,12aR,12bR,14bS)-benzyl 10-hydroxy-1,2,6a,6b,9,9,12a-heptamethyl-1,2,3,4,4a,5,6,6a,6b,7,8,8a,9,10,11,12,12a,12b,13,14b-icosahydropicene-4-a-carboxylate
Using ursolic acid as the starting material, the title compound was prepared in accordance to the procedure described for the preparation of (1R,3aS,5aR,5bR,7aR,9S,11aR,11bR,13aR,13bR)-benzyl 9-hydroxy-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)icosahydro-1H-cyclopenta[a]chrysene-3a-carboxylate. (intermediate 1), (white solid, 98%) 1 H NMR (400 MHz, CHLOROFORM-d) δ ppm 0.79 (s, 3H), 0.86 (d, J=6.53 Hz, 3H), 0.90 (s, 3H), 0.93-0.96 (m, 3H), 0.99 (s, 3H), 1.08 (s, 3H), 1.23-1.42 (m, 7H), 1.42-1.53 (m, 4H), 1.59-1.92 (m, 10H), 1.96-2.08 (m, 1H), 2.23-2.31 (m, 1H), 3.22 (dt, J=11.04, 5.52 Hz, 1H), 4.96-5.14 (m, 2H), 5.25 (t, J=3.64 Hz, 1H), 7.35 (s, 5H).
Intermediate B1: (4aS,6aS,6bR,8aR,10S,12aR,12bR,14bS)-benzyl 10-hydroxy-2,2,6a,6b,9,9,12a-heptamethyl-1,2,3,4,4a,5,6,6a,6b,7,8,8a,9,10,11,12,12a,12b,13,14b-icosahydropicene-4-a-carboxylate
The title compound was obtained following the procedure described above for (1R,3aS,5aR,5bR,7aR,9S,11aR,11bR,13aR,13bR)-benzyl 9-hydroxy-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)icosahydro-1H-cyclopenta[a]chrysene-3a-carboxylate. (intermediate 1), using oleanoic acid as the starting material, (white solid, 94%). 1 H NMR (400 MHz, CHLOROFORM-d) δ ppm 0.62 (s, 3H), 0.70-0.74 (m, 1H), 0.78 (s, 3H), 0.89 (s, 3H), 0.91 (s, 3H), 0.93 (s, 3H), 0.99 (s, 3H), 1.02-1.08 (m, 1H), 1.13 (s, 3H), 1.16-1.30 (m, 4H), 1.30-1.37 (m, 2H), 1.37-1.48 (m, 2H), 1.51-1.53 (m, 1H), 1.60-1.63 (m, 2H), 1.64-1.66 (m, 1H), 1.67-1.71 (m, 1H), 1.71-1.77 (m, 1H), 1.86 (dd, J=8.78, 3.51 Hz, 2H), 1.92-2.05 (m, 1H), 2.86-2.97 (m, 1H), 3.16-3.28 (m, 1H), 5.01-5.16 (m, 2H), 5.30 (t, J=3.51 Hz, 1H), 7.35 (s, 5H).
Preparation of Intermediates A2, and B2
Swern Oxidation
Intermediate A2: (1S,2R,4aS,6aS,6bR,8aR,12aR,12bR,14bS)-benzyl 1,2,6a,6b,9,9,12a-heptamethyl-10-oxo-1,2,3,4,4a,5,6,6a,6b,7,8,8a,9,10,11,12,12a,12b,13,14b-icosahydropicene-4-a-carboxylate
To a solution of oxalyl chloride (2.57 mL, 5.14 mmol) in methylene chloride (5 mL) at −78° C. under nitrogen was added dropwise a solution of DMSO (0.46 mL 6.4 mmol) in methylene chloride (5 mL). The mixture was allowed to warm to −50° C. To this was added a solution of the (1S,2R,4aS,6aS,6bR,8aR,10S,12aR,12bR,14bS)-benzyl 10-hydroxy-1,2,6a,6b,9,9,12a-heptamethyl-1,2,3,4,4a,5,6,6a,6b,7,8,8a,9,10,11,12,12a,12b,13,14b-icosahydropicene-4-a-carboxylate (intermediate A1) (2.34 gm, 4.28 mmol) in methylene chloride (15 mL) forming a white milky suspension. The mixture was stirred for an additional 15 minutes at −50° C. after the addition, it was then treated with triethylamine (1.79 mL, 12.84 mmol) and the reaction mixture was slowly warmed to RT. It was diluted with methylene chloride (100 mL), washed with water (2×100 mL), followed by brine (50 mL). The organic phase was separated out, dried over anhydrous sodium sulfate, and concentrated in vacuo to a syrup. This crude material was partitioned over a silica gel column, eluted with 9:1, hexanes:ethyl acetate solvent to give the title compound as a pale solid (2.22 g, 95%). 1 H NMR (400 MHz, CHLOROFORM-d) δ ppm 0.69 (s, 3H), 0.87 (d, J=6.53 Hz, 3H), 0.93-0.97 (m, 3H), 1.03 (s, 3H), 1.05 (s, 3H), 1.09 (s, 6H), 1.26-1.40 (m, 4H), 1.40-1.54 (m, 5H), 1.59 (d, J=9.03 Hz, 2H), 1.70 (br. s., 2H), 1.93 (dd, J=9.54, 3.26 Hz, 4H), 1.97-2.08 (m, 2H), 2.29 (d, J=11.04 Hz, 1H), 2.38 (ddd, J=15.94, 6.90, 3.76 Hz, 1H), 2.49-2.61 (m, 1H), 4.97-5.03 (m, 1H), 5.10-5.15 (m, 1H), 5.27 (t, J=3.51 Hz, 1H), 7.31-7.39 (m, 5H).
Intermediate B2: (4aS,6aS,6bR,8aR,12aR,12bR,14bS)-benzyl 2,2,6a,6b,9,9,12a-heptamethyl-10-oxo-1,2,3,4,4a,5,6,6a,6b,7,8,8a,9,10,11,12,12a,12b,13,14b-icosahydropicene-4-a-carboxylate
The title compound was obtained via Swern oxidation as described above using intermediate B1 as starting material, (pale solid, 94%). 1 H NMR (400 MHz, CHLOROFORM-d) δ ppm 0.66 (s, 3H), 0.91 (s, 3H), 0.93 (s, 3H), 1.03 (s, 3H), 1.05 (s, 3H), 1.09 (s, 3H), 1.14 (s, 3H), 1.17-1.24 (m, 2H), 1.25-1.50 (m, 8H), 1.57-1.78 (m, 6H), 1.84-1.94 (m, 3H), 1.95-2.05 (m, 1H), 2.37 (ddd, J=15.81, 6.78, 3.76 Hz, 1H), 2.50-2.60 (m, 1H), 2.93 (dd, J=13.93, 3.89 Hz, 1H), 5.04-5.09 (m, 1H), 5.09-5.14 (m, 1H), 5.32 (t, J=3.64 Hz, 1H), 7.35-7.37 (m, 5H).
Preparation of Intermediates A3 and B3
Intermediate A3: (1S,2R,4aS,6aS,6bR,8aR,12aR,12bR,14bS)-benzyl 1,2,6a,6b,9,9,12a-heptamethyl-10-(trifluoromethylsulfonyloxy)-1,2,3,4,4a,5,6,6a,6b,7,8,8a,9,12,12a, 12b,13,14b-octadecahydropicene-4-a-carboxylate
The title compound was prepared using the procedure described previously for the preparation of (1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-benzyl 5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-9-(trifluoromethylsulfonyloxy)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylate (intermediate 3), using ketone intermediate A2 as starting material (45%). 1 H NMR (400 MHz, CHLOROFORM-d) δ ppm 0.67 (s, 3H), 0.87 (d, J=6.53 Hz, 3H), 0.93-0.97 (m, 3H), 0.99 (s, 3H), 1.04 (s, 3H), 1.08 (s, 3H), 1.14 (s, 3H), 1.17-1.21 (m, 1H), 1.21-1.47 (m, 5H), 1.50 (dd, J=13.05, 3.26 Hz, 2H), 1.56 (s, 3H), 1.58-1.78 (m, 3H), 1.78-1.97 (m, 3H), 1.97-2.07 (m, 2H), 2.15 (dd, J=17.07, 6.78 Hz, 1H), 2.30 (d, J=11.54 Hz, 1H), 4.97-5.02 (m, 1H), 5.10-5.15 (m, 1H), 5.27 (t, J=3.51 Hz, 1H), 5.59 (dd, J=6.78, 2.01 Hz, 1H), 7.35 (s, 5H); 19 F NMR (376.46 MHz, CHLOROFORM-d) δ ppm −74.83.
Intermediate B3: (4aS,6aS,6bR,8aR,12aR,12bR,14bS)-benzyl 2,2,6a,6b,9,9,12a-heptamethyl-10-(trifluoromethylsulfonyloxy)-1,2,3,4,4a,5,6,6a,6b,7,8,8a,9,12,12a,12b,13,14b-octadecahydropicene-4-a-carboxylate
The title compound was prepared using the procedure described previously for the preparation of (1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-benzyl 5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-9-(trifluoromethylsulfonyloxy)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylate (intermediate 3), using ketone intermediate B2 as starting material (29%). 1 H NMR (400 MHz, CHLOROFORM-d) δ ppm 0.65 (s, 3H), 0.91 (s, 3H), 0.94 (s, 3H), 0.97 (s, 3H), 1.04 (s, 3H), 1.05-1.12 (m, 1H), 1.14 (s, 6H), 1.16-1.28 (m, 3H), 1.28-1.42 (m, 2H), 1.42-1.54 (m, 2H), 1.57-1.65 (m, 2H), 1.68 (d, J=14.56 Hz, 2H), 1.73 (d, J=4.52 Hz, 1H), 1.78-1.84 (m, 2H), 1.86 (dd, J=5.90, 4.14 Hz, 1H), 1.90-1.97 (m, 1H), 1.98-2.04 (m, 1H), 2.12 (dd, J=17.07, 6.78 Hz, 1H), 2.93 (dd, J=13.93, 4.14 Hz, 1H), 5.03-5.14 (m, 3H), 5.33 (t, J=3.51 Hz, 1H), 5.58 (dd, J=6.78, 2.01 Hz, 1H), 7.34-7.38 (m, 5H); 19 F NMR (376.46 MHz, CHLOROFORM-d) δ ppm −74.84.
Intermediate A4: Preparation of Intermediates A4 and B4
(1S,2R,4aS,6aS,6bR,8aR,12aS,12bR,14bS)-benzyl 10-(4-(methoxycarbonyl)phenyl)-1,2,6a,6b,9,9,12a-heptamethyl-1,2,3,4,4a,5,6,6a,6b,7,8,8a,9,12,12a,12b,13,14b-octadecahydropicene-4-a-carboxylate
The title compound was prepared via from triflate intermediate A3 using the Suzuki coupling procedure described previously for the preparation of (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-benzyl 9-(4-(methoxycarbonyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylate (intermediate 4), (68%). 1 H NMR (400 MHz, CHLOROFORM-d) δ ppm 0.73 (s, 3H), 0.88 (d, J=6.53 Hz, 3H), 0.93-0.97 (m, 9H), 1.06 (s, 3H), 1.12 (s, 3H), 1.14-1.19 (m, 1H), 1.25 (d, J=12.30 Hz, 2H), 1.31-1.45 (m, 4H), 1.45-1.54 (m, 2H), 1.57-1.62 (m, 1H), 1.65 (dd, J=13.05, 4.02 Hz, 1H), 1.68-1.79 (m, 3H), 1.80-1.87 (m, 1H), 1.91-1.98 (m, 2H), 2.02 (dd, J=12.92, 4.64 Hz, 1H), 2.10 (dd, J=17.07, 6.27 Hz, 1H), 2.31 (d, J=11.04 Hz, 1H), 3.92 (s, 3H), 4.98-5.03 (m, 1H), 5.11-5.15 (m, 1H), 5.29-5.34 (m, 2H), 7.21 (d, J=8.53 Hz, 2H), 7.31-7.39 (m, 5H), 7.94 (d, J=8.28 Hz, 2H).
Intermediate B4: (4aS,6aS,6bR,8aR,12aS,12bR,14bS)-benzyl 1044-(methoxycarbonyl)phenyl)-2,2,6a,6b,9,9,12a-heptamethyl-1,2,3,4,4a,5,6,6a,6b,7,8,8a,9,12,12a,12b,13,14b-octadecahydropicene-4-a-carboxylate
The title compound was prepared via from triflate intermediate B3 using the Suzuki coupling procedure described previously for the preparation of (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-benzyl 9-(4-(methoxycarbonyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylate (intermediate 4), (65%). 1 H NMR (400 MHz, CHLOROFORM-d) δ ppm 0.70 (s, 3H), 0.92 (s, 3H), 0.95 (s, 9H), 1.04 (s, 3H), 1.08-1.15 (m, 1H), 1.17 (s, 3H), 1.19-1.25 (m, 2H), 1.27 (br. s., 2H), 1.30-1.38 (m, 2H), 1.40 (dd, J=8.03, 3.51 Hz, 1H), 1.43-1.54 (m, 2H), 1.58-1.68 (m, 3H), 1.68-1.78 (m, 3H), 1.90 (dd, J=6.15, 3.89 Hz, 1H), 1.92-2.03 (m, 2H), 2.07 (dd, J=17.07, 6.27 Hz, 1H), 2.95 (dd, J=13.80, 4.02 Hz, 1H), 3.92 (s, 3H), 5.04-5.15 (m, 2H), 5.31 (dd, J=6.15, 1.88 Hz, 1H), 5.36 (t, J=3.39 Hz, 1H), 7.21 (d, J=8.53 Hz, 2H), 7.33-7.38 (m, 5H), 7.94 (d, J=8.28 Hz, 2H).
Preparation of Intermediates A5 and B5
Intermediate A5: (1S,2R,4aS,6aS,6bR,8aR,12aS,12bR,14bS)-tert-butyldimethylsilyl 10-(4-(methoxycarbonyl)phenyl)-1,2,6a,6b,9,9,12a-heptamethyl-1,2,3,4,4a,5,6,6a,6b,7,8,8a,9,12,12a,12b,13,14b-octadecahydropicene-4-a-carboxylate
Palladium catalyzed hydrosilylation of the benzyl esters intermediate A4 as described in the preparation of 1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-tert-butyldimethylsilyl 9-(4-(methoxycarbonyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylate, (intermediate 5) afforded the title compound (57%). 1 H NMR (400 MHz, CHLOROFORM-d) δ ppm 0.24 (s, 3H), 0.25 (s, 3H), 0.87-0.90 (m, 6H), 0.93-0.98 (m, 18H), 1.09 (s, 3H), 1.12 (s, 3H), 1.16-1.51 (m, 6H), 1.52-1.59 (m, 7H), 1.59-1.88 (m, 4H), 1.88-2.07 (m, 3H), 2.11 (dd, J=17.07, 6.27 Hz, 1H), 2.22 (d, J=10.29 Hz, 1H), 3.92 (s, 3H), 5.30-5.34 (m, 2H), 7.22 (d, J=8.28 Hz, 2H), 7.94 (d, J=8.28 Hz, 2H);
Intermediate B5: (4aS,6aS,6bR,8aR,12aS,12bR,14bS)-tert-butyldimethylsilyl 10-(4-(methoxycarbonyl)phenyl)-2,2,6a,6b,9,9,12a-heptamethyl-1,2,3,4,4a,5,6,6a,6b,7,8,8a,9,12,12a,12b,13,14b-octadecahydropicene-4-a-carboxylate
Palladium catalyzed hydrosilylation of the benzyl esters intermediate B4 as described in the preparation of 1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-tert-butyldimethylsilyl 9-(4-(methoxycarbonyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylate, (intermediate 5) afforded the title compound (54%). 1 H NMR (400 MHz, CHLOROFORM-d) δ ppm 0.25 (s, 3H), 0.26 (s, 3H), 0.87 (s, 3H), 0.92 (s, 3H), 0.93-0.97 (m, 18H), 1.07 (s, 3H), 1.12-1.17 (m, 2H), 1.18 (s, 4H), 1.21-1.30 (m, 3H), 1.30-1.53 (m, 5H), 1.62-1.80 (m, 5H), 1.82-1.95 (m, 1H), 1.95-2.03 (m, 2H), 2.07 (dd, J=17.07, 6.27 Hz, 1H), 2.88 (dd, J=13.93, 4.64 Hz, 1H), 3.92 (s, 3H), 5.31 (dd, J=6.27, 1.76 Hz, 1H), 5.35 (t, J=3.51 Hz, 1H), 7.22 (d, J=8.53 Hz, 2H), 7.94 (d, J=8.28 Hz, 2H).
Preparation of Intermediates A6 and B6
Intermediate A6: (1S,2R,4aS,6aS,6bR,8aR,12aS,12bR,14bS)-10-(4-(methoxycarbonyl)phenyl)-1,2,6a,6b,9,9,12a-heptamethyl-1,2,3,4,4a,5,6,6a,6b,7,8,8a,9,12,12a,12b,13,14b-octadecahydropicene-4-a-carboxylic acid
The title compound was prepared following the procedure describe for the preparation of (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-9-(4-(methoxycarbonyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid (example 7) using intermediate A5 as starting material, (98%). 1 H NMR (400 MHz, CHLOROFORM-d) δ ppm 0.87 (s, 3H), 0.89 (d, J=6.53 Hz, 3H), 0.93 (s, 3H), 0.94 (s, 3H), 0.96 (s, 3H), 0.98 (s, 3H), 1.03 (t, J=7.28 Hz, 2H), 1.08-1.11 (m, 3H), 1.13 (s, 3H), 1.19 (s, 2H), 1.22-1.82 (m, 10H), 1.84-2.06 (m, 2H), 2.06-2.15 (m, 1H), 2.23 (d, J=11.04 Hz, 1H), 3.32-3.51 (m, 1H), 3.92 (s, 3H), 5.32 (dd, J=5.90, 1.63 Hz, 2H), 7.20 (d, J=8.28 Hz, 2H), 7.94 (d, J=8.28 Hz, 2H).
Intermediate B6: (4aS,6aS,6bR,8aR,12aS,12bR,14bS)-10-(4-(methoxycarbonyl)phenyl)-2,2,6a,6b,9,9,12a-heptamethyl-1,2,3,4,4a,5,6,6a,6b,7,8,8a,9,12,12a,12b,13,14b-octadecahydropicene-4-a-carboxylic acid
The title compound was prepared following the procedure describe for the preparation of (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-9-(4-(methoxycarbonyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid (example 7) using intermediate B5 as starting material, (95%). 1 H NMR (400 MHz, CHLOROFORM-d) δ ppm 0.85 (s, 3H), 0.91-0.97 (m, 12H), 1.03 (t, J=7.28 Hz, 2H), 1.08 (s, 3H), 1.12-1.16 (m, 1H), 1.18 (s, 3H), 1.21 (d, J=4.52 Hz, 2H), 1.26 (br. s., 2H), 1.28 (br. s., 1H), 1.32-1.43 (m, 2H), 1.43-1.53 (m, 2H), 1.53-1.61 (m, 2H), 1.63 (d, J=4.27 Hz, 1H), 1.71 (d, J=6.02 Hz, 1H), 1.74-1.82 (m, 2H), 1.82-1.96 (m, 2H), 2.01 (dd, J=7.91, 3.64 Hz, 1H), 2.03-2.13 (m, 1H), 2.87 (dd, J=13.68, 3.89 Hz, 1H), 3.33-3.46 (m, 1H), 3.92 (s, 3H), 5.31 (dd, J=6.15, 1.63 Hz, 1H), 5.36 (t, J=3.39 Hz, 1H), 7.20 (d, J=8.28 Hz, 2H), 7.94 (d, J=8.53 Hz, 2H).
Preparation of Examples 12 and 13
Example 12
(1S,2R,4aS,6aS,6bR,8aR,12aS,12bR,14bS)-10-(4-carboxyphenyl)-1,2,6a,6b,9,9,12a-heptamethyl-1,2,3,4,4a,5,6,6a,6b,7,8,8a,9,12,12a,12b,13,14b-octadecahydropicene-4-a-carboxylic acid
Saponification of the intermediates A6 was conducted as followed: to a solution of (1S,2R,4aS,6aS,6bR,8aR,12aS,12bR,14bS)-10-(4-(methoxycarbonyl)phenyl)-1,2,6a,6b,9,9,12a-heptamethyl-1,2,3,4,4a,5,6,6a,6b,7,8,8a,9,12,12a,12b,13,14b-octadecahydropicene-4-a-carboxylic acid (intermediate A6) (20 mg, 0.035 mmol) in a mixture of dioxane (1 mL) and methanol (0.5 mL) was added a 1N solution of NaOH (0.5 mL, 0.5 mmol). The mixture was warmed to 65° C. for 2 h. The crude product was further purified by preparative HPLC(YMC Combiprep ODS 30×50 mm S5 column) eluted with gradient mixture of MeOH/water/TFA. The desired fractions were combined, evaporated to afford the title compound (12 mg, 61%).
Example 13
(4aS,6aS,6bR,8aR,12aS,12bR,14bS)-10-(4-carboxyphenyl)-2,2,6a,6b,9,9,12a-heptamethyl-1,2,3,4,4a,5,6,6a,6b,7,8,8a,9,12,12a,12b,13,14b-octadecahydropicene-4-a-carboxylic acid
The title compound was prepared following the saponification method described above using (4aS,6aS,6bR,8aR,12aS,12bR,14bS)-10-(4-(methoxycarbonyl)phenyl)-2,2,6a,6b,9,9,12a-heptamethyl-1,2,3,4,4a,5,6,6a,6b,7,8,8a,9,12,12a,12b,13,14b-octadecahydropicene-4-a-carboxylic acid (intermediate B6) as starting material (76%). 1 H NMR (400 MHz, Methanol-d 4 ) δ ppm 0.91 (d, 3H), 0.93 (s, 3H), 0.95-1.00 (m, 10H), 1.14 (s, 3H), 1.17 (s, 3H), 1.27-1.57 (m, 7H), 1.57-1.73 (m, 6H), 1.79 (d, J=16.31 Hz, 2H), 1.88-2.11 (m, 5H), 2.15 (dd, J=17.07, 6.27 Hz, 1H), 2.24 (d, J=11.29 Hz, 1H), 5.30 (t, J=3.39 Hz, 1H), 5.33 (dd, J=6.27, 1.76 Hz, 1H), 7.24 (d, J=8.53 Hz, 2H), 7.93 (d, J=8.53 Hz, 2H). For intermediate 21- 1 H NMR (400 MHz, Methanol-d 4 ) δ ppm 0.91 (s, 3H), 0.93 (s, 3H), 0.96 (s, 3H), 0.98 (d, J=2.01 Hz, 6H), 1.12 (s, 3H), 1.16 (d, J=13.80 Hz, 2H), 1.21 (s, 3H), 1.31 (d, J=10.79 Hz, 2H), 1.35-1.49 (m, 3H), 1.49-1.67 (m, 5H), 1.67-1.82 (m, 5H), 1.82-1.98 (m, 2H), 1.98-2.06 (m, 2H), 2.07-2.18 (m, 1H), 2.89 (dd, J=13.68, 3.64 Hz, 1H), 5.25-5.38 (m, 2H), 7.24 (d, J=8.03 Hz, 2H), 7.93 (d, J=8.28 Hz, 2H).
Biology Data for the Examples
“μM” means micromolar;
“mL” means milliliter;
“μl” means microliter;
“mg” means milligram;
“μg” means microgram;
The materials and experimental procedures used to obtain the results reported in Tables 1-2 are described below.
HIV cell culture assay—MT-2 cells and 293T cells were obtained from the NIH AIDS Research and Reference Reagent Program. MT-2 cells were propagated in RPMI 1640 media supplemented with 10% heat inactivated fetal bovine serum, 100 μg/ml penicillin G and up to 100 units/ml streptomycin. The 293T cells were propagated in DMEM media supplemented with 10% heat inactivated fetal bovine serum (FBS), 100 units/ml penicillin G and 100 μg/ml streptomycin. The proviral DNA clone of NL 4-3 was obtained from the NIH AIDS Research and Reference Reagent Program. A recombinant NL 4-3 virus, in which a section of the nef gene from NL4-3 was replaced with the Renilla luciferase gene, was used as a reference virus. In addition, residue Gag P373 was converted to P373S. Briefly, the recombinant virus was prepared by transfection of the altered proviral clone of NL 4-3 . Transfections were performed in 293T cells using LipofectAMINE PLUS from Invitrogen (Carlsbad, Calif.), according to manufacturer's instruction. The virus was titered in MT-2 cells using luciferase enzyme activity as a marker. Luciferase was quantitated using the Dual Luciferase kit from Promega (Madison, Wis.), with modifications to the manufacturer's protocol. The diluted Passive Lysis solution was pre-mixed with the re-suspended Luciferase Assay Reagent and the re-suspended Stop & Glo Substrate (2:1:1 ratio). Fifty (50) μL of the mixture was added to each aspirated well on assay plates and luciferase activity was measured immediately on a Wallac TriLux (Perkin-Elmer). Antiviral activities of inhibitors toward the recombinant virus were quantified by measuring luciferase activity in cells infected for 4-5 days with NLRluc recombinants in the presence serial dilutions of the inhibitor. The EC 50 s data for the compounds is shown in Table 2. Table 1 is the key for the data in Table 2.
Results
TABLE 1
Biological Data Key for EC 50 s
Compounds with EC 50 > 1 μM
Compounds with EC 50 < 1 μM
Group “B”
Group “A”
TABLE 2
Example
EC50
1a
B
1b
A
2a
B
2b
A
3a
2.0 μM
3b
A
4a
A
4b
B
4c
A
4d
A
4e
A
4f
A
4g
B
4h
A
4i
B
4j
B
4k
A
4l
B
4m
B
4n
A
4o
A
5a
A
5b
A
5c
0.23 μM
5d
A
5e
B
5f
A
5g
B
5h
B
5i
B
5j
A
5k
A
5l
B
5m
A
5n
A
5o
0.5 μM
5p
A
5q
B
5r
A
5s
A
5t
A
5u
A
6a
A
6b
A
7
B
8
A
9
A
10
A
11
B
12
A
13
A
14
13.4 nM
The foregoing description is merely illustrative and should not be understood to limit the scope or underlying principles of the invention in any way. Indeed, various modifications of the invention, in addition to those shown and described herein, will become apparent to those skilled in the art from the following examples and the foregoing description. Such modifications are also intended to fall within the scope of the appended claims. | Compounds having drug and bio-affecting properties, their pharmaceutical compositions and methods of use are set forth. In particular, modified C-3 betulinic acid and other structurally related natural products derivatives that possess unique antiviral activity are provided as HIV maturation inhibitors. These compounds are useful for the treatment of HIV and AIDS. | 2 |
[0001] This invention relates to heated mirrors.
[0002] Mirrors for use in steamy atmospheres where condensation affects visibility, for example in showers and bathrooms, can be warmed above condensation temperature by applying hot water that is readily available from the shower or the hand basin. Mirrors are known that employ a reservoir behind the mirror surface for filling with hot water. However, these known mirrors are bulky and lack utility because the reservoir is difficult to fill.
[0003] This invention is more particularly concerned with mirror equipment of the type that is manipulated by hand at each use in order to apply hot water to the mirror.
[0004] An example of such equipment is known from patent specification U.S. Pat. No. 4,655,559. In that known equipment, the mirror is provided on the front of a reservoir, from the bottom of which a pin projects. The pin fits into a socket in a bracket, which is connected by a ball and a socket joint to a sucker for attachment to a wall. By disconnecting the pin and socket joint, the mirrored reservoir can be removed for emptying and recharging with hot water to reduce the tendency of the mirror to fog-up. The equipment of U.S. Pat. No. 4,655,559 requires the user to remove the mirror from its support then fill the reservoir by holding its open end in the shower water flow, or by immersing it in a hand basin or the like. The reservoir must be emptied before reuse. However, when a single cavity is filled with water in this way it is difficult to get the water to flow into the cavity. For convenience, the water entry area must be large enough to allow water to flow easily into the cavity in a reasonable time. Therefore, the water volume in the single cavity must be greater than is required for heating the mirror surface. This difficulty arises because the water attempts to enter the cavity from a generally restricted entrance aperture at one end of the cavity, but it is prevented from entering by the air trying to expel from the cavity. Furthermore, when filled from a shower spray the reservoir opening must be unduly large in order to catch the dispersed drops of water. When emptying the cavity, the water is hampered in its egress by a combination of capillary action and the blocking effect of air flowing into the cavity. If the water entry point is made larger to achieve a convenient filling rate of the reservoir, the whole device must be made correspondingly larger.
[0005] When constructing a portable heated mirror device it is desirable that the construction be as slimline as practicable, so that the equipment may be easily stored in a shaving kit bag for example. Also, it is desirable that the equipment be a light as practicable when charged with water so that sucker type support devices are more effective.
[0006] In accordance with one aspect of the present invention, a heated mirror of the general type mentioned above is characterised in that the mirror is provided with features disposed behind the mirrored surface for gathering water, and structures disposed behind the mirrored surface for retaining water, wherein the water gathering features are several and are adjacent at least part of the surface area of the back of the mirror, and wherein the water retaining structures are several, and extend outward from adjacent the mirrored surface to form a generally open compartment such that the compartment so formed may be filled with water, which structures cover at least part of the back of the mirror.
[0007] By virtue of the relatively large surface area available for the water to enter into the reservoir, it is filled almost instantly when exposed to the shower spray or immersed in water.
[0008] In another embodiment, the mirror is provided with an absorbent material disposed behind the mirrored surface wherein the material may absorb heated water so that the heat in the water can be transferred to the body of the mirror over time. By virtue of the relatively large surface area for the water to enter into the absorbent material, it is filled almost instantly when exposed to the shower spray or immersed in water.
[0009] In another embodiment the mirror material may be provided with cavities over the surface area of the mirror so that these can adsorb or be filled with heated water so that the heat in the water can be transferred to the mirror body over time.
[0010] By incorporating such a water storage device, a water heated mirror that includes a water reservoir may be made more convenient for the user due to the quickness of the filling and emptying of the water reservoir. When showering, the user does not have to present a filling aperture precisely to the water source but merely waves the larger collecting surface of the present invention under the general water flow. Further, the mirror may be constructed to be less bulky, lighter in weight, especially when charged with water, and more portable, for fitting into a shaving kit bag for example.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] Specific embodiments of the present invention will now be described, by way of example, with reference to the accompanying drawings, in which:
[0012] [0012]FIG. 1 is a sectioned view illustrating difficulties of filling water reservoirs in shaving mirrors.
[0013] [0013]FIG. 2 is a sectioned view of an embodiment with compartmented water gathering and retaining features on the back vertical surface of the mirror.
[0014] [0014]FIG. 3 is an oblique view of a second embodiment with cellular water gathering and retaining structures on the rear vertical surface of the mirror and incorporates a magnified section.
[0015] [0015]FIG. 4 is a cross-sectional view of a mirror material containing cavities for filling with water
DETAILED DESCRIPTION
[0016] The problems experienced when filling water reservoirs, in particular those associated with water-heated mirrors of the prior art, are demonstrated in FIG. 1. The size of the mirror [ 1 ] may vary, but at least 150 mm of mirror height and 100 mm of width is required to efficiently accommodate the facial reflection when shaving or removing make-up for instance. Thus, the function of the equipment dictates that the height and width of the reservoir [ 2 ] must be approximately proportional to those shown in FIG. 1. In FIG. 1, the effective area available for water [ 5 ] gathering is the opening [ 3 ] where the water flow [ 4 ] enters the water storage reservoir [ 2 ]. Increasing the size of the opening [ 3 ] is not practical for gathering water [ 5 ] from a shower head water flow [ 4 ] because the geometry of the water flow from shower heads does not fit the shape of the reservoir entrance [ 3 ], and to compound this problem the individual water jets are spaced too far apart to supply the water volume needed when only a relatively small gathering aperture is available.
[0017] [0017]FIG. 2A shows equipment of the present invention where water [ 5 ] gathering features [ 6 ] and cellular water retaining structures [ 7 ] cover the back of the mirror [ 1 ]. The effective area available for water gathering is the area [ 3 A] where water flow [ 4 ] enters the water storage structures [ 7 ] over a major portion of the mirror back. The water gathering features [ 6 ] are comprised of the spaces between the louvre-like water retaining structures [ 7 ]. The cells bounded by the structures [ 7 ] are filled almost instantly by the water flow [ 4 ] because of their generally open aspect. The copious flow of water into the cells bounded by the retaining structures [7], and the resultant overflow of the cells, ensures that the initial coldness of the equipment is removed quickly, and the final reservoir of water will be more effective in maintaining a fog-free state for a longer period.
[0018] It will be appreciated that although louvres are shown in a generally linear configuration in the drawing, the water gathering features and retaining structures can be of any suitable shape.
[0019] In a further embodiment of the invention, FIG. 3 shows a cellular configuration of water gathering and storage where a large surface area for water gathering is provided by a sponge like material [ 8 ] adjacent the back vertical surface of the mirror [ 1 ]. In this embodiment the cellular spaces [ 9 ] are smaller than the compartments delineated by the water volumes [ 5 ] shown in FIG. 2, but they both employ the principle of retaining water on the vertical surface of the mirror assembly and thus provide a substantially larger surface area for ingress of water [ 4 ] into the storage means relative to the storage capacity. The sponge material [ 8 ] is charged in much the same way as the compartments [ 7 ] shown in FIG. 2.
[0020] In FIG. 4 the mirror body [ 1 ] is provided with cavities [ 10 ] on at least one vertical face of the mirror [ 1 ] in quantities that in combination present a large surface area for filling relative the surface area of the mirror. These holes or cavities may be relatively large or microscopic. Microscopic holes may be placed partially through the mirror body or right through the mirror body and may be applied in a density that does not unduly affect the reflective qualities of the mirror. | Compact features provide faster and more efficient gathering and storage of a sufficient reservoir of heated water to heat a shaving mirror to non-fogging temperature. The features are arranged on the vertical surfaces of the mirror to enable water to enter the reservoir over a large surface area relative to the mirror size. | 0 |
CROSS REFERENCE TO RELATED APPLICATION
This application claims priority from German Patent Application Nos. 103 15 136.2 and 103 49 407.3, which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
The invention relates to an apparatus at a spinning preparation machine, for example a cleaner, opener, carding machine or the like, for detecting waste which is separated out from fibre material, for example cotton.
The fibre material typically consists of foreign matter and good fibres, and may be collected in a collecting device, wherein there is provided an optical measuring device having a brightness sensor, which measuring device examines the waste. In a known apparatus (EP-A-0 399 315), the beater pins of a cleaning roller convey the fibre flocks over cleaning bars which are adjustable so that the intensity of cleaning can be varied. Below the cleaning bars, a brightness sensor measures the brightness as a measure of the contaminant content of the offtake (waste), which has been separated out by the cleaning bars and is collected in a funnel-like collecting device. At prespecified time intervals, the offtake is drawn off under suction by way of a suction conveyor arranged at the lower end of the collecting device. The brightness—measured by the brightness sensor—of the separated-out waste, in the form of a signal, is input into a control system and displayed on a display. One disadvantage is that the sensor serves only for detecting the contaminant content; the content of good fibres is not detected. It is furthermore disadvantageous that the determined degree of cleaning is investigated, by sensors, in the offtake chamber of the cleaning machine. Finally, the brightness, that is to say the degree of brightness—measured by the sensor—of the offtake is merely input into the control system without, however, any optimum operating point of the cleaning machine being derived therefrom.
It is an aim of the invention to provide an apparatus of the kind described at the beginning which avoids or mitigates the mentioned disadvantages and which especially makes it possible for the content of good fibres in the offtake to be detected by simple means and allows optimum adjustment of the composition of the offtake, especially to have a high content of foreign matter (trash) and a low content of good fibres.
SUMMARY OF THE INVENTION
The invention provides a spinning preparation machine in which waste can be separated from fibre material, having a sensor arrangement including a light source and a brightness sensor for examining waste, and further having a measurement element, wherein the waste can be conveyed past the sensor arrangement and the brightness sensor is arranged to receive light from the light source reflected by the waste, the received light being convertible into electrical signals which are measurable by the measurement element.
The measures according to the invention make it possible for the content of good fibres in the offtake to be detected automatically and allow optimum adjustment of the composition of the offtake (trash/good fibres) by simple means. The brightness sensor and the subsequent evaluation provide precise information relating to the content of good fibres in the offtake, that information being usable for adjustment of the separating elements. In the process, a continuous, objective and, accordingly, personnel-independent assessment of the separated-out waste can be carried out. It is, especially, possible to determine, and if necessary to influence, the amount of good fibres that are, undesirably, also separated out. Existing machine elements can be so adjusted in dependence upon the results obtained that a predetermined, desired waste composition is obtained automatically. It is especially advantageous that the variation in the brightness signal (coefficient of variation/standard deviation of light reflection) corresponds to the quantitative distribution curve of the waste (trash/good fibres), from which an optimum operating point can be derived for adjustment of the separating elements for the cleaning of the fibre material. The function between the coefficient of variation and, for example, the position of the adjustable guide vanes of the cleaning machine may exhibit a characteristic change in the gradient (gradient endpoint or range) which corresponds to the optimum operating point for cleaning. Determining the optimum operating point can be carried out by means of an arrangement that is very simple in terms of apparatus, which constitutes a further advantage.
The collecting device may be a pneumatic pipe-line. The collecting device may be a suction offtake hood.
Advantageously, the waste is moved through the collecting device. The brightness sensor may be arranged in the wall region of the pipe-line or suction offtake hood. The brightness sensor may be located in the region of an end face of the pipe-line or suction offtake hood. The brightness sensor may comprise at least one photoelectric element, for example, at least one photodiode. The brightness sensor may be capable of detecting changes in voltage caused by differences in brightness. Advantageously, the brightness sensor is connected to an electronic evaluation device. The light source may be a direct-current illuminator. The light source may be an alternating-current illuminator. The light source is advantageously arranged in the immediate vicinity of the brightness sensor, for example, next to the brightness sensor. Advantageously, the sensor system operates in incident light. Advantageously, the variation in the brightness of the good fibres is arranged to be determined. Advantageously the coefficient of variation of the brightness of the good fibres is arranged to be determined. Advantageously, the standard deviation of the brightness of the good fibres is arranged to be determined. Advantageously, detection and assessment of the waste are carried out automatically. Advantageously, detection and assessment of the waste are carried out continuously. Advantageously, the measurement results of the evaluation device are compared with prespecified quantities. Advantageously, in the event of a departure from prespecified quantities, the waste separation can be modified. Advantageously, at least one opto-electronic brightness measurer is integrated into the suction offtake lines through which the waste is taken off under suction. Advantageously, more than one electronic evaluation device is provided. Advantageously, more than one opto-electronic brightness measurer is connected to evaluation devices. Advantageously, the evaluated measurement results relating to the consistency of the waste are compared with prespecified values and used for automatically modifying machine elements influencing separation. Advantageously, the at least one evaluation device is in communication with the associated machine control. Advantageously, the evaluated measurement results of the separation procedures are shown on the machine operating and display unit. Advantageously, the evaluated measurement results of the separation procedures are passed on to other, possibly superordinate and central, systems. Advantageously, at least one opto-electronic brightness measurer is associated with each machine. Advantageously, at least one opto-electronic brightness measurer is arranged on each side of a machine. Advantageously, the at least two brightness sensors are in communication with a central evaluation device. Advantageously, different light sources are provided. Advantageously, light sources of different colours are provided, for example red light and infra-red light. Advantageously, at least one source of incident light is provided. Advantageously, the evaluated measurement results are used for adjusting at least one guide vane associated with the roller. Advantageously, the evaluated measurement results are used for adjusting at least one separating blade associated with the roller. Advantageously, the at least one electronic evaluation device (measuring element) is in communication with an electronic control and regulation device, for example a microcomputer. Advantageously, the machine elements such as guide vanes, separating blades and the like are arranged to be automatically adjusted in dependence upon the evaluated measurement results. Advantageously, the cleaning capability of the machine is modifiable in dependence upon the evaluated measurement results. Advantageously, the nature of the waste (amount, composition) is modifiable in dependence upon the evaluated measurement results. Advantageously, at least one separate brightness sensor is associated with each suction offtake location or guide vane. Advantageously, the brightness sensor is associated with a central waste-collecting line. Advantageously, a window for the brightness sensor is provided in each waste-collecting line. Advantageously, a window for an illumination device is provided in each waste-collecting line. Advantageously, the evaluated measurement results are used for determining the ratio of the good fibre content to the contaminant content. Advantageously, the evaluated measurement results are used for assessing the quality of the fibre material being processed. Advantageously, a machine is in communication with a central evaluation device, to which more than one brightness sensor is connected. Advantageously, the electronic control and regulation device, for example a computer, has a memory for comparison data. Advantageously, the evaluation device is in communication with a superordinate electronic evaluation system, for example KIT. Advantageously, the measurement values of the brightness sensor are convertible into electrical signals. Advantageously, the evaluated measurement results are used in a control and regulation circuit for optimising the cleaning of the fibre material. Advantageously, the illumination device or light source operates using visible light. Advantageously, the content of good fibres is arranged to be determined. Advantageously, at least one angle-measuring device is connected to the control and regulation device. Advantageously, at least one brightness sensor is connected to the control and regulation device. Advantageously, at least one actuating element is connected to the control and regulation device. Advantageously, the sensor arrangement is used for determining a blockage of fibre material in the collecting line. Advantageously, a blockage in a suction hood is determined. Advantageously, a static state of the electrical signal caused by the blockage is arranged to be detected. Advantageously, exceeding, or falling below, a limit value for the electrical signal caused by the blockage is arranged to be detected. Advantageously, the machine control issues an error message on the basis of the blockage.
The invention also provides an apparatus at a spinning preparation machine, for example a cleaner, opener, carding machine or the like, for detecting waste which is separated out from fibre material, for example cotton, and consists of foreign matter and good fibres and which is collected in a collecting device having a brightness sensor, which measuring device examines the waste, characterised in that the waste material is moved past at least one sensor arrangement responding to good fibres, and the sensor arrangement comprises a light source, the light reflected by the moving good fibres being detected by the brightness sensor and being converted into electrical signals, which are measured by a measurement element.
The invention also provides a method of monitoring waste in a spinning preparation machine, comprising conveying the waste past a location in which it can be examined by a sensor arrangement, so illuminating waste in said location that reflected light from the waste can be detected by a brightness sensor, converting data relating to the brightness of the waste to electrical signals, and evaluating the electrical signals to ascertain information relating to the composition of the waste.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 a is a diagrammatic cross-sectional side view of a cleaning machine having several suction hoods for waste;
FIG. 1 b is a side view of the cleaner of FIG. 1 a having apparatuses according to the invention;
FIG. 2 is a cross-sectional front view, along I—I in FIG. 1 b , of a part of a cleaner similar to that of FIG. 1 b having an apparatus according to the invention arranged at a suction offtake channel;
FIG. 2 a shows an apparatus according to the invention arranged at a connection piece of a suction offtake arrangement;
FIG. 3 a shows a waste-separating location with a waste-separating arrangement having an adjustable guide vane;
FIG. 3 b shows the waste-separating arrangement of FIG. 3 a with the guide vane in a different position;
FIG. 3 c is a top view of a part of the waste-separating arrangement of FIGS. 3 a , 3 b , including the guide vane together with an actuating motor and an angle-measuring element;
FIG. 4 is a top view of a part of the cleaner according to FIG. 1 b ;
FIG. 5 is a generalised circuit diagram of an electronic control and regulation device having connected apparatuses according to the invention, an evaluation device, an angle-measuring device for guide vane angles, an operating and display device and an actuating device for guide vanes;
FIG. 6 is a diagrammatic side view of a feed device for a carding machine together with apparatuses according to the invention at suction waste-offtake hoods;
FIG. 7 shows the apparatus according to the invention comprising a photodiode, a light source and a measuring device for data collection at a waste pipe-line;
FIG. 8 is a graph showing the standard deviation (CV %) of the measurement voltage and the measurement voltage in dependence upon the guide vane position (or the width of the separation opening) and
FIG. 9 is a graph showing the waste composition in dependence upon the guide vane position (or the width of the separation opening).
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
With reference to FIG. 1 a , the fibre material to be cleaned (arrow F), especially cotton, in flock form, is fed to the cleaning apparatus, for example a CVT 4 cleaning apparatus made by Trützschler GmbH & Co. KG of Mönchengladbach, Germany, which is arranged in an enclosed housing. That is accomplished, for example, by means of a charging shaft (not shown), a conveyor belt or the like. The lap is fed, by two feed rollers 1 , 2 , with nipping, to a pinned roller 3 , which is rotatably mounted in the housing and rotates in an anti-clockwise direction (arrow A). Downstream of the pinned roller 3 there is arranged a clothed roller 4 covered by a sawtooth clothing. The roller 3 has a circumferential speed of about 10 to 21 m/sec. The roller 4 has a circumferential speed of about 15 to 25 m/sec. Roller 5 has a higher circumferential speed than roller 4 , and roller 6 has a higher circumferential speed than roller 5 . Downstream of rollers 3 and 4 there are successively arranged two further sawtooth rollers 5 and 6 , the directions of rotation of which are denoted by reference letters C and D, respectively. Rollers 3 to 6 have a diameter of about from 150 to 300 mm. The pinned roller 3 is enclosed by the housing. Associated with the pinned roller 3 is a separation opening 7 for removing fibre contaminants, the size of which opening is modified or modifiable according to the degree of contamination of the cotton. Associated with the separation opening 7 is a separating edge 12 , for example a blade. In the direction of arrow A there are provided, at the roller 3 , further separation opening 8 and a separating edge 13 . A separation opening 9 and a separating edge 14 are associated with the sawtooth roller 4 , a separation opening 10 and a separating edge 15 are associated with the sawtooth roller 5 , and a separation opening 11 and a separating edge 16 are associated with the sawtooth roller 6 . A suction offtake hood 17 to 21 is associated with each separating blade 12 to 16 . Reference letter E denotes the work direction of the cleaner.
In accordance with FIG. 1 b , a suction offtake line 22 , 23 , 24 , 25 and 26 is associated with each suction offtake hood 17 , 18 , 19 , 20 and 21 , respectively. The suction offtake lines 22 to 26 are in communication with a common suction offtake channel 27 . The rigid suction offtake lines 22 to 26 and the suction offtake channel 27 are of integral construction of, for example, sheet metal or plastics material. The lengths of the suction offtake lines 22 to 26 differ according to the distance between the suction offtake hood 17 to 21 and the suction offtake channel 27 . The cross-sections 27 I to 27 V of the suction offtake channel 27 —seen in the direction of flow (arrow K)—are located downstream of the entry of each suction offtake line 22 to 26 . The end of the suction offtake channel 27 is connected to a suction source (not shown). The directions of flow within the suction offtake lines 22 to 26 are shown by arrows L to P.
The mode of operation is as follows: The lap consisting of fibre flocks (F) is fed from the feed rollers 1 , 2 , with nipping, to the pinned roller 3 , which combs through the fibre material and takes up fibre tufts on its pins. When the roller 3 passes the separation opening 7 and the separating edge 12 , the centrifugal force, in dependence upon the circumferential speed and curvature of that roller and also upon the size of the separation opening 7 , which is matched to that first separation step, causes waste (short fibres and coarse contaminants) and a certain (per se undesirable) amount of good fibres to be flung out from the fibre material remaining on the roller; the material passes through the separation opening 7 into a suction offtake hood 17 (contaminants) in the housing. The fibre material pre-cleaned in that manner is taken off the first roller 3 by the tips of the clothing of the clothed roller 4 and is further opened out. When the rollers 4 , 5 and 6 pass the separation openings 9 , 10 and 11 , respectively, having separating edges 14 , 15 , and 16 , respectively, further contaminants are flung out from the system of fibres as a result of the centrifugal force.
Arrows B, C and D denote the directions of rotation of the clothed rollers 4 , 5 and 6 , respectively. Reference numerals 17 to 21 denote suction offtake devices for the contaminants leaving by the separation openings 7 to 11 , respectively. The directions of rotation A, B, C and D of rollers 3 , 4 , 5 and 6 , respectively, are different at adjacent rollers. At the end of the final roller 6 there is provided a pneumatic suction offtake device 22 for the cleaned fibre material (arrow H). The circumferential speed of each downstream roller is greater than the circumferential speed of the respective upstream roller. Reference numerals 23 ′ to 26 ′ denote adjustable air-guiding elements mounted at the air entry openings of the suction offtake hoods 18 to 21 , by means of which elements the amount of air drawn in can be adjusted. In the walls of the suction offtake channels 27 a , 27 b for the suction offtake hoods 17 to 21 there is mounted at each end face, that is to say coaxially with respect to the suction offtake hood 17 to 21 , a transparent pane 40 a to 40 e (see FIG. 2 ) so that it is possible to see into the suction offtake hood 17 to 21 from the outside. Associated with each of the panes 40 a to 40 e is a sensor arrangement 42 according to the invention (individual sensor arrangements being shown as 42 a to 42 g in the drawings), located outside the suction offtake channels 27 a , 27 b , by means of which the waste flowing through the suction offtake hood 17 to 21 and into the suction offtake channel 27 a , 27 b is detected by the sensor arrangement 42 . Reference numerals 139 , 140 and 141 indicate fixing devices.
In accordance with FIG. 2 , the suction offtake hood 17 is arranged between the two frame walls 28 , 29 (housing walls); a connection piece 30 a , 30 b is provided outside the walls 28 , 29 at each end 17 a , 17 b of the suction offtake hood 17 so that the suction offtake hood 17 passes through two openings in the frame walls 28 , 29 . A resilient annular seal 32 , for example made from foamed material, is placed around the connection pieces 30 . In the arrangement of FIG. 1 b , one end region 22 a of the suction offtake line 22 opens out into the suction offtake channel 27 a ; the other end region 22 b of the suction offtake line 22 opens out into the suction offtake channel 27 b . Reference numeral 34 denotes a fastening element, for example a screw connection. The ends of the suction offtake channels 27 a , 27 b are connected to a common suction offtake channel 44 (see FIG. 4 ), which is connected to a suction source (not shown). The connection of the suction offtake line 22 a to the suction offtake hood 17 and the suction offtake channel 27 a corresponds to the connection of the suction offtake line 22 b to the suction offtake hood 17 and the suction offtake channel 27 b . On each outer face of the suction offtake channels 27 a , 27 b there is mounted a transparent pane 40 a and 40 b , respectively, with which there is associated a camera 41 a and 41 b , respectively, outside the suction offtake channels 27 a and 27 b , respectively, which camera is used for detecting the waste. In FIG. 4 , only the sensor arrangements on channel 27 b are shown; the sensor arrangements on channel 27 a are of the same general construction but are not shown in FIG. 4 . Arrows Q and R denote the flow directions of the suction offtake streams inside the suction offtake hood 17 .
The cleaning apparatus illustrated in FIGS. 1 a , 1 b and 2 has at openings 8 to 11 devices by means of which the amount and also, to some extent, the nature of the waste being separated (foreign matter, trash, neps, good fibres etc.) can be adjusted or influenced. Those devices are in the form of motor-adjustable guide vanes 37 a to 37 d (referred to collectively below as 37 ) mounted in the region of the opener and cleaning rollers 3 to 6 upstream of the separating blades. It is possible, by means of the angular position α of those vanes 37 to influence the amount and also, to a certain extent, the nature of the material separated I ( FIGS. 3 a , 3 b ), a large angle of opening α resulting in a relatively large amount of separated material I and a small angle resulting in a correspondingly smaller amount. Stipulating the desired amount of separated material I at the same time determines very especially the cleaning action of the machine on the good material. Because it is generally the case that, with this kind of separation I, “good” fibre material will always be separated out as well, it is, in practice, necessary to find an acceptable compromise. This means that as much “bad material” as possible is separated out whilst, at the same time, separating out a minimum amount of good fibres. In order to be able to assess the waste I separated out and consequently to change the possible settings, the waste I is separated out, collected and, finally, visually assessed in the manner according to the invention.
In accordance with FIG. 2 , a transparent pane 40 a is mounted in the wall surface of the suction offtake channel 27 b , the centre-point of which pane is aligned with the axis of the suction offtake hood 17 . Associated with the pane 40 a , on the outside of the suction offtake channel 27 b , is a sensor arrangement 42 a (brightness sensor) in the form of a photodiode (see FIG. 7 ). In addition, a light source 41 (see FIG. 7 ) is provided directly next to the photodiode.
In accordance with FIG. 2 a , a pane 40 g is arranged in the wall surface of the connection piece 33 b , which connects the suction offtake channel 27 b to the outlet from the suction offtake hood 17 . Associated with the pane 40 g , on the outside, is a brightness sensor 42 g.
In accordance with FIG. 4 , the waste K 1 to K 8 from the individual separation locations is combined on each side of the machine to form combined streams M, N, drawn off continuously by means of a partial vacuum and conveyed to a central filtration and separation system 44 . In this case, in accordance with the invention, there is integrated in the waste channel 27 b , at the level of, that is to say aligned with, each suction offtake hood 17 to 21 , a brightness sensor 42 a to 42 d , together with appropriate illumination 41 a to 41 d (not shown in FIG. 4 ) and evaluation unit. The system is so arranged that fibres, foreign matter and other matter flying past in the line 27 b can be detected. The system is furthermore so arranged that it is possible to distinguish good fibres in the waste and to provide information relating thereto. In dependence upon corresponding specified requirements, the machinery influencing the composition of the waste I (e.g. the guide vanes 37 ) is then automatically adjusted until the desired waste quality has been achieved.
In accordance with FIG. 5 , there are connected to an electronic control and regulation device 43 (machine control), for example a microcomputer, three sensor systems 42 a , 42 b , 42 c by way of three evaluation devices 44 a , 44 b , 44 c , an operating and display device 50 , three angle-measuring devices 46 a , 46 b , 46 c for guide vane angles α ( FIGS. 3 a , 3 b ) and three vane-adjusting devices 45 a , 45 b , 45 c for adjustment of the guide vanes 37 a , 37 b and 37 c , respectively.
FIG. 6 shows a carding machine, for example a DK 903 high-performance carding machine made by Trützschler GmbH & Co. KG. There are provided, in the feed system of lickers—in 47 a , 47 b , 47 c , a suction waste-offtake hood 48 a , 48 b and 48 c at each roller, respectively, and also a connecting line 49 for the suction offtake hoods 48 a to 48 c . Associated with each of the suction offtake hoods 48 a to 48 c and with the connecting line 49 is a sensor system 42 a , 42 b , 42 c and 42 d (see FIG. 7 ).
In accordance with FIG. 7 , there is provided in the wall surface of the waste line 27 an opening in which there are arranged a brightness sensor 42 in the form of a photodiode and a light source 41 in the form of a direct-current visible-light illuminator. The photodiode 42 (photovoltaic element) is a signal transducer. The photodiode 42 is connected, by way of lines 42 1 , 42 2 , with a measurement apparatus 44 for data collection (voltage measurement apparatus). The system is based on the detection and evaluation of changes in voltage or resistance caused by reflection differences (differences in brightness caused by a difference in reflection) in spaces containing moving waste. For that purpose there is required a direct-current illuminator or high-frequency alternating-current illuminator, which is mounted at the end face or tangentially on the pipe-line or suction offtake hood of the spinning or cleaning room machine. Directly next to or even inside that illuminator there is a photosensitive element which receives the light reflected by the good fibres, converts it into current and measures the variation in reflection. The reflection is always detected in reflected incident light. An image is not required so that the detection problems caused by honeydew and other contaminants are avoided. It is solely the variations in the level of reflection (which are dependent upon the content of good fibres) that are used because it is only the variance that provides reliable information relating to the correctness of the operating point and the associated separation element setting. The optimum operating point is achieved at maximum contaminant separation and, at the same time, minimum good-fibre separation. A large amount of good fibres produces a high variation in reflection so that the variation in the current produced is correspondingly high or the remaining resistance is correspondingly low. In dependence upon that level, the separating unit can then be appropriately adjusted in order to control the amount of good fibres in the waste (cf. FIGS. 3 a , 3 b ).
FIG. 8 shows the dependence of the voltage at the measurement apparatuses 44 a to 44 c and of the coefficient of variation of the voltage upon the guide vane angle. The coefficient of variation in % is defined as:
CV
=
100
·
s
x
_
CV=coefficient of variation
s=standard deviation
x =mean
In operation, for a specific fibre material, the angle α of the guide vane 37 b is successively increased and the corresponding voltage values are detected at the measurement apparatus 44 . A large amount of good fibres in the waste results in a correspondingly high voltage value because of a correspondingly high light reflection. The voltage measurement values of the measurement apparatuses 44 a to 44 c and the guide vane angles α of the angle-measuring devices 46 a to 46 c are input into the computer 43 , which calculates the coefficient of variation (CV %) of the voltage and the functional dependence of the coefficient of variation on the guide vane angle α in accordance with the graph in FIG. 8 . In the curve according to FIG. 8 , at an angle α=13.1°, there is a characteristic change in the gradient which corresponds to the optimum operating point of the cleaning machine. At angle settings α>13.1°, the content of good fibres in the waste increases steeply, in undesirable manner, compared to the foreign matter and trash content (cf. FIG. 9 ). Then, by way of the actuating elements 45 a to 45 c , for example stepper motors, the inclination α of the guide vanes 37 a to 37 c is set to α=13.1° in accordance with the optimum operating point. The procedure described above is carried out automatically—during ongoing production or in a preliminary test run. The optimum operating point can be monitored and, in the event of departures therefrom, can be re-set automatically.
By means of the apparatus according to the invention, the irregularity of the stream of waste separated out is assessed in terms of its degree of opening. The irregularity is measured on the basis of the standard deviation of the light reflected by the individual items separated out. As a result of the incident light method, the contaminant content of the items is invisible to the sensor so that, with this measurement method, neither the contaminant content nor the brightness of the separated-out waste is assessed but rather only the variation in the brightness of the good fibres.
In order to measure the quantitative waste distribution (trash/good fibres) it is also possible, in principle, to use infra-red light because the trash content of the waste reflects strongly in the infra-red range. From the voltage (resistance) difference between white-light and infra-red illumination it is possible to calculate the contents of trash and good fibres. The area of use encompasses all fibre- and waste-conveying channels but not waste chambers containing waste that is at rest.
The sensor in accordance with the invention can advantageously used to determine a state of blockage in the suction offtake hood, in which case the machine control issues an error message. That may be advantageously accomplished by means of the fact that the normally dynamic signal changes to a static state as a result of the blockage, that static signal course being interpreted as an indication of a blockage, or by means of the fact that the signal exceeds or falls below certain limit values as a result of the blockage.
Although the foregoing invention has been described in detail by way of illustration and example for purposes of understanding, it will be obvious that changes and modifications may be practised within the scope of the appended claims. | In an apparatus at a spinning preparation machine, for example a cleaner, opener, carding machine or the like, for detecting waste which is separated out from fibre material, for example cotton, and consists of foreign matter and good fibres and which is collected in a collecting device, there is provided an optical measuring device having a brightness sensor, which measuring device examines the waste.
In order to make it possible, by simple means, for the content of good fibres in the waste to be detected and to allow optimum adjustment of the composition of the waste, especially with a high content of trash and low content of good fibres, the waste material is moved past at least one sensor arrangement responding to good fibres, and the sensor arrangement comprises a light source, the light reflected by the moving good fibres being detected by the brightness sensor and being converted into electrical signals, from which the good fibre content can be determined. | 3 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the priority of Korean Patent Application No. 10-2009-0130055 filed on Dec. 23, 2009, in the Korean Intellectual Property Office, the disclosure of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a multilayer ceramic capacitor and a method of fabricating the same, and more particularly, to a multilayer ceramic capacitor capable of preventing cracking and delamination due to a difference in thermal expansion coefficients while stably securing capacitance and a method of fabricating the same.
2. Description of the Related Art
In general, a multilayer ceramic capacitor includes a plurality of ceramic dielectric sheets and internal electrodes inserted between the plurality of ceramic dielectric sheets. The multilayer ceramic capacitor can implement high capacitance with a small size and can be easily mounted on a substrate, such that it has been widely used as a capacitive part for various electronic devices.
Recently, with the development of compact multi-functional electronic products, chip components are becoming smaller yet having higher performances. As a result, there has been increased demand for a compact and highly capacitive multilayer ceramic capacitor. Therefore, a multilayer ceramic capacitor having a thickness of 2 μm and a stack of 500 layers or more has recently been fabricated.
However, a volume ratio occupied by internal electrode layers increases due to the thinning and high lamination of the ceramic dielectric layers, such that cracking or dielectric breakdown may occur in the ceramic laminate due to thermal impact applied to a circuit board by firing, reflow solder, or the like during a mounting process or the like.
In detail, cracking occurs when stress generated due to the difference in thermal expansion coefficients between materials forming the ceramic layer and the internal electrode layer is applied to the ceramic laminate. In particular, cracking mainly occurs at both edges of the upper and lower portions of the multilayer ceramic capacitor.
SUMMARY OF THE INVENTION
An aspect of the present invention provides a multilayer ceramic capacitor capable of effectively preventing cracking and delamination in a ceramic laminate due to a difference in thermal expansion coefficients while stably securing capacitance and a method of fabricating the same.
According to an aspect of the present invention, there is provided a multilayer ceramic capacitor including: a capacitor body formed by alternately stacking a dielectric layer having a thickness of td and more than one opposing pair of a first internal electrode having a thickness of te and a second internal electrode having the same thickness as the first internal electrode, and having the dielectric layer therebetween; and a protective layer formed by stacking a dielectric material layer on at least one of an upper surface and a lower surface of the capacitor body in order to have a thickness of tc, wherein when a thickness from an end of a region where the first internal electrode and the second internal electrode oppose each other to side and end surfaces of the capacitor body is a, it satisfies the following Equation 1.
10< tc /( te+td )<30 Equation 1
Where the multilayer ceramic capacitor may satisfy the following Equation 2.
0.2< tc/ta< 0.8 Equation 2
Where the number of stacked dielectric layers may be 100 to 1000.
According to another aspect of the present invention, there is provided a multilayer ceramic capacitor including: a capacitor body formed by alternately stacking a dielectric layer having a thickness of td and more than one opposing pair of a first internal electrode having a thickness of te and a second internal electrode having the same thickness as the first internal electrode, and having the dielectric layer therebetween; and a protective layer formed by stacking a dielectric material layer on at least one of an upper surface and a lower surface of the capacitor body in order to have a thickness of tc, wherein when a thickness from an end of a region where the first internal electrode and the second internal electrode oppose each other to side and end surfaces of the capacitor body is a, it satisfies the following Equation 2.
0.2< tc/ta< 0.8 Equation 2
Where the number of stacked dielectric layers may be 100 to 1000.
According to another aspect of the present invention, there is provided a method of fabricating a multilayer ceramic capacitor including: forming a capacitor body by alternately stacking a dielectric layer having a thickness of td and more than one opposing pair of a first internal electrode having a thickness of te and a second internal electrode having the same thickness as the first internal electrode, and having the dielectric layer therebetween; forming a protective layer by stacking a second dielectric layer on at least one of an upper surface and a lower surface of the capacitor body so that a dielectric material layer has a thickness of tc; pressurizing the capacitor body; and firing the capacitor body, wherein when a thickness from an end of a region where the first internal electrode and the second internal electrode oppose each other to side and end surfaces of the capacitor body is a, it satisfies the following Equation 1.
10< tc /( te+td )<30 Equation 1
where the method of fabricating the multilayer ceramic capacitor may satisfy the following Equation 2.
0.2< tc/ta< 0.8 Equation 2
At the forming of the capacitor body, the number of stacked dielectric layers may be 100 to 1000.
The method of fabricating the multilayer ceramic capacitor may further include cutting the capacitor body between the pressurizing and the firing in order to form an individual unit.
According to another aspect of the present invention, there is provided a method of fabricating a multilayer ceramic capacitor including: forming a capacitor body by alternately stacking a dielectric layer having a thickness of td and more than one opposing pair of a first internal electrode having a thickness of te and a second internal electrode having the same thickness as the first internal electrode, and having the dielectric layer therebetween; and forming a protective layer by stacking a dielectric material layer on at least one of an upper surface and a lower surface of the capacitor body in order to have a thickness of tc; pressurizing the capacitor body; and firing the capacitor body, wherein when a thickness from an end of a region where the first internal electrode and the second internal electrode oppose each other to side and end surfaces of the capacitor body is a, it satisfies the following Equation 2.
0.2< tc/ta< 0.8 Equation 2
At the forming of the capacitor body, the number of stacked dielectric layers may be 100 to 1000.
The method of fabricating the multilayer ceramic capacitor may further include cutting the capacitor body between the pressurizing and the firing in order to form an individual unit.
BRIEF DESCRIPTION OF THE DRAWINGS
The above and other aspects, features and other advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a perspective view schematically showing a multilayer ceramic capacitor according to an exemplary embodiment of the present invention;
FIG. 2 is a cross-sectional view taken along line A-A of FIG. 1 ;
FIG. 3 is a cross-sectional view taken along line B-B of FIG. 1 ; and
FIGS. 4A through 4C are cross-sectional views schematically showing main fabricating processes of a multilayer ceramic capacitor according to an exemplary embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Hereinafter, exemplary embodiments will be described in detail with reference to the accompanying drawings so that they can be easily practiced by those skilled in the art to which the present invention pertains. However, in describing the exemplary embodiments of the present invention, detailed descriptions of well-known functions or constructions are omitted so as not to obscure the description of the present invention with unnecessary detail.
In addition, like reference numerals denote parts performing similar functions and actions throughout the drawings.
It will be understood that when an element is referred to as being “connected with” another element, it can be directly connected with the other element or may be indirectly connected with the other element with element (s) interposed therebetween. Unless explicitly described to the contrary, the word “comprise” and variations such as “comprises” or “comprising,” will be understood to imply the inclusion of stated elements but not the exclusion of any other elements.
Hereinafter, a multilayer ceramic capacitor and main fabricating processes according to exemplary embodiment of the present invention will be described with reference to FIGS. 1 through 4C .
FIG. 1 is a perspective view schematically showing a multilayer ceramic capacitor according to an exemplary embodiment of the present invention, FIG. 2 is a cross-sectional view taken along line A-A′ of FIG. 1 , FIG. 3 is a cross-sectional view taken along line B-B′ of FIG. 1 , FIGS. 4A through 4C are cross-sectional views schematically showing main fabricating processes of a multilayer ceramic capacitor according to an exemplary embodiment of the present invention.
Referring to FIG. 1 , a multilayer ceramic capacitor according to an embodiment of the present invention may include a capacitor body 1 and an external electrode 2 .
The capacitor body 1 includes a plurality of dielectric layers 6 having a thickness of td stacked therein and a first internal electrode 4 a and a second internal electrode 4 b having a thickness of te that may be alternately stacked to oppose each other, having the dielectric layer 6 therebetween. The dielectric layer 6 may be made of barium titanate (Ba 2 TiO 3 ) and the first and second internal electrodes 4 a and 4 b may be made of nickel (Ni), tungsten (W), cobalt (Co), however, they are not limited thereto.
The external electrode 2 may be formed at both ends of the capacitor body 1 . The external electrodes 2 are formed to be electrically connected to the first and second internal electrodes 4 a and 4 b that are exposed to the outer surface of the capacitor body 1 , thereby making it possible to perform the role of external terminals. The external electrode 2 may be made of copper (Cu), however it is not limited thereto.
Referring to FIGS. 2 and 3 , the multilayer ceramic capacitor according to one embodiment of the present invention may include an effective layer 20 where the dielectric layer 6 and the first and second internal electrodes 4 a and 4 b are alternately stacked. In addition, the multilayer ceramic capacitor may include a protective layer 10 formed by stacking the dielectric material layer on the upper and lower surfaces of the effective layer 20 .
The protective layer 10 is formed by continuously stacking a plurality of dielectric material layers so that the plurality of dielectric material layers have the same thickness on at least one of the upper and lower surfaces of the effective layer 20 , preferably, on both the upper and lower surfaces thereof, thereby making it possible to protect the effective layer 20 from external impacts or the like.
When the first and second internal electrodes 4 a and 4 b of the effective layer 20 are made of nickel (Ni), the thermal expansion coefficient thereof is about 13×10 −6 /° C. and the thermal expansion coefficient of the dielectric layer 6 made of ceramic is about 8×10 −6 /° C. When thermal impact is applied to the circuit board by firing, reflow solder or the like, during a mounting process, due to the difference in the thermal expansion coefficients between the dielectric layer 6 and the first and second internal electrodes 4 a and 4 b , stress is applied to the dielectric layer 6 . Therefore, internal structural defects such as cracking, delamination, or the like occur in the dielectric layer 6 due to stress from thermal impact, thereby degrading heat-resistance and humidity-resistance characteristics and making it possible that the reliability of products will be degraded.
Herein, the difference in firing shrinkage becomes large due to the difference in the thermal expansion coefficients and the occurrence of internal structural defects is likely to be increased, as the thickness ratio of the protective layer 10 is increased, as compared to the thickness of the first and second internal electrodes 4 a and 4 b.
Therefore, as shown in FIG. 2 , in the multilayer ceramic capacitor according to an embodiment of the present invention, since the thickness ratio (tc/(te+td)) between the protective layer 10 and a single layer that includes the first internal electrode and the second internal electrode 4 a and 4 b and the dielectric layers 6 is 10 to 30, the protective layer 10 is fabricated to be thinner than that of the prior art. As described above, since the protective layer 10 is thinner than protective layers common in the prior art, the number of stacked layers is also increased, thereby making it possible to increase the capacitance thereof.
In addition, since the thickness ratio between the protective layer 10 and the side and end surfaces of the multilayer ceramic capacitor is 0.2 to 0.8, the protective layer 10 is fabricated to be thinner than the prior art. As described above, since the protective layer 10 is thinner than protective layers common in the prior art, the number of stacked layers is also increased, thereby making it possible to increase the capacitance thereof.
Meanwhile, since the capacitance of the multilayer ceramic capacitor is in inverse proportion to the thickness of the dielectric layer 6 that is positioned between the first and second internal electrodes 4 a and 4 b , as the thickness tc of the dielectric material layer of the outside portion is relatively thin, the capacitance of the multilayer ceramic capacitor is increased. In addition, as the amount of thickness “a” that the outside portion of the dielectric layer 6 is formed to have is relatively thin, the capacitance of the multilayer ceramic capacitor is thereby increased.
Since it is important to prevent cracking and delamination due to thermal impact while stably securing capacitance, the amount of thickness tc that the dielectric material layer of the protective layer 10 is formed to have, as compared to a single layer formed of the first internal electrode 4 a or the second internal electrode 4 b and a single dielectric layer making up part of the effective layer 20 or the amount of thickness tc that the protective layer 10 is formed to have, as compared to the thickness a of the outside portion, may be determined by experimentation.
TABLE 1
Thickness
ratio of
protective
layer per
single
Number of
Number of
layer
stacked
Capacitance
generated
Example
(tc/te + td))
layers
(μF)
cracks
1
5
213
1.14
2/100
2
10
208
1.12
0/100
3
15
203
1.09
0/100
4
20
198
1.02
0/100
5
25
193
0.98
0/100
6
30
188
0.97
0/100
7
35
183
0.93
4/100
8
40
178
0.83
9/100
TABLE 2
Thickness
ratio of
protective
layer to
side
Number of
Number of
surface
stacked
Capacitance
generated
Example
(tc/a)
layers
(μF)
cracks
1
0.1
396
10.8
5/100
2
0.2
391
10.8
0/100
3
0.3
387
10.7
0/100
4
0.4
381
10.5
0/100
5
0.5
376
10.4
0/100
6
0.6
371
10.2
0/100
7
0.7
366
9.9
0/100
8
0.8
361
9.7
0/100
9
0.9
356
9.4
2/100
10
1.0
351
9.2
10/100
Table 1 demonstrates that the number of stacked layers, the capacitance, and the number of generated cracks, with respect to the thickness ratio between the protective layer 10 and a single layer of the multilayer ceramic capacitor, are measured.
Table 2 demonstrates that the number of stacked layers, the capacitance, and the number of generated cracks with respect to the thickness ratio between the protective layer 10 and the side and end surfaces of the multilayer ceramic capacitor are measured.
Referring to Tables 1 and 2, when the thickness ratio between the protective layer 10 and a single layer of the multilayer ceramic capacitor is calculated to be in the range of 10 to 30, it can be appreciated that cracking does not occur and the capacitance is increased by 5% to 10% as compared to the prior art.
When the thickness ratio between the protective layer 10 and the side and end surfaces is in the range of 0.2 to 0.8, it can be appreciated that cracking does not occur and capacitance is also increased by 5% to 10% as compared to the prior art. It can be appreciated that the reliability of products is affected according to the reduction.
On the other hand, when the thickness ratio of the protective layer 10 to a single layer of the multilayer ceramic capacitor is calculated to be 35 or more and the thickness ratio between the protective layer 10 and the side and end surfaces of the multilayer ceramic capacitor is calculated to be 0.9 or more, cracking occurs. When the thickness ratio between the protective layer 10 and a single layer of the multilayer ceramic capacitor is calculated to be 5 or less and the thickness ratio between the protective layer 10 and the side and end surfaces of the multilayer ceramic capacitor is calculated to be 0.1 or less, the protection function of the internal electrode is not implemented properly, diminishing the humidity-resistance characteristic, thereby degrading reliability.
Embodiment
As shown in FIG. 4A , the dielectric layer 6 of the capacitor body 1 was formed to include a binder, a plasticizer, and a residual dielectric material. A conductive internal electrode 4 is printed on the dielectric layer 6 obtained by molding a slurry including the construction material. The thickness ratio between the protective layer 10 and a single layer of the multilayer ceramic capacitor was variously changed so that it was in the range of 10 to 30 and the thickness ratio between the protective layer 10 and the side and end surfaces was variously changed that it was in the range of 0.2 to 0.8. Next, the multilayer ceramic capacitor was fabricated by performing bonding, firing, and plating processes after being pressurized as shown in FIG. 4B and being cut as shown in FIG. 4C .
As set forth above, according to exemplary embodiments of the present invention, the multilayer ceramic capacitor that can prevent cracking and delamination due to the difference in the thermal expansion coefficients while stably securing capacitance and the method of fabricating the same can be provided.
In addition, according to exemplary embodiments of the present invention, the correlation between the reliability of the multilayer ceramic capacitor and the thickness of the dielectric material layer can be proposed.
While the present invention has been shown and described in connection with the exemplary embodiments, it will be apparent to those skilled in the art that modifications and variations can be made without departing from the spirit and scope of the invention as defined by the appended claims. | There is provided a multilayer ceramic capacitor including: a capacitor main body formed by stacking a dielectric layer having a thickness of td and alternately stacking more than one opposing pair of a first internal electrode having a thickness of te and a second internal electrode having the same thickness as the first internal electrode, and having the dielectric layer therebetween; and a protective layer formed by stacking a second dielectric layer on at least one of an upper surface and a lower surface of the capacitor main body so that a dielectric material layer has a thickness of tc, wherein when a thickness from an end of a region where the first internal electrode and the second internal electrode oppose each other to side and end surfaces of the capacitor main body is a, it satisfies the following Equation 1 and a method of fabricating a multilayer ceramic capacitor are provided.
10< tc /( te+td )<30 Equation 1 | 7 |
BACKGROUND OF THE INVENTION
The present invention is directed to a potent tight-binding multisubstrate adduct inhibitor of glycinamide ribonucleotide transformylase (GAR TFase; E.C. 2.1.2.2). GAR TFase is a crucial, reduced folate-requiring enzyme involved early in de novo purine biosynthesis, catalyzing the formyl transfer from (6R, alpha-S)-10-formyl H 4 folate to glycinamide ribonucleotide (GAR). It has thus attracted some interest as a target enzyme for the design of pharmacologically active substances, especially anti-neoplastic agents. See, Chabner, B.A., et al., in "Chemistry and Biology of Pteridines, Proc. 8th International Symposium," Cooper and Whitehead, eds. pp. 945-51, deGruyter, Berlin, 1986.
The inhibitor compounds disclosed herein will be useful as an anti-gout and/or anti-neoplastic therapeutic agent or as a potentiator for other such agents.
Specific potent inhibitors of enzymes have previously been designed using the ideas of Pauling and Jencks, which stress the importance of the enzyme's ability to stabilize a substrate's passage through its transition state to product. Much of this stabilizing energy is derived from the binding energy acquired when substrate combines with enzyme. See for example, L. Pauling, Chem. Eng. News, 24, 1375 (1946); W. P. Jencks, Chemistry and Enzymology, (Dover Publications, Inc., New York, 1987) and Gandour et al., "Transition States of Biochemical Process", (Plenum Press, New York, (1978); Collins et al., J. Biol. Chem., 246, 6599-6605 (1971); Bartlett et al., J. Am. Chem. Soc., 106, 4282-4283 (1984); Chan et al., Heterocycles, 23, 3079-3085 (1986) and Park et al., J. Med. Chem., 22, 1134-1137 (1979); Wolfenden, Annu. Rev. Biophys. Bioeng., 5, 271-305 (1976) and Wolfenden, Acc. Chem. Res., 5, 10-18 (1972).
A number of potent specific inhibitors of enzymes have been designed using the concept of multisubstrate adduct inhibition (or MAI). See, Gandour and Schowen, eds., "Transition States of Biochemical Processes," Plenum Press, New York, 1978; and Broom, Federation Proc., 45, 2779-2783 (1986). For a recent list of specific enzyme inhibitors, see Wolfenden, et al., in "Enzyme Mechanisms", Page and Williams, eds., pp. 97-102, Royal Society of Chemistry, London, 1987.
The tying together of both substrates of a bimolecular, enzyme-catalyzed reaction yields a molecule possessing the binding stabilization of both individual substrates, in addition to the entropic advantage of reduced molecularity (Jencks, W.P., Advances in Enzymology, 43, 219-410 (1975)). However, it should be noted that a multisubstrate adduct inhibitor is not intended to mimic the transition state of a catalyzed reaction.
The degree to which an enzyme-inhibitor complex remains associated with the desired substrate is a measure of the inhibitor's potency. A common measure for the effectiveness of an inhibitor is its dissociation constant, K D , or its inhibition constant, K I . To the first approximation, these are the same, and are a ratio of free inhibitor and enzyme to the enzyme inhibitor complex. The smaller the number, the less free enzyme is present, and the better the inhibitor.
Prior to the present invention, other inhibitors of GAR TFase have been produced, but none were as potent in vitro as the commonly used anti-folate agent methotrexate (which is specific for another enzyme important to purine biosynthesis, dihydrofolate reductase [DHFR]). The highly active GAR TFase inhibitor of the present invention thus represents a breakthrough in this area.
There are a modest number of compounds actually tested against GAR TFase. Those with published K I values (inhibition constants) include the work of Caperelli et al., (J. Med. Chem., 29, 2117-2119 (1986) and J. Med. Chem., 30, 1254-1256 (1987)) who have shown that the substitution at N 10 of DDF with various substituted alkyl, acyl, benzyl, and heterocyclic groups produce modest inhibition of murine lymphoma GAR TFase, with K I 's ranging from 1.3 to 33 uM. These compounds were also shown to inhibit thymidylate synthase (TS) and dihydrofolate reductase (DHFR), illustrating a great lack of specificity for GAR TFase. See, Jones et al., J. Med. Chem., 28, 1468-1476 (1985).
The inhibitor of the present invention is conservatively about 10 5 times more potent (based on a comparison of the K I values) than the above-mentioned compounds and has no significant inhibitory effect on DHFR or TS. ##STR2## appears to be an inhibitor of GAR TFase. This inhibitor, when tested against solid tumors in mice, was indirectly shown to inhibit GAR TFase and to cause depletion of intracellular pools of ATP and GTP, end products of purine biosynthesis. See, Taylor et al., J. Med. Chem., 28, 914-921 (1985); Moran et al., Proc. Amer. Assoc. Cancer Research, 26, 231 (1985) and Beardsley et al., "Chemistry and Biology of Pteridines, Proc. 8th International Symposium," B. A. Cooper and Whitehead, V. M., eds. (deGruyter: Berlin, pp. 953-7 (1986).
Since no data was reported for the activity of DDATHF against purified GAR TFase (i.e., there is no K I given) it is difficult to compare DDATHF to the inhibitors of the present invention in terms of potency. DDATHF appears to show impressive activity against a variety of solid tumors in mice whereas methotrexate (MTX), a common anti-folate in use today, shows minimal activity against these same tumors. Beardsley et al., Chemistry and Biology of Pteridines, 53-957 (1986).
None of the previously discussed inhibitors are multisubstrate adduct inhibitors. The series of DDF analogues tested by Caperelli et al., were poor inhibitors of GAR TFase both in respect to their potency and specificity. The compound of Taylor et al. may have sites of action other then GAR TFase and a quantitative account of its activity against a purified GAR TFase has yet to be reported.
Two previous attempts at the synthesis of a multisubstrate adduct inhibitor for GAR TFase have been reported. For example, Licato, Jr., in his Ph.D. Dissertation (U. Utah) reported the unsuccessful efforts toward the synthesis of the following compound: ##STR3## See, Diss. Abstr. Inc., B, 47, 2918 (1987).
In J. Med. Chem., 31, 697-700 (1988), Temple and his coworkers reported the synthesis of several potential anticancer agents which were designed to be effective as GAR TFase inhibitors. These tetrahydrofolic acid (THF) derivatives included the following: ##STR4## No useful biological activity was reported for any of these compounds against GAR TFase.
The synthetic approach of the present invention, has been found capable of generating the most potent and specific inhibitor of the GAR TFase enzyme yet described anywhere in the literature.
SUMMARY OF THE INVENTION
The present invention is directed to several related potent tight binding multisubstrate adduct inhibitors (MAIs) of glycinamide ribonucleotide transformylase (GAR TFase; E.C. 2.1.2.2), a folate requiring enzyme of de novo purine biosynthesis. Each of these compounds will be useful as an anti-gout, and/or anti-neoplastic therapeutic agent or as a potentiator for other such agents.
The inhibitors of the present invention have the following general Formula (I) [wherein stereochemistry, unless otherwise defined, is deemed to be variable]: ##STR5## wherein R=H or PO 3 , and pharmacologically acceptable salts thereof.
The term "pharmacologically acceptable salts" refers to salts prepared from pharmaceutically acceptable non-toxic bases including inorganic bases and organic bases. Salts derived from inorganic bases include sodium, potassium, lithium, ammonium, calcium, magnesium, ferrous, zinc, copper, manganous, aluminum, ferric, manganic, and the like. Particularly preferred are the ammonium, potassium, sodium, calcium and magnesium salts. Salts derived from pharmaceutically acceptable organic non-toxic bases include salts of primary, secondary, and tertiary amines, substituted amines including naturally occurring substituted amines, cyclic amines and basic anion exchange resins, such as isopropylamine, trimethylamine, diethylamine, triethylamine, tripropylamine, ethanolamine, 2-dimethylaminoethanol, 2-diethylaminoethanol, tromethamine, lysine, arginine, histidine, caffeine, procaine, hydrabamine, methylglucamine, theobromine, purines, piperazine, piperidine, N-ethylpiperidine, polyamine resins and the like. Particularly preferred organic non-toxic bases are isopropylamine, diethylamine, ethanolamine, piperidine, tromethamine, choline and caffeine.
Typically, the compounds of the present invention wherein R is either H or PO 3 , are prepared as a mixture (1:1) of alpha and beta anomers (at location C 1 '), and these mixtures are considered a part of the present invention. However, the compounds are readily separated by conventional methods and the separated compounds are considered to be preferred embodiments of the present invention.
More preferred compounds of Formula (I) are the separated alpha and beta anomers containing the phosphoribosyl group, i.e., those wherein R=PO 3 .
The most preferred compound of Formula (I) is the beta anomer, N 10 -[5'-phosphoribosyl-1'-β-amino -carbonylmethyl-1-thioacetyl]-5,8-dideazafolate, which has the stereochemical formula: ##STR6##
BRIEF DESCRIPTION OF THE DRAWING
The FIGURE illustrates the preferred GAR TFase expression vector, pJS167.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
As described above, the present invention is most preferably directed to the beta anomer of TGDDF (for ThioGarDideazaFolate), which has the chemical name -N 10 -[5'-phosphoribosyl-1'-β-aminocarbonylmethyl -1-thioacetyl]-5,8-dideazafolate.
This compound represents the first successful multisubstrate adduct inhibitor for GAR TFase which includes nearly all of the structural features of the two substrates, and provides the molecule with a very high specific affinity for the enzyme.
All of the inhibitors of the present invention consist of two components, a folate component and a ribonucleotide component. Each component further corresponds to a normal substrate of the enzyme. The general synthetic strategy for the formation of the compounds is illustrated in Scheme I (below).
In general, this synthetic route relies upon the synthesis of each half of the desired compound separately, and thereafter utilizes a regiospecific and mild aqueous coupling reaction to join the two halves.
For the folate half, an analogue of the natural substrate was selected, 5,8-dideazafolate (DDF, 4a) instead of the natural substrate. Activation of the DDF molecule in the requisite site is readily accomplished, yielding bromoacetyl-DDF (4b).
For the ribonucleotide half, thioGAR, a GAR analogue was selected as most appropriate. The only difference between the natural substrate and thioGAR is the sulfur on the side chain in the place of a nitrogen. This provides a reactive end on thioGAR, one which allows the final coupling reaction to generate the desired compound without subsequent removal of protecting groups.
The coupling reaction itself matches the highly nucleophilic end on the thioGAR with the highly electrophilic end on bromoacetyl-DDF, (Daubner, et al., Biochem., 25, 2951-2957 (1986)). ##STR7##
Design and synthesis of a complementary nucleophilic GAR analog (thioGAR) allowed a convergent and regiospecific synthesis under mild conditions providing a product with inherent hydrolic and oxidative stability. The mercapto analog of GAR allowed the coupling reaction to be carried out at neutral pH in an aqueous buffered medium.
ThioGAR was prepared by the route outlined in Scheme 2, the centerpiece of which was the DCC coupling of tribenzoyl ribosylamine 5 with S-protected mercaptoacetic acid (Schendel & Stubbe, Biochem., 25: 4356-4365 (1986). ##STR8##
In Schemes I and II, the reagents and conditions for each of the reaction steps listed were as follows:
a: DCC, Ph 3 CSCH 2 CO 2 H, acetone, RT, 14 hr.
b: NaOMe, MeOH, RT, 45 min.
c: 10 eq. POCl 3 , (MeO) 3 PO, 0 o , 2 hr.
d: 80% trifluoroacetic acid/H 2 O, RT, 45 min.
e: Aq. NH 3 to pH 7.5, 100 mM HEPES, pH 7.5
f: 100 mM HEPES, pH 7.5, 60°, 1 hr.
As illustrated, the synthesis is a convergent method employing a directed coupling in aqueous solution as the last step. This avoids the deprotection problems encountered in one previously attempted synthesis of a specific MAI for GAR TFase, Licato, supra.
This synthetic scheme has several very important advantages. First, the DDF cofactor is fully active with all types of GAR TFase isolated. (Daubner et al., Biochem., 25, 2951-2957 (1986); Inglese et al., Federation Proc., 46, 2218 (1987)). Secondly, the fully oxidized, carbocyclic quinazoline ring system makes this compound completely air-stable. Thirdly, the C 6 asymmetric center of the tetrahydrofolate has been replaced by an achiral center, again making synthetic transformations easier.
This synthesis was based in part on the previously described compound N 10 -(bromoacetyl)-5,8-dideazafolate, an electrophilic irreversible inactivator of the enzyme. (Daubner, et al., Biochem., 25, 2951-2957 (1986)).
As shown in Scheme II, S-trityl mercaptoacetic acid was formed by the condensation of equimolar amounts of triphenylmethanol with mercaptoacetic acid in excess trifluoroacetic acid. Coupling of the acid with tribenzoyl ribosylamine, 5, was promoted by DCC. The tribenzoyl riboside, 6, was deprotected with NaOMe in MeOH, giving the water insoluble trityl thio-riboside 7. The crude riboside was phosphorylated with a 10-fold molar excess of phosphoryl chloride at 0° C. in trimethyl phosphate (Yoshikawa, et al., Tet. Lett., 50, 5065 (1967)). After hydrolytic workup, the product could be purified either by Sephadex® A-25 (Pharmacia) ion exchange chromatography, or by preparative RP-HPLC. The latter allowed separation of anomers.
Deprotection of 8 to ThioGAR, and coupling with compound 4b were accomplished in one step, using oxygen-free reagents. TritylthioGAR, 8, was treated with 1 ml of 80% aqueous TFA, then neutralized to produce a buffered pH 7.5 solution. Addition of the bromoacetyl folate derivative 4b, and reaction at 60o for one hour gave an adduct which could be purified on RP-HPLC using gradient elution (CH 3 CN in H 2 O. Both solvents (12% at 0.7 ml/min.) gave pure single anomers of the adduct, with the beta anomer eluting before the alpha. The solution of pure anomer must be neutralized (aqueous NH 3 ) before concentration (Speed-vac); else in the presence of TFA, anomerization occurs.
The reaction catalyzed by GAR TFase as based on a direct displacement process is shown below in Scheme III. The two substrates in the forward direction are glycinamide ribonucleotide (GAR) and N 10 -formyltetrahydrofolate (N 10 --CHO--H 4 F). In accordance with the teachings of this invention, a multisubstrate adduct inhibitor should contain sufficient characteristics of the two substrates to convey strong affinity for the target enzyme. ##STR9##
The interaction of beta-TGDDF (β-TGDDF) with GAR TFase was characterized by the effect of the inhibitor on the activity of the enzyme as well as independent measures of its affinity for GAR TFase.
The thermodynamic dissociation constant, K D , for the E.β-TGDDF complex was measured by following the enhancement of the inhibitor's 395 nm fluorescence (excitation at 275 nm) upon binding to GAR TFase. A concentrated E. coli GAR TFase solution was added to an 11 nM solution of purified β-TGDDF; for each addition, the fluorescence at three different wavelengths (396, 400, and 405 nm) was measured. Fluorescence titration data was analyzed by the method of Taira and Benkovic, J. Med. Chem., 31, 129-137 (1988).
The average value for K D calculated from the three wavelengths is 250 pM, with a standard error of about 50 pM. The alpha-anomer K D is 5.8 nM, and clearly its binding affinity for GAR TFase is lower than the beta-anomer.
Beta-TGDDF acts as a slow, tight-binding inhibitor against four species of GAR TFase; E. coli, Avian, HeLaO, and L1210. All assays were carried out by following the increase of 5,8-dideazafolate absorbence at 295 nm in buffered medium at 26° C. To initiate the reaction, enzyme (1 nM final concentration) was added to a mixture of saturating substrates and variable amounts of inhibitor. A characteristic family of curves was obtained, showing slow, tight-binding inhibition. See, Morrison, Trends Biochem. Sc., 7, 102 (1982) and Morrison, et al., Adv. Enzymology, Relat. Areas Mol. Biol., 57, 201-301 (1987).
As has been described above, the compounds of the present invention are useful for inhibiting the GAR TFase enzyme in animals, including humans. The invention thus further provides a method for the inhibition of this enzyme in animals, including mammals, and especially humans, which comprises the administration of a clinically useful amount of a compound of Formula (I) in a pharmaceutically useful form, once or several times a day or other appropriate schedule, orally, rectally, parenterally, or applied topically.
Thus there is provided as a further, or alternative aspect of the invention, the compounds of the present invention for use in therapy, as GAR TFase inhibitors. For example, it is believed that the compounds of the present invention, as effective inhibitors of the GAR TFase enzyme in vivo, will be useful in the treatment and/or prevention of gout in patients suffering from inherited superactivity of PRPP synthetase. See, M. A. Becker et al., Arthritis and Rheumatism, Vol. 29, pp. 880-888 (1986) and M. A. Becker et al., Biochim. Biophys. Acta, Vol. 882, pp. 168-176 (1986).
It is further believed that enzyme inhibitors of this type are useful as anti-neoplastic therapeutic agents or as potentiators for other such agents. For example, the suspected GAR TFase inhibitor, DDATHF, has been shown to have anti-tumor,activity against a wide variety of tumor cells in vivo and in vitro. These cells include inter alia; HL-60, 6C3HED lymphosarcoma, X-5563 and B-16 melanoma, and L1210 and P388 leukemia. See C. Shih et al., Proc. Amer. Assoc. Cancer Res., Vol. 29, 283, Abstr. No. 1125 (1988); G. P. Beardsley et al., Proc. Amer. Assoc. Cancer Res., Vol. 27, 259, Abstr. No. 1027 (1986); R. G. Moran et al., Proc. Amer. Assoc. Cancer Res., Vol. 28, 274, Abstr. No. 1084 (1987); J. A. Sokoloski et al., Proc. Amer. Assoc. Cancer Res., Vol. 29, 77, Abstr. No. 306 (1988); G. Pizzorno et al., Proc. Amer. Assoc. Cancer Res., Vol. 29, 281, Abstr. No. 1118 (1988); E. C. Taylor et al., "Chemistry and Biology of Pteridines," pp. 116-119, Walter de Gruyter & Co., Berlin/New York (1983), E. C. Taylor et al., "Chemistry and Biology of Pteridines,"
pp. 61-64, Walter deGruyter & Co., Berlin/New York (1986), G.P. Beardsley et al., "Chemistry and Biology of Pteridines," pp. 954-957, Walter deGruyter & Co., Berlin/New York (1986), European Patent Publication No. 248,573, and PCT Patent Publication No. WO 86/05181.
The amount of compound of Formula (I) required to be effective as a therapeutic agent will, of course, vary and is ultimately at the discretion of the medical or veterinary practitioner. The factors to be considered include the condition being treated, the route of administration, and nature of the formulation, the mammal's body weight, surface area, age and general condition, and the particular compound to be administered.
A suitable effective enzyme inhibitor dose is in the range of about 0.1 to about 120 mg/kg body weight, preferably in the rang®of about 1.5 to 50 mg/kg, for example 10 to 30 mg/kg. The total daily dose may be given as a single dose, multiple doses, e.g., two to six times per day or by intravenous infusion for selected duration. For example, for a 75 kg mammal, the dose range would be about 8 to 9000 mg per day, and a typical dose would be about 2000 mg per day. If discrete multiple doses are indicated, treatment might typically be 500 mg of a compound of Formula (I) given 4 times per day in a pharmaceutically useful formulation.
While it is possible for the active compound (defined herein as a compound of Formula (I), or salt thereof) to be administered alone, it is preferable to present the active compound in a pharmaceutical formulation. Formulations of the present invention, for medical use, comprise the active compound together with one or more pharmaceutically acceptable carriers thereof and optionally other therapeutic ingredients. The carrier(s), must be pharmaceutically acceptable in the sense of being compatible with the other ingredients of the formulation and not deleterious to the recipient thereof.
The present invention, therefore, further provides a pharmaceutical formulation comprising one or more of the compounds of Formula (I), in the form of the free acid, ester derivative, or pharmacologically acceptable salt thereof, together with a pharmaceutically acceptable carrier therefore.
There is also provided a method for the preparation of a pharmaceutical formulation comprising bringing into association a compound of Formula (I) an ester, or pharmacologically acceptable salt thereof, and a pharmaceutically acceptable carrier therefore.
The formulations include those suitable for oral, rectal or parenteral (including subcutaneous, intramuscular and intravenous) administration. Preferred are those suitable for oral or parenteral administration.
The formulations may conveniently be presented in unit dosage form and may be prepared by any of the methods well known in the art of pharmacy. All methods include the step of bringing the active compound in association with a carrier which constitutes one or more accessory ingredients. In general, the formulations are prepared by uniformly and intimately bringing the active compound into association with a liquid carrier or a finely divided solid carrier or both and then, if necessary, shaping the product into desired formulations.
Formulations of the present invention suitable for oral administration may be presented as discrete units such as capsules, cachets, tablets or lozenges, each containing a predetermined amount of the active compound; as a powder or granules; or a suspension in an aqueous liquid or non-aqueous liquid such as a syrup; an elixir, an emulsion or a draught.
A tablet may be made by compression or molding, optionally with one or more accessory ingredients. Compressed tablets may be prepared by compressing in a suitable machine the active compound in a free-flowing form such as a powder or granules, optionally mixed with a binder, lubricant, inert diluent, surface active or dispersing agent. Molded tablets may be made by molding in a suitable machine, a mixture of the powdered active compound with any suitable carrier.
A syrup may be made by adding the active compound to a concentrated, aqueous solution of a sugar, for example sucrose, to which may also be added any accessory ingredients. Such accessory ingredient(s) may include flavorings, an agent to retard crystallization of the sugar or an agent to increase the solubility of any other ingredient, such as a polyhydric alcohol for example glycerol or sorbitol.
Formulations for rectal administration may be presented as a suppository with a conventional carrier such as cocoa butter.
Formulations suitable for parenteral administration conveniently comprise a sterile aqueous preparation of the active compound which is preferably isotonic with the blood of the recipient. Such formulations suitably comprise a solution of a pharmaceutically and pharmacologically acceptable acid addition salt of a compound of the Formula (I) that is isotonic with the blood of the recipient. Thus, such formulations may conveniently contain distilled water, 5% dextrose in distilled water or saline and a pharmaceutically and pharmacologically acceptable acid addition salt of a compound of the Formula (I) that has an appropriate solubility in these solvents, for example the hydrochloride, isethionate and methanesulfonate salts, preferably the latter.
Useful formulations also comprise concentrated solutions or solids containing the compound of Formula (I) which upon dilution with an appropriate solvent give a solution suitable for parenteral administration as above.
In addition to the aforementioned ingredients, the formulations of this invention may further include one or more accessory ingredient(s) selected from diluents, buffers, flavoring agents, binders, surface active agents, thickeners, lubricants, preservatives (including antioxidants) and the like.
In analyzing the biological activity of the compounds of the present invention, GAR TFase from E. coli was used. This enzyme behaves like the mammalian and avian enzyme with respect to substrate specificity, yet is a simple and effective system having only one biological activity. That is, unlike the avian trifunctional GAR TFase, the E. coli species has a sole function. This follows from the genetic evidence of Smith and Daum, J. Biol. Chem., 262, 10565-10569 (1987) as w®11 as the work of Schrimsher et al., Biochemistry, 25, 4366-4371 (1986) who have shown that AIR SYNthase from E. coli is a monofunctional protein, whereas, in chicken it belongs to a trifunctional protein containing, the activates: GAR SYNthase, GAR TFase, and AIR SYNthase.
The E. coli GAR TFase binding constants for the compounds of the present invention and other folate analogs are shown in Table I below:
TABLE I______________________________________BINDING CONSTANTS FOR FOLATE ANALOGSWITH E. coli GAR TFaseCompound K.sub.D (uM) K.sub.I (uM) K.sub.m (uM)______________________________________10-CHO-DDF -- -- 36beta-GAR -- 20DDF -- 28.1 --beta-TGDDF 2.5 × 10.sup.-4 -- --alpha-TGDDF 5.8 × 10.sup.-3 -- --alpha,beta- 1.7 --dephospho-TGDDF______________________________________
The specificity of beta-TGDDF for GAR TFase from species other than E. coli was assayed in a general manner by measuring the activity of GAR TFase at a concentration of 1 nM from avian, HeLa, and L121? sources in the presence of 20 nM beta-TGDDF. All GAR TFase's were inhibited by roughly the same magnitude and all showed inhibition of a slow, tight binding nature.
Table II illustrates the specificity of beta-TGDDF for GAR TFase in comparison with other reduced-folate utilizing enzymes. This test, was conducted using the same [I]/[E]ratios as stated previously.
TABLE II______________________________________INHIBITORY PROPERTIES OF BETA-TGDDFWITH FOLATE UTILIZING ENZYMESEnzyme Source Inhibition______________________________________GAR TFase (E. coli) +GAR TFase (avian) +GAR TFase (HeLa O) +GAR TFase (L1210) +AICAR TFase (avian) -DHFR (E. coli) -DHFR (mouse) -TS (L. casei) -______________________________________
This marks the first time that GAR TFase from E. coli has been purified to homogeneity. The enzyme was first overproduced using the high copy plasmid pJS85. The initial expression vector constructed consisted of a promoterless puMN operon cloned into the lambda pL expression vector, pJS88 to create plasmid pJSI19 (FIG. 1). Plasmid pJS88 is a lambda pL expression vector similar to those described by Remault et al., Gene, 15, 81-93 (1981). Upon characterization, plasmid pJS119 was found to overproduce both AIR SYNthase (purM) and GAR TFase (purN) but the over expression of GAR TFase was not coordinate with AIR SYNthase.
Because of the non-coordinate expression of AIR SYNthase and GAR TFase in plasmid pJS119, an expression vector designed to maximize the overproduction of GAR TFase was constructed. In a series of manipulations functionally equivalent to the deletion of the AIR SYNthase (purM) coding region, plasmid pJ167 was created (FIG. 1). This expression system produces approximately 10-fold the amount of active GAR TFase per cell as pJS85.
The enzyme was first purified from the pJS85 clone using a combination of conventional chromatography separations. A final HPLC step using the Mono Q column allowed purification to greater then 95%. The same purification scheme was used for the pJS167 clone which gives from 2-8% GAR TFase per cell (based on densitometry of crude lysate) as opposed to <0.5% GAR TFase obtained from pJS85.
E. coli GAR TFase is a small, single subunit protein with a molecular weight of 23,212 daltons. This weight was calculated from the peptide sequence deduced from the cDNA (Smith & Daum, J. Biol. Chem., 262, 10565-10569 (1987)). The molecular weight of the purified protein obtained from SDS-PAGE is very close, approximately 25,000 daltons. Ultracentrifugal sedimentation velocity experiments performed on the protein under reducing and nonreducing conditions give an average molecular weight of 24,000 daltons, indicating that under the concentration and conditions studied E. coli GAR TFase is a monomer in solution.
The following examples are provided by the way of illustration of the present invention and should in no way be construed as a limitation thereof. All temperatures, unless otherwise indicated, are reported in degrees Celsius (°C.).
GENERAL EXPERIMENTAL PROCEDURES
All reagents were of the highest grade commercially available. Reagents for the synthesis of the inhibitor were purchased from Aldrich Chemical Co. Prostatic acid phosphatase, NADPH, dUMP, Tris, Hepes and A25-sephadex were purchased from Sigma Chemical Co.
E. coli GAR TFase was prepared and purified as described below. L1210 and HeLa GAR TFase were purified according to published procedures. AICAR TFase was prepared according to published procedures.
Continuous UV assays were recorded on a Beckman (Gilford) Model DUR recording quartz spectrophotometer or a Cary 219 spectrophotometer. UV spectra were recorded on a Perkin-Elmer Lamda Array 3840 UV/VIS spectrophotometer interfaced to a P & E 7300 PC. 1 H NMR were collected on a Bruker WB-360 spectrophotometer with chemical shifts being referenced versus the transmitter offset for HDO or CHCl 3 . All spectra taken in D 2 O were HDO surpressed. Fluorescence spectra were recorded on an SLM Amico 8000C spectrophotometer.
HPLC was carried out on a Waters 600E with detection by a Waters 990 Photodiode Array Detector controlled by a NEC PowerMate 2 PC. HPLC columns used were either reverse phase (Perkin-Elmer/Analytical C18, 4.6 mm ID×24.5 cm) or anion exchange (Whatman Partisil 10 SAX, 4.6 mm ID×25 cm, standard analytical) unless otherwise stated.
HPLC Solvents:
Solvent A; 0.01M NH 4 H 2 PO 4 , pH 3.5, 7% EtOH;
Solbent B; 1M NH 4 H 2 PO 4 , pH3.5, 7% EtOH;
Solvent C; H 2 O, 0.1% TFA;
Solvent D; CH 3 CN, 0.07% TFA;
HPLC--Stationary and Mobile Phases:
Condition A; Anion exchange chromatography, with the following mobile phase: 100% Solvent A isocratic for 2 min. followed by a 1% per min. linear gradient to 50% Solvent B flowrate 1 ml/min., column monitoring at 238 nm.
Condition B; Reverse phase chromatography using the following mobile phase: 93% Solvent C, 7% Solvent D for 2 min. followed by a gradient from 7% to 50% D over 50 min.; flowrate 1 ml/min., column monitoring at 230 nm.
Condition C; Reverse phase chromatography using the following mobile phase: 12% Solvent D in 88% Solvent C; flowrate 0.7 ml/min., column monitoring at 230 nm.
Condition D: Reverse phase chromatography using a Whatman Partisil M9 10/50 ODS-3 column and the following mobile phase: 93% Solvent C, 7% Solvent D for 2 min. followed by a gradient from 7% to 50% D over 50 min.; flowrate 2 ml/min., column monitoring at 250 nm.
Escherichia coli strain TX635 (F lacZ + cI857, (Mieschendahl & Muller-Hill, J. Bacteriol., 164, 1366-1369 (1985)) contains an episome borne temperature sensitive lambda repressor and was used as a host for the lambda pL plasmids. Strains were made competent and transformed by the procedure of Dagert and Ehrlich, Gene, 6, 23-28 (1979). The minimal medium of Neidhardt et al., J. Bacteriol., 119, 736-747 (1974) and the rich media described by Miller, Experiments in Molecular Genetics, pp. 1-466, Cold Spring Harbor (1972) were used for the growth of the E. coli K12 strains. The recombinant DNA techniques employed were those described by Tiedeman et al., J. Biol. Chem., 260, 8676-8679 (1985).
EXAMPLE 1
N 10 (Bromoacetyl)-5,8-Dideazafolate (DDF)
N 10 -bromoacetylaton of DDF, to generate the affinity label, N 10 -(bromoacetyl)-DDF, was accomplished using the method of Daubner et al., Biochemistry, 25, 2951-2957 (1986).
The affinity label was purified by reverse phase HPLC using a Perkin-Elmer/analytical C18 column and eluting with a linear gradient of 0.1% trifluoroacetic acid/H 2 O and a limiting buffer of 0.08% trifluoroacetic acid/45% acetonitrile at a rate of 0.36% limiting buffer employing a flowrate of 0.7 ml/min. The peak of interest had a retention time of approximately t r =55 min. Once collected, the sample was brought to dryness on a Savant Speed-Vac. The detector wavelength was 310 nm. Approximately 1 umole of material was applied to the column with each injection (typically 100 ul of a 10 mM solution in 20 mM K 2 HPO 4 , pH 7.5 was injected). Solutions of the affinity label were prepared in either 20 mM K 2 HPO 4 , pH 7.5 or 20 mM Tris, pH 7.5. The concentration was determined using the extinction coefficient ε=4.19 mM -1 cm -1 for 310 nm.
EXAMPLE 2
S-Trityl Mercaptoacetic Acid
This compound was synthesized by the condensation of triphenylmethanol (2.84 g, 10.8 mmoles) with mercaptoacetic acid (0.75 ml, 10.8 mmoles) in 19 ml trifluoracetic acid. The TFA was removed in vacuo, giving an orange oil, which was purified by dissolution in ether and extraction with 1 N NaOH. The aqueous phase was acidified with 6N HCl, and extracted with two 30 ml portions of ether. The ethereal phase was dried over MgSO 4 and evaporated to give 3.41 g (93%) of a white solid.
NMR (CDCl 3 )δ7.42 (m, 6H), 7.23 (m, 9H), ca. 5.2 (hr. s, 1H), 3.05 (s, 2H).
EXAMPLE 3
Tri-O-Benzoyl-N-(2-tritylmercaptoacetyl)-1-ribosylamine
To an acetone solution of 4.1 mmoles of the tri-O-benzoylribosylamine, in 80 ml acetone, was added 1.63 g (4.88 mmoles) of S-trityl-mercaptoacetic acid, followed by 1 g (4.85 mmoles) of dicyclohexylcarbodiimide (DCC). The reaction was stirred at room temperature for 14 hours, then filtered and concentrated in vacuo. The concentrated product was dissolved in 40 ml ether, filtered, washed with 30 ml each of water, 3% Na 2 CO 3 , and brine, and dried over Na 2 SO 4 . Rotary evaporation gave a white solid, which was further purified by flash chromatography on silica gel, eluting with 3% ethyl acetate in CHCl 3 .
While anomers were separable by chromatography, the alpha/beta mixture was used in the following examples.
NMR (CDCl 5 )δ8.05 (d, 3W), 7.95 (d, 2H), 7 (d, 2H), 76.7 2 (m, 3HO, 6.01 (dd, 1H), 5.68 (dd, 1H), 4.5 (m, 5H), 3.18 (d, 1H), 3.1 (d, 1H).
Mass Spectral Data (FAB; positive ion); 778 (10%, M+1), 536 (8%, M+1-trityl), 445 (63%, M+1-side chain), 486 (100%).
EXAMPLE 4
N-(2-tritylmercaptoacetyl)-1-ribosylamine
To a solution of tribenzoyl riboside (278 mg, 0.36 mmoles) in 5 ml absolute methanol was added 0.18 mmoles sodium methoxide in methanol and the solution was stirred at room temperature for 45 min. The resulting trityl thio-riboside was treated with Amberlite® IR-120 + , filtered, concentrated by rotary evaporation and dried in a vacuum desiccator for 16 hours. Yield: 86%.
NMR (CDCl 3 )δ7.4 (m, 6H), 7.25 (m, 9H), 7.0 (d, 1H), 5.38 (dd, 1H), 5.05 (dd, 1H), 4.1-3.65 (m, 5H), 3.05 (d, 1H), 2.97 (d, 1H).
Mass spectral data (1, CH 4 ): 2.42 (80%, trityl cation), 183 (100%, M+1-Trityl-S-H 2 O). [The molecular ion was not apparent.]
EXAMPLE 5
5-phospho-N-(2-tritylmercaptoacetyl)-1-ribosylamine
The crude riboside from Example 4 (0.36 mmoles) was dissolved in 5 ml trimethyl phosphate, and cooled to 0°. Phosphoryl chloride (0.3 ml, 3.6 mmoles) was added over 3 min., and the reaction was stirred at 0o for 1.5 hr. To this reaction mixture was added water and 5 N NaOH sufficient for neutralization. The neutral solution was maintained at pH 7 for 1 hr. by periodic additions of 1 N NaOH, after which time it was washed with ether, and purified on a 20 ml Sephadex® A-25 chromatography (loading in 100 ml distilled water and elution with a 100 ml linear 0-500 mM NH 4 HCO 3 gradient), followed by preparative HPLC (Whatman® magnum C-18 column; elution with 70% H20/30% CH 3 CN, with 0.1% trifluoracetic acid in each solvent). The anomers could be separated under the latter conditions, with the B-anomer eluting before the alpha-anomer. For small amounts of anomeric mixtures, the ion exchange product (contaminated by buffer and phosphate) could be loaded onto a Waters Sep-Pak in distilled water, and eluted with 30% MeOH/H 2 O.
NMR (D 2 O)δ7.31 ppm (d, 7.2 Hz, 6H), 7.21 (m, 9H), 4.92 (d, 4.4 Hz, 1H), 3.97 (t, 5.0 Hz, 1H), 3.85 (q, 3.7 Hz, 1HO, 3.75 (m, 2H), 3.08 (d, 15.85 Hz, 1H), 2.99 (d, 15.73 Hz, 1H).
Mass spectral data (FAB; position ion); m/e 590 (55%, M+1), 568 (45%, M-Na+H+1), 435 (53%, M-sidechain+1), 413 (65%, M-sidechain-Na+H+1).
EXAMPLE 6
N 10 -[5'-phosphoribosyl-1'-β-aminocarbonylmethyl-1-thioacetyl[-5,8-dideazafolate, alpha,beta-TGDDF
Deprotection of the thioGAR and coupling to N 10 (bromoacetyl)-5,8-dideazafolate were accomplished in one step as follows:
The compound isolated in Example 5 (ca. 1 mg) was placed in a 10 ml rb. flask under an argon atmosphere. One ml of 80% TFA/20% H 2 O (argon deoxygenated) was added and the mixture stirred for 45 min. at room temperature.
Treatment of an aliquot of the reaction mixture with dithionitrobenzoic acid (DTNB, Riddles et al., Anal. Bioch., 94, 75-81 (1979)) allowed determination of the degree of deprotection. The reaction mixture was then cooled to Oo and 5 ml of 5 N NaOH added over 2 min. One ml of 500 mM HEPES buffer and 100 ul of 5 mM EDTA were added, and the pH was adjusted to 7.5 with 1 N NaOH. All solutions had been deoxygenated with argon.
To this mixture was added the compound of Example 1 (0.2 mg in 100 ul water); the resulting mixture was heated at 60° for one hour.
The adduct was purified on HPLC using condition B. Repurification using condition C gave pure single anomers of the adduct.
NMR spectrum of an anomeric mixture (D 2 O);δ 7.7-7.5 (m, 3, p-phenylene and H-5), 7.42 (t, 1, H-7), 7.2-7.14 (m, 3,p-phenylene and H-8), 5.44 (d, 1, alpha-anomeric Cl'H), 5.24 (d, 1, beta-anomeric Cl'H), 4.87 (s, 2, C9-CH 2 ), 4.36 (m, 1, glutamic acid C alpha -H), 4.2-3.7 (4, C5'CH 2 , C2'CH), 3.21 (m, 4, CH 2 SCH 2 ), 2.16 (t, 2, J B-Y =7.4 Hz, glutamic acid C y --H), 1.95 (two multiplets, 2, glutamic acid C B --H).
UV (50 mM HEPES, pH=7.5):λmax 230 (ε=54.5 cm -1 mM -1 ),λsh 255 (ε=26.1 cm -1 mM -1 ), λmax 310 (ε=4.19 cm -1 mM -1 ).
EXAMPLE 7
Chemical Synthesis of Alpha/beta dephospho-TGDDF
The nonphosphorylated derivative of TGDDF was prepared using chemistry similar to that of Examples 1-6 except that thioGAR riboside was substituted for thioGAR. Purification by reverse phase HPLC, however, failed to separate the alpha and beta anomers.
EXAMPLE 8
Enzymatic Synthesis of Alpha/beta dephospho-TGDDF
To 40 ul of 50 uM solution of alpha beta-TGDDF buffered to pH 4.0 with 20 mM sodium acetate was added 4 ul of prostatic acid phosphatase (1 mg lyophilized enzyme/1 ml H 2 O). The reaction was allowed to stir 2 hrs. at 22° after which time the solution was injected onto either anion exchange or reverse phase HPLC system using conditions A or B, respectively.
EXAMPLE 9
Construction of AIR Synthase and GAR TFase Expression Vector: pJS119
Plasmid pJSI19 (FIG. 1.) was constructed by two successive subclonings of restriction fragments that covered the nucleotide sequence 732 to 2746 (the numbering scheme refers to the published sequence (Smith and Duam, J. Biol. Chem., 261, 10632-10636 (1986) and J. Biol. Chem., 262, 10565-10569 (1987)) and removes the purMN promoter and purR binding site.
The first restriction fragment subcloned was a 186 bp HinPI fragment (nucleotide 732-919) treated with T4 DNA polymerase to create blunt ends and cloned into the SmaI site of M13mp18 (Yanisch-Perron et al., Gene, 33, 103-119 (1985)). After DNA sequencing to verify fragment identify and determine the orientation, the restriction fragment in the correct orientation to maintain purMN expression from the lac promoter was transferred to plasmid pUC18 (ibid) by restriction digest to form plasmid pJS117. The remainder of the purMN operon was added as a PpuMI-XhoII restriction fragment into the PpuMI-BamHI sites of plasmid pJS117 to form plasmid pJS118. An EcoRI-SalI restriction digest was then used to transfer the promoterless purMN operon into plasmid pJS88 to form, plasmid pJSI19 and transformed into strain TX635.
EXAMPLE 10
Construction of a GAR TFase expression vector: pJS167
This plasmid was created by a series of manipulation equivalent to the deletion of purM coding region (FIG. 1). This was accomplished by synthesizing complementary oligonucleotides which consisted of purMN sequence from the unique PpuMI site at nucleotide 770 to the purM initiation codon at nucleotide 780. The sequence continued with the purN ATG initiation codon at nucleotide 780. The sequence continued with the purN ATG initiation codon at nucleotide 1817 to the SspI site an nucleotide 1823 within th®purN gene. This maintained the purM Shine-Dalgarno ribosome binding site in addition to introducing the ATG initiation codon of purN to replace the purM GTG initiation codon. KpnI and BamHI linkers and translational stop codons were also included in the oligonucleotide sequence to aid in cloning. After annealing of the complementary strands, the fragment was cloned into M13mp18 KpnI-BamHI sites. Colorless plaques were sequenced to verify the insert and nucleotide sequence. This fragment was then recovered by PpuMI-BamHI restriction digest and cloned into the PpuMI-BamHI sites of plasmid pJSI17 to create an intermediate plasmid pJ193. A, 747 bp SspI fragment (nucleotide 1823-2570) was then cloned into the intermediate plasmid pJS193 to reconstruct the purN coding region and creating plasmid pJS194. The modified purN gene was then transferred to plasmid pJS88 by an EcoRI-Sal/I digest to create the GAR TFase expression plasmid pJS167 in host strain TX635.
EXAMPLE 11
E. coli GAR TFase Purification
E. coli strain TX393 containing the multicopy plasmid pJS85 with a DNA insert containing GAR TFase (Smith and Daum, supra, was grown in M9CA media (Maniatis et al., Molecular Cloning: A Laboratory Manual, pp. 440-441, Cold Spring Harbor (1982)) supplemented with 30 mg/L ampicillin. Growths were started with a 1% culture inoculum and maintained at 37° C. The cells were harvested in the late log phase by centrifugation to yield typically 2.5 g/L.
E. coli strain TX635 containing either the lambda expression plasmid pJSI19 or pJS167 was grown in the rich media described above supplemented with 30 mg/L ampicillin. The cells were grown at 30° C. to confulence and then temperature jumped to 42° C. for up to 9 hours as in the case of pJS167 to obtain maximum protein production. Cells were harvested by centrifugation.
All buffers contained 50 mM Tris, pH 7.5 and 1 mM EDTA in addition to other components specified below, unless otherwise indicated. All cell manipulations were done at 4° C. unless otherwise stated.
The cells (14.6g) were resuspended in 25 ml of buffer that contained 5 mg of PMSF (carried into solution with 50 ul of DMF). The cells were disrupted by adding 38 mg of egg white lysozyme in 1 ml of buffer and 2.6 ml of Triton X100/glycerol (1.2 ml of glycerol per 50 ul of 10% Triton X100). The suspension was vortexed for 1 minute and allowed to stand at 40C for 40 minutes. The lysed cells were passed through a 17 gauge syringe 5x to shear DNA. The cell debris was removed by centrifugation at (17,000 rpm) 34,800 g for 20 minutes.
To the supernatant (-30 ml) was added 292 mg of streptomycin sulfate in 2 ml of lysis buffer via a syringe driver over 10 hrs. with gentle stirring. The milky white suspension was centrifuged at (15,000 rpm) 27,000 g for 20 minutes. The supernatant (˜30 ml) was dialized (1 1/8, 12,000 cut off dialyzer tubing) against 2×2.5L of buffer.
This protein solution was diluted to 150 ml with buffer and applied (˜23 ml/min.) to a column of QAE A25 Sephadex (2.5×28 cm) previously equilibrated with buffer. The column was washed with buffer until the absorbance (280 nm) at the column outlet was less than 0.1 (˜1L) and developed with a 2 L linear gradient of KCl (0.05 to 0.5 M KCl) in the equilibration buffer.
Fractions (˜14 ml) from the QAE-Sephadex column that contained GAR TFase activity, determined by the spectrophotometric assay, that eluted at 250 mM KCl were pooled (˜290 ml) and concentrated to 10 ml by using an amicon ultrafiltration apparatus with a YM10 membrane.
Half of this concentrated protein solution was applied to a column (2.5×51 cm) of Sephadex G-100 equilibrated with buffer. The flow rate was 4-5 ml/hr. Fractions (2 ml) were collected and those containing GAR TFase were pooled (22 ml) and concentrated (3 ml). This step was repeated for the remaining 5 ml of protein concentrate.
Depending on the purity of this material, as judged by densitometry of SDS-PAGE gels and reverse phase HPLC (monitored at 200 and 280 nm), an additional step was sometimes added. The>90% pure protein was further purified at room temperature (˜5° C.) on a Mono Q HR5/5 column (Pharmacia, FPLC) using a linear gradient of KCl (0-50 mM) in buffer at a rate of 10% 1M KCl per min. The elution was followed at 280 nm using an in-line detector (Pharmacia). Active fractions from the center of the major peak were pooled, dialyzed against buffer, and frozen in liquid nitrogen as 1-2 mg/ml solutions.
The present invention has been described in detail, including the preferred embodiments thereof. However, it will be appreciated that those skilled in the art, upon consideration of the present disclosure, may make modifications and/or improvements on this invention and still be within the scope and spirit of this invention as set forth in the following claims. | The present invention is directed to several multisubstrate adduct inhibitors of glycinamide ribonucleotide transformylase (GAR TFase; E.C. 2.1.2.2), a folate-requiring enzyme of de novo purine biosynthesis. The compounds of the present invention will be useful to provide anti-gout and/or anti-neoplastic therapeutic agents or will serve as potentiators for other such agents. The most prefeffed, potent tight-binding multisubstrate adduct inhibitor of glycinamide ribonucleotide transformylase, is N 10 -[5'-phosphoribosyl-1'-β-aminocarbonylmethyl-1-thioacetyl]-5,8-dideazafolate, which has the chemical formula: ##STR1## | 2 |
BACKGROUND OF THE INVENTION
The present invention relates to a laminated product comprising a substratum layer of an olefinic thermoplastic elastomer and a surface skin layer, and to a constructional gasket.
A variety of materials have heretofore been employed for parts and portions requiring rubbery elasticity in the field of automobile parts, industrial machinery parts, electric and electronic parts, and constructional materials. For example, for doors, leafs and sashes of buildings there are provided guide members called gasket which facilitate an opening-closing operation for going-in-and-out and for ventilation, and which, moreover, make possible an operation of tightly shutting doors against the portions that come into contact with the doors.
For the gasket to be used for construction, there have heretofore been used mainly soft synthetic resins such as soft poly (vinyl chloride) resin and vulcanized rubbers such as ethylene-propylene-diene copolymer rubber.
Further, for the portions requiring a higher performance of sliding property, special materials have been employed such as foamed silicone rubbers.
The hitherto used gaskets made of soft synthetic resins and made of vulcanized rubber are not particularly superior in sliding property and, hence, their function as gasket tends to be lowered, what with permanent set in fatigue and what with big deformation occurring through a prolonged use. Further, the vulcanized rubber, since being a thermosetting type rubber, cannot be put to recycled use.
Although the above-mentioned problem can be solved by using such a material excellent in sliding property as foamed silicone rubber, the arising problem is that the rubber is expensive compared with generally used soft synthetic resins and vulcanized rubbers.
OBJECTS AND SUMMARY OF THE INVENTION
The first object of the present invention is to provide a constructional gasket excellent in durability, excellent in the property of giving a tight contact upon closing doors or the like and excellent in the property of giving a lilting slide upon opening doors or the like by using an economical and recyclable laminated material.
The second object of the present invention is to provide a constructional gasket superior in durability and in sealing and hermetic property for doors and windows by using an olefinic thermoplastic elastomer composition capable of being reclaimed which can be produced simply without employing a crosslinking agent with a single production process and moreover produced at a low cost.
Namely, the present invention includes the following inventions.
(i) A laminate comprising an olefinic thermoplastic elastomer which comprises:
(a) a substratum layer comprising an olefinic thermoplastic elastomer composition (A) having the following characteristics {circle around (1)} to {circle around (3)}:
{circle around (1)}
9 ≦Y −0.43 X ≦27 (1)
wherein X denotes the JIS A-hardness value (a dimensionless value) of the olefinic thermoplastic elastomer composition determined according to the prescription of JIS K6301 and Y represents the compression set value (expressed by %) of the olefinic thermoplastic elastomer composition determined according to the prescription of JIS K6301 under a condition of 70° C. and 22 hours,
{circle around (2)} a tensile strength value in the range from 5 to 30 MPa determined according to the prescription of JIS K6301 and
{circle around (3)} an elongation set value of 18% or less determined according to the prescription of JIS K6301, and
(b) a surface skin layer comprising an ultra high molecular weight polyolefin composition (B) having an intrinsic viscosity [η] measured in decalin at 135° C. in the range from 3.5 to 8.3 dl/g.
(ii) A laminate as defined in the above (i), wherein the olefinic thermoplastic elastomer composition (A) is obtainable by dynamically heat treating 5 to 60 parts by weight of a polyethylene resin (a-1) and 40 to 95 parts by weight of an ethylene-α-olefin-based copolymer (a-2) having a Mooney viscosity ML 1+4 (100° C.) of 90 to 250 and an ethylene content of 70 to 95 mole % [the total amount of (a-1) and (a-2) being 100 parts by weight.]
(iii) A laminate as defined in the above (i), wherein the olefinic thermoplastic elastomer composition (A) is obtainable by dynamically heat treating 5 to 60 parts by weight of a polypropylene resin (a-3) and 40 to 95 parts by weight of an α-olefin-based copolymer (a-4) having a Mooney viscosity ML 1+4 (100° C.) of 60 to 250 [the total amount of (a-3) and (a-4) being 100 parts by weight.]
(iv) A laminate as defined in the above (i), wherein the ultra high molecular weight polyolefin composition (B) is an ultra high molecular weight polyolefin composition comprising an ultra high molecular weight polyolefin (b-1) having an intrinsic viscosity [η] measured in decalin at 135° C. in the range from 10 to 40 dl/g and a polyolefin (b-2) having an intrinsic viscosity [η] measured in decalin at 135° C. in the range from 0.1 to 5 dl/g, and the ultra high molecular weight polyolefin (b-1) is present in a ratio of 15 to 40% by weight to the total amount of 100% by weight of the ultra high molecular weight polyolefin (b-1) and the polyolefin (b-2).
(v) A laminate as defined in the above (ii), wherein the olefinic thermoplastic elastomer composition (A) contains 30 parts by weight or less of a polypropylene resin (a-5) to the total amount 100 parts by weight of the polyethylene resin (a-1) and the ethylene-α-olefin-based copolymer (a-2).
(vi) A laminate as defined in any one of the above (i) to (v), wherein the surface skin layer comprising the ultra high molecular weight polyolefin composition (B) is composed of 10 to 90 parts by weight of the ultra high molecular weight polyolefin composition (B) and 90 to 10 parts by weight of an olefinic thermoplastic elastomer composition (C) comprising a crystalline polyolefin resin and a rubber [the total amount of (B) and (C) being 100 parts by weight].
(vii) A laminate as defined in any one of the above (i) to (v), wherein the surface skin layer comprising the ultra high molecular weight polyolefin composition (B) is composed of 10 to 90 parts by weight of the ultra high molecular weight polyolefin composition (B), 90 to 10 parts by weight of the olefinic thermoplastic elastomer composition (C) comprising a crystalline polyolefin resin and a rubber [the total amount of (B) and (C) being 100 parts by weight] and 0.1 to 25 parts by weight of an organopolysiloxane (D).
(viii) A glass-run channel for automobile comprising a laminate as defined in any one of the above (i) to (vii).
(ix) A constructional gasket comprising a laminate as defined in any one of the above (i) to (vii).
(x) A constructional gasket comprising an olefinic thermoplastic elastomer composition (A) having the following characteristics {circle around (1)} to {circle around (3)}:
{circle around (1)}
9 ≦Y −0.43 X <27 (1)
wherein X denotes the JIS A-hardness value (a dimensionless value) of the olefinic thermoplastic elastomer composition determined according to the prescription of JIS K6301 and Y represents the compression set value (expressed by %) of the olefinic thermoplastic elastomer composition determined according to the prescription of JIS K6301 under a condition of 70° C. and 22 hours,
{circle around (2)} a tensile strength value in the range from 5 to 30 MPa determined according to the prescription of JIS K6301 and
{circle around (3)} an elongation set value of 18% or less determined according to the prescription of JIS K6301.
(xi) A constructional gasket as defined in the above (x), wherein the olefinic thermoplastic elastomer composition (A) is obtainable by dynamically heat treating 5 to 60 parts by weight of a polyethylene resin (a-1) and 40 to 95 parts by weight of an ethylene-α-olefin-based copolymer (a-2) having a Mooney viscosity ML 1+4 (100° C.) of 90 to 250 and an ethylene content of 60 to 95 mole % [the total amount of (a-1) and (a-2) being 100 parts by weight].
(xii) A laminate as defined in the above (x), wherein the olefinic thermoplastic elastomer composition (A) is obtainable by dynamically heat treating 5 to 60 parts by weight of polypropylene resin (a-3) and 40 to 95 parts by weight of an a α-olefin-based copolymer (a-4) having a Mooney viscosity ML 1+4 (100° C.) of 60 to 250 [the total amount of (a-3) and (a-4) being 100 parts by weight].
(xiii) A constructional gasket as defined in the above (xi), wherein the olefinic thermoplastic elastomer composition (A) contains 30 parts by weight or less of a polypropylene resin (a-5) to the total amount 100 parts by weight of the polyethylene resin (a-1) and the ethylene-α-olefin-based copolymer (a-2).
Hereinafter, the present invention is explained in detail.
The olefinic thermoplastic elastomer based laminate of the present invention is constituted by a substratum layer comprising an olefinic thermoplastic elastomer composition (A) and a surface skin layer comprising a specific ultra high molecular weight polyolefin composition (B).
The above-mentioned components constituting these layers are explained first.
Olefinic Thermoplastic Elastomer Composition (A)
The olefinic thermoplastic elastomer composition (A) used in the present invention is an elastomer having the following characteristics {circle around (1)} to {circle around (3)}:
{circle around (1)}
9 ≦Y −0.43 X ≦27 (1)
preferably
9 ≦Y −0.43 X ≦27 (1′)
more preferably
10 ≦Y −0.43 X ≦26 (1″)
wherein X denotes the JIS A-hardness value (a dimensionless value) of the olefinic thermoplastic elastomer composition determined according to the prescription of JIS K6301 and Y represents the compression set value (expressed by %) of the olefinic thermoplastic elastomer composition determined according to the prescription of JIS K6301 under a condition of 70° C. and 22 hours,
{circle around (2)} a tensile strength value in the range from 5 to 30 MPa, preferably 8 to 30 MPa, more preferably 12 to 30 MPa determined according to the prescription of JIS K6301, and
{circle around (3)} an elongation set value of 18% or less, preferably 0.5 to 15%, more preferably 0.5 to 12% determined according to the prescription of JIS K6301.
The methods for determining the above characteristics {circle around (1)} to {circle around (3)} are as follows.
The JIS A-hardness:
Determined according to the prescription of JIS K6301 as an instantaneous value using a Type A hardness tester operated with a spring.
The compression set value:
Determined according to the prescription of JIS K6301 as the permanent set (residual strain) using a stubby cylindrical test specimen having a diameter of 29.0 mm and a thickness of 12.7 mm after the specimen has been held pressed for 22 hours under a condition of 25% compression ×70° C.
The tensile strength:
Determined according to the prescription of JIS K6301 using a JIS No. 3 dumbbell specimen at a drawing velocity of 200 mm/min.
The elongation set value:
Determined according to the prescription of JIS K6301 as the permanent set (residual elongation) using a JIS No. 3 dumbbell specimen after the specimen has been maintained under 100% elongation for 10 minutes and, then, kept for 10 minutes with relieved tension before the determination of the permanent set (residual elongation).
The olefinic thermoplastic elastomer composition (A) used in the present invention is constituted preferably by a polyethylene resin (a-1) and an ethylene-α-olefin-based copolymer (a-2), and a polypropylene resin (a-5) incorporated where deemed necessary.
For the polyethylene resin (a-1) to be employed according to the present invention, known polyethylene resins can be used without any restriction, such as a high density polyethylene, a medium density polyethylene, a low density linear polyethylene and a low density polyethylene, wherein preference is given to low density linear polyethylene, in particular, to that obtained using a metallocene catalyst.
The polyethylene resin (a-1) has preferably a melt flow rate (MFR, determined according to ASTM D1238 at 190° C. under a load of 2.16 kg) of 0.01 to 100 g/10 min., more preferably 0.01 to 50 g/10 min. In using as the polyethylene resin (a-1) an ultra high molecular weight polyethylene having a MFR lower than 0.1 g/10 min., which has ordinarily an intrinsic viscosity [η], determined in decalin at 135° C., in the range from 7 to 40 dl/g, such an ultra high molecular weight polyethylene may preferably be used as a mixture composed of 15 to 40% by weight of a low to high molecular weight polyethylene having an intrinsic viscosity [η], determined in decalin at 135° C., in the range from 0.1 to 5 dl/g and of 85 to 60% by weight of an ultra high molecular weight polyethylene of intrinsic viscosity [η] in the range from 7 to 40 dl/g, wherein the intrinsic viscosity [η] of the mixture as a whole may preferably be in the range from 3.5 to 8.3 dl/g.
The polyethylene resin (a-1) may favorably have a density in the range from 0.88 to 0.98 g/cm 3 , preferably from 0.90 to 0.95 g/cm 3 .
When a low density linear polyethylene is to be used for the polyethylene resin (a-1), it is favorable to use one which has an MFR (ASTM D1238, 190° C., load 2.16 kg) of 0.1 to 30 g/10 min., preferably 0.2 to 20 g/10 min., and a density of 0.88 to 0.95 g/cm 3 , preferably 0.91 to 0.94 g/cm 3 .
When a low density linear polyethylene is used for the polyethylene resin (a-1), a formed article exhibiting superior appearance can be obtained without occurrence of neither a rough nor sticky surface by extrusion molding or injection molding, as contrasted to the case of using a medium or a high density polyethylene.
The polyethylene resin (a-1) may be either a homopolymer of ethylene or a copolymer of a predominant proportion of ethylene with minor proportion, for example, not higher than 10 mole %, of other comonomer(s). For such comonomers, there may be enumerated α-olefins having 3 to 20 carbon atoms, preferably 3 to 8 carbon atoms, and vinyl monomers, such as vinyl acetate and ethyl acrylate. For the α-olefin to be incorporated as other comonomer, there may be exemplified propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene. Such other comonomer may be incorporated either alone or in a combination of two or more.
The polyethylene resin (a-1) may be either one single polyethylene product or a blend of polyethylene products.
The ethylene- α-olefin-based copolymer (a-2) employed in the present invention is one having a Mooney viscosity ML 1+4 (100° C.) of 90 to 250, preferably 100 to 200, more preferably 110 to 180, and an ethylene content of 70 to 95 mole %, preferably 75 to 90 mole %, more preferably 75 to 85 mole %. Here, the ethylene content indicates an ethylene content to the total content of α-olefins (including ethylene).
The ethylene-α-olefin-based copolymer (a-2) may either be a copolymer of ethylene with an α-olefin having 3 to 20 carbon atoms, preferably 3 to 8 carbon atoms or a copolymer of ethylene, the α-olefin and comonomer(s) other than α-olefins. Such comonomer(s) other than α-olefins may include a non-conjugated polyene. Further, the ethylene-α-olefin-based copolymer (a-2) may either be a random copolymer or a block copolymer.
Concrete examples of the ethylene-α-olefin-based copolymer (a-2) include ethylene-α-olefin copolymers and ethylene-α-olefin-non-conjugated polyene copolymers. Among them, ethylene-α-olefin-non-conjugated polyene copolymers are preferred.
As the α-olefin to be copolymerized with ethylene in the ethylene-α-olefin-based copolymer (a-2), there may be enumerated, for example, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene and 1-octene. The α-olefin may either be incorporated alone or in a combination of two or more.
As the non-conjugated polyene to be copolymerized with ethylene and α-olefin in the ethylene-α-olefin-based copolymer (a-2), there may be enumerated, for example, non-conjugated diene, such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylenenorbornene and ethylidenenorbornene. The non-conjugated polyene may either be incorporated alone or in a combination of two or more. The ethylene-α-olefin-non-conjugated polyene copolymer has an iodine value usually in the range of 0.1 to 50, preferably in the range of 5 to 30.
The ethylene-α-olefin-based copolymer (a-2) may either be incorporated alone or in a combination of two or more.
Of the olefinic thermoplastic elastomer composition (A) used in the present invention, a composition composed of the polyethylene resin (a-1) and the ethylene-α-olefin-based copolymer (a-2) is obtained preferably by subjecting a mixture containing 5 to 60% by weight, preferably 10 to 50% by weight of the polyethylene resin (a-1) and 40 to 95% by weight, preferably 50 to 90% by weight of the ethylene-α-olefin-based copolymer (a-2) to the total amount of the polyethylene resin (a-1) and the ethylene-α-olefin-based copolymer (a-2) to a dynamic heat treatment in the absence of crosslinking agent as described below. When the contents of the polyethylene resin (a-1) and the ethylene-α-olefin-based copolymer (a-2) are in the above-mentioned range, superior rubbery elasticity is exhibited.
The olefinic thermoplastic elastomer composition (A) used in the present invention may incorporate a polypropylene resin (a-5). As the polypropylene resin (a-5), every known polypropylene resin can be used without any restriction. Concrete examples therefor include those given below:
1) Homopolymers of propylene
2) Random copolymers of propylene and other α-olefin(s), i.e., propylene-α-olefin random copolymers, in molar proportions in the range of 90 mole % or more for the former and 10 mole % or less for the latter.
3) Block copolymers of propylene and other α-olefin(s), i.e., propylene-α-olefin block copolymers, in molar proportions in the range of 70 mole % or more for the former and 30 mole % or less for the latter.
For the α-olefin to be copolymerized with propylene, there may be exemplified concretely those having 2 to 20 carbon atoms, preferably 2 to 8 carbon atoms, such as ethylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene.
As the polypropylene resin (a-5), there may favorably be employed homopolymers of propylene of above 1) and propylene-α-olefin random copolymers of above 2), wherein special preference is given to those which have MFR values (ASTM D1238, 230° C., 2.16 kg load) in the range from 0.1 to 50 g/10 min.
The polypropylene resin (a-5) may either be a single polymer product or a blend of polymer products.
The content of the polypropylene resin (a-5) in the olefinic thermoplastic elastomer composition (A) according to the present invention may usually be 30 parts or less by weight, preferably 2 to 30 parts by weight, more preferably 5 to 20 parts by weight per 100 parts by weight of the total amount of the polyethylene resin (a-1) plus the ethylene-α-olefin-based copolymer (a-2).
If the content of the polypropylene (a-5) is in the above range, a formed product exhibiting superior appearance with scarce occurrence of rough or sticky surface can be produced by, for example, extrusion molding and injection molding.
The olefinic thermoplastic elastomer composition (A) used in the present invention may be composed of a polypropylene resin (a-3) and an α-olefin-based copolymer (a-4).
As the polypropylene resin (a-3) to be used in the present invention, there may be enumerated the same as stated previously as the polypropylene resin (a-5). In employing, as the olefinic thermoplastic elastomer composition (A), a combination of an olefinic thermoplastic elastomer composition which is composed of the polypropylene resin (a-3) and the α-olefin-based copolymer (a-4), and an olefinic thermoplastic elastomer composition which is composed of the above polyethylene resin (a-1), the ethylene-α-olefin-based copolymer (a-2) and the polypropylene resin (a-5), the polypropylene resin (a-3) and the polypropylene resin (a-5) may either be identical or different.
The α-olefin-based copolymer (a-4) used in the present invention is one having a Mooney viscosity ML 1+4 (100° C.) of 60 to 250, preferably 100 to 200, more preferably 110 to 180.
The α-olefin-based copolymer (a-4) is a copolymer comprising at least two kinds of α-olefin having 2 to 20, preferably 2 to 8 carbon atoms and may be copolymerized with comonomer(s) other than α-olefin. Such comonomer(s) other than α-olefin may include a non-conjugated polyene. Further, the α-olefin-based copolymer (a-4) may either be a random copolymer or a block copolymer.
Concrete examples of the α-olefin-based copolymer (a-4) include propylene-α-olefin-based copolymers (a-4a) and ethylene-α-olefin-based copolymers (a-4b). Among them, propylene-α-olefin-based copolymers (a-4a) are preferred.
When the α-olefin-based copolymer (a-4) used in the present invention is a propylene-α-olefin-based copolymer (a-4a), it may be one having a Mooney viscosity ML 1+4 (100° C.) of 60 to 250, preferably 65 to 200, more preferably 68 to 180 and a propylene content of 55 to 95 mole %, preferably 60 to 90 mole %, more preferably 68 to 90 mole %. Here, the propylene content means a propylene content to the total α-olefin content (including propylene).
The propylene-α-olefin-based copolymer (a-4a) may be a copolymer comprising propylene and α-olefin having 2 or 4 to 20, preferably 2 or 4 to 8 carbon atoms, and maybe copolymerized with comonomer(s) other than α-olefin. Such comonomer(s) other than α-olefin may include a non-conjugated polyene. Further, the propylene-α-olefin-based copolymer (a-4a) may either be a random copolymer or a block copolymer.
Concrete examples of the propylene-α-olefin-based copolymer (a-4a) include propylene-α-olefin copolymers and propylene-α-olefin-non-conjugated polyene copolymers. Among them, propylene-α-olefin copolymers are preferred.
As the α-olefin to be copolymerized with propylene in the propylene-α-olefin-based copolymer (a-4a), there may be enumerated, for example, ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene and 1-octene. The above-mentioned α-olefin may either be incorporated alone or in a combination of two or more.
As the non-conjugated polyene to be copolymerized with propylene and the above α-olefin in the propylene-α-olefin-based copolymer (a-4a), there may be enumerated, for example, non-conjugated diene, such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylenenorbornene and ethylidenenorbornene. The non-conjugated polyene may either be incorporated alone or in a combination of two or more. The propylene-α-olefin-non-conjugated polyene copolymer has an iodine value usually in the range of 0.1 to 50, preferably in the range of 5 to 30.
When the α-olefin-based copolymer (a-4) is an ethylene-α-olefin-based copolymer (a-4b), as the α-olefin to be copolymerized with ethylene, there may be enumerated, for example, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene and 1-octene. The α-olefin may either be incorporated alone or in a combination of two or more.
In the ethylene-α-olefin-based copolymer (a-4b), as the non-conjugated polyene to be copolymerized with ethylene and the α-olefin, there may be enumerated, for example, non-conjugated dine, such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylenenorbornene and ethylidenenorbornene. The non-conjugated polyene may either be incorporated alone or in a combination of two or more. The ethylene-α-olefin-non-conjugated polyene copolymer has an iodine value usually in the range of 0.1 to 50, preferably in the range of 5 to 30.
The α-olefin-based copolymer (a-4) may either be incorporated alone or in a combination of two or more.
Of the olefinic thermoplastic elastomer composition (A) used in the present invention, a composition composed of the polypropylene resin (a-3) and the α-olefin-based copolymer (a-4) is obtained preferably by subjecting a mixture containing 5 to 60% by weight, preferably 10 to 50% by weight of the polypropylene resin (a-3) and 40 to 95% by weight, preferably 50 to 90% by weight of the α-olefin-based copolymer (a-4) to the total amount of the above polypropylene resin (a-3) and the α-olefin-based copolymer (a-4) to a dynamic heat treatment in the absence of crosslinking agent as described below. When the contents of the polypropylene resin (a-3) and the α-olefin-based copolymer (a-4) are in the above-mentioned range, superior rubbery elasticity is exhibited.
Of the olefinic thermoplastic elastomer composition (A) used in the present invention, a composition composed of the polypropylene resin (a-3) and the α-olefin-based copolymer (a-4) may incorporate such a polyethylene resin that has been mentioned previously as the polyethylene resin (a-1). At that time the content of the polyethylene resin in the olefinic thermoplastic elastomer composition (A) is usually 30 parts by weight or less, preferably 2 to 30 parts by weight, more preferably 5 to 20 parts by weight to the total 100 parts by weight of the above polypropylene resin (a-3) and α-olefin-based copolymer (a-4)
The olefinic thermoplastic elastomer composition (A) according to the present invention exhibits a better rubbery elasticity without being crosslinked (vulcanized) using a crosslinking agent or crosslinking assistant. Further, the olefinic thermoplastic elastomer composition (A) which forms a substratum layer in the laminate of the present invention is not an elastomer of thermosetting type as a conventional vulcanized rubber but is an elastomer of thermoplastic type, so that it can be put to recycled use. There is no need for a crosslinking agent, so that no process step of kneading therewith is required and it can be obtained simply and efficiently in an economical way by only a single step of dynamic heat treatment.
The olefinic thermoplastic elastomer composition (A) used in the present invention may, on requirement, contain additives known per se, such as softening agent, heat stabilizer, age resistor, weather resisting agent, anti-static agent, filler, colorant and lubricant, within the extent not obstructing the purpose of the invention.
For the softening agent, there may be employed favorably those based on mineral oil. Such mineral oil based-softening agents may favorably include those based on paraffin, naphthene and aromatics which are employed commonly in rubber industry.
Production of Olefinic Thermoplastic Elastomer Composition (A)
The olefinic thermoplastic elastomer composition (A) according to the present invention can preferably be produced by mixing, in a specific proportion mentioned above, the above polyethylene resin (a-1), ethylene-α-olefin-based copolymer (a-2) and optionally incorporated resins and additives and by subjecting the mixture to dynamic heat treatment in the absence of crosslinking agent.
Further, the olefinic thermoplastic elastomer composition (A) according to the present invention can also be produced by mixing, in a specific proportion mentioned above, the above polypropylene resin (a-3), α-olefin-based copolymer (a-4) and optionally incorporated resins and additives and by subjecting the mixture to dynamic heat treatment in the absence of crosslinking agent.
Here, the word “dynamic heat treatment” means a technical measure, in which a composition comprising each component mentioned above, for example, the polyethylene resin (a-1), ethylene-α-olefin-based copolymer (a-2) and optionally incorporated resins and additives is melt-kneaded, namely, kneaded in a molten state. The dynamic heat treatment can be realized on a kneading apparatus, for example, a mixing roll, an intensive mixer, such as a Bumbury's mixer or kneader, and a kneading machine, such as a single screw extruder or a twin screw extruder, wherein it is preferable to employ a twin screw extruder. The dynamic heat treatment may favorably be realized in a kneading apparatus of non-open type in, preferably, an inert atmosphere, such as nitrogen gas.
The dynamic heat treatment may favorably be effected at a kneading temperature usually in the range from 150 to 280° C., preferably from 170 to 240° C. for duration in the range from 1 to 20 minutes, preferably 1 to 5 minutes. Usually, the shearing force appearing upon the kneading may favorably be in the range from 10 to 10 4 sec −1 , preferably 10 2 to 10 4 sec- −1 in terms of the shearing velocity.
When the dynamic heat treatment is effected using a twin screw extruder, it may preferably conducted under a condition satisfying the following provision {circle around (4)}:
{circle around (4)}
4.8<[( T −130)/100]+2.2 log P +log Q −log R <7.0 (2)
preferably
5.0<[( T −130)/100]+2.2 log P +log Q −log R <6.8 (2′)
more preferably
5.3<[( T −130)/100]+2.2 log P +log Q −log R <6.5 (2″)
in which T represents the temperature (° C.) of the resin mixture at the die outlet of the twin screw extruder, P is the screw diameter (mm) of the twin screw extruder, Q is the maximum shearing velocity (sec −1 ) at which the resin mixture is kneaded in the twin screw extruder and is defined by the formula Q=(P×π×S)/U with P being as above, S being the number of revolutions per second (rps) and U being the gap (mm) between the inner face of the barrel wall and the kneading segment of the screw at the narrowest portion thereof, and R is the extrusion through-put (kg/hr) of the twin screw extruder.
The olefinic thermoplastic elastomer composition obtained by the dynamic heat treatment on a twin screw extruder in the absence of crosslinking agent under the condition satisfying the provision ({circle around (4)}) given above is superior in the tensile strength value, elongation set value, compression set value and appearance of the formed product made thereof.
The method for producing the olefinic thermoplastic elastomer composition (A) according to the present invention can produces an olefinic thermoplastic elastomer composition excellent in rubbery elasticity simply and efficiently by a single step, without using crosslinking agents such as organic peroxides and vulcanizing assistants such as divinyl compounds which are used in the manufacture of conventional vulcanized rubbers, by mixing, in a specified proportion described above, each component above-mentioned, for example, the above polyethylene resin (a-1) and the ethylene-α-olefin-based copolymer (a-2), or the above polyethylene resin (a-1) and the ethylene-α-olefin-based copolymer (a-2) and optionally added resins and additives and by subjecting the mixture to the dynamic heat treatment. There is no need for using a crosslinking agent and a vulcanizing assistant, so that there is required no complicated vulcanizing process step, and this can afford to produce the elastomer products at a low cost.
Ultra High Molecular Weight Polyolefin Composition (B)
In the laminated body of the present invention, the surface skin layer may comprise the ultra high molecular weight polyolefin composition (B), or the ultra high molecular weight polyolefin composition (B) and, on requirement, the olefinic thermoplastic elastomer composition (C) and the organopolysiloxane (D).
The ultra high molecular weight polyolefin composition (B) used in the present invention is, concretely, one having an intrinsic viscosity [η], determined in decalin at 135° C., in the range from 3.5 to 8.3 dl/g.
The ultra high molecular weight polyolefin composition (B) employed in the present invention may be a blend of an ultra high molecular weight polyolefin (b-1) having an intrinsic viscosity [η], determined in decalin at 135° C., in the range from 10 to 40 dl/g and a polyolefin (b-2) having an intrinsic viscosity [η], determined in decalin at 135° C., in the range from 0.1 to 5 dl/g. This blend may preferably contain the ultra high molecular weight polyolefin (b-1) in a proportion of 15 to 40% by weight per the total 100% by weight of the ultra high molecular weight polyolefin (b-1) and the polyolefin (b-2).
The above-mentioned ultra high molecular weight polyolefin and the polyolefin comprise a homopolymer of α-olefin, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene and 3-methyl-1-pentene or a copolymer thereof, wherein preference is given to a homopolymer of ethylene and a copolymer of ethylene and other α-olefin(s) having a predominant component of ethylene.
The ultra high molecular weight polyolefin composition (B) may incorporate 1 to 20 parts by weight of a liquid or solid softening agent (lubricating oil) per the total 100 parts by weight of the ultra high molecular weight polyolefin (b-1) and the polyolefin (b-2).
For the liquid softening agent, mineral oil type softening agents and synthetic softening agents are used. Such mineral oil type softening agents include, concretely, petroleum base lubricating oil such as paraffin type and naphthene type, liquid paraffin, spindle oil, refrigerator oil, dynamo oil, turbine oil, machine oil and cylinder oil. As the synthetic softening agent, there are used synthetic hydrocarbon oil, polyglycol oil, polyphenyl ether oil, ester oil, phosphate oil, polychlorotrifluoroethylene oil, fluoroester oil, chlorinated biphenyl oil and silicone oil.
As the solid softening agent, graphite and molybdenum disulfide are mainly used, and, in addition, boron nitride, tungsten disulfide, lead oxide, glass powder and metal soap may also be employed. The solid softening agent can be used alone or in a combination with the liquid softening agent and can be incorporated in the ultra high molecular weight polyolefin in the form of, for example, powder, sol, gel and suspensoid.
The above ultra high molecular weight polyolefin composition (B) may incorporate, where deemed necessary, additives such as heat stabilizer, anti-static agent, weather resisting agent, age resistor, filler, colorant and lubricant, within the extent not obstructing the purpose of the present invention.
Olefinic Thermoplastic Elastomer Composition (C)
In the laminated material of the present invention, the olefinic thermoplastic elastomer composition (C), which is incorporated on requirement in the ultra high molecular weight polyolefin composition (B) to be used for the surface skin layer, is composed of a crystalline polyolefin resin and a rubber.
As the crystalline polyolefin resin used for the olefinic thermoplastic elastomer composition (C), there are enumerated homopolymers or copolymers of α-olefin having 2 to 20 carbon atoms.
Concrete examples of the above crystalline polyolefin resin include the following (co)polymers.
(1) Homopolymers of ethylene (made by any one of low pressure method or high pressure method)
(2) Copolymers of ethylene with other α-olefin(s) or with vinyl monomer, such as vinyl acetate and ethyl acrylate, in molar proportions of 10 mole % or less
(3) Homopolymers of propylene
(4) Random copolymers of propylene and other α-olefin in a molar ratio of 10 mole % or less
(5) Block copolymers of propylene and other α-olefin in a molar ratio of 30 mole % or less
(6) Homopolymers of 1-butene
(7) Random copolymers of 1-butene and other α-olefin in a molar ratio of 10 mole % or less
(8) Homopolymers of 4-methyl-1-pentene
(9) Random copolymers of 4-methy-1-pentene and other α-olefin in a molar ratio of 20 mole % or less.
The above-mentioned α-olefin includes, concretely, ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene.
For the rubber used in the olefinic thermoplastic elastomer composition (C), though there is no restriction, rubbers of olefinic copolymer are preferable.
The above olefinic copolymer type rubbers are amorphous and random elastic copolymers with the major component of α-olefin of 2 to 20 carbon atoms, and include amorphous α-olefin copolymers comprising two or more α-olefins and α-olefin-non-conjugated diene copolymers comprising two or more α-olefins and non-conjugated diene.
Concrete examples of such olefinic copolymer type rubbers are given in the following.
(1) Rubbers of ethylene-α-olefin copolymer [Ethylene/α-olefin (mole ratio)=about 90/10 to 50/50]
(2) Rubbers of ethylene-α-olefin-non-conjugated diene copolymer [Ethylene/α-olefin (mole ratio)=about 90/10 to 50/50]
(3) Rubbers of propylene-α-olefin copolymer [Propylene/α-olefin (mole ratio)=about 90/10 to 50/50]
(4) Rubbers of butene-α-olefin copolymer [Butene/α-olefin (mole ratio)=about 90/10 to 50/50]
As the above-mentioned α-olefin, there are enumerated the same as those given as the concrete examples of the α-olefins constituting the above crystalline polyolefin resin.
As the above-mentioned non-conjugated diene, there are enumerated, concretely, dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylenenorbornene and ethylidenenorbornene.
The Mooney viscosity ML 1+4 (100° C.) of these copolymer rubbers is preferably 10 to 250, more preferably 40 to 150. The iodine value is, if the above non-conjugated diene is copolymerized, preferably 25 or less.
The olefinic copolymer type rubber mentioned above may be present in any state of the crosslink, i.e., un-crosslinked state, partially crosslinked state and perfectly crosslinked state, in the thermoplastic elastomer. In the present invention, however, it is preferable to be present in the crosslinked state, particularly it is preferable to be present in the state of partial crosslink.
The rubber used for the olefinic thermoplastic elastomer composition (C) includes, other than the above olefinic copolymer type rubbers, other rubbers, for example, diene type rubbers such as styrene-butadiene rubbers (SBR), nitrile rubbers (NBR), natural rubbers (NR) and butyl rubbers (IIR); SEBS; and polyisobutylene.
In the olefinic thermoplastic elastomer composition (C) according to the present invention, the formulation ratio by weight of the crystalline polyolefin resin and the rubber (crystalline polyolefin resin/rubber) is usually in the range from 90/10 to 5/95, preferably from 70/30 to 10/90.
Further, when a combination of the olefinic copolymer type rubber and other rubber is employed as the rubber, the other rubber is incorporated usually in a proportion of 40 parts by weight or less, preferably 5 to 20 parts by weight per the total 100 parts by weight of the crystalline polyolefin resin and the rubber.
The olefinic thermoplastic elastomer composition (C) preferably used in the present invention is composed of a crystalline polypropylene, and an ethylene-α-olefin copolymer rubber or an ethylene -α-olefin-non-conjugated copolymer rubber. These are present in the partially crosslinked state in the olefinic thermoplastic elastomer composition (C), and in addition the proportion by weight of the crystalline polypropylene and the rubber (crystalline polypropylene/rubber) is in the range from 70/30 to 10/90.
The above olefinic thermoplastic elastomer composition (C) may incorporate, where deemed necessary, additives such as mineral oil type softening agent, heat stabilizer, anti-static agent, weather resisting agent, age resistor, filler, colorant and lubricant, within the extent not obstructing the purpose of the present invention.
Concrete examples of the olefinic thermoplastic elastomer composition (C) preferably used in the present invention include a thermoplastic elastomer which is obtained by mixing 70 to 10 parts by weight of a crystalline polypropylene (C-1), 30 to 90 parts by weight of an ethylene-propylene copolymer rubber or an ethylene-propylene-diene copolymer rubber (C-2) (the total sum of the components (C-1) and (C-2) being 100 parts by weight) and 5 to 100 parts by weight of a rubber (C-3) other than the above rubber (C-2) and/or a mineral oil type softening agent (C-4), and obtained by subjecting the mixture to dynamic heat treatment in the presence of an organic peroxide to make the crosslinking of the rubber (C-2) take place.
The organic peroxide mentioned above includes, concretely, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexyne-3, 1,3-bis(tert-butylperoxyisopropyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl 4,4-bis(tert-butylperoxy)valerate, benzoyl peroxide, p-chlorobenzoylperoxide, 2,4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate, tert-butylperoxyisopropylcarbonate, diacetyl peroxide, lauroyl peroxide and tert-butyl cumyl peroxide.
Of these, in the viewpoint of odor and scorch stability a-preferred are 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexyne-3, 1,3-bis(tert-butylperoxyisopropyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane and n-butyl 4,4-bis(tert-butylperoxy)valerate. Among these, 1,3-bis(tert-butylperoxyisopropyl)benzene is most preferable.
In the olefinic thermoplastic elastomer composition (c), the organic peroxide is used in a ratio of usually 0.05 to 3 parts by weight, preferably 0.1 to 1 part by weight to the total 100 parts by weight of the crystalline polyolefin resin plus the rubber.
Upon crosslinking treatment by the above organic peroxides, there can be incorporated peroxy crosslinking aids such as sulfur, p-quinone dioxime, p,p′-dibenzoylquinone dioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine and trimethylolpropane-N,N′-m-phenylene dimaleimide, or divinylbenzene, triallyl cyanurate, polyfunctional methacrylate monomers such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate and allyl methacrylate, and polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate.
By using the above compounds, uniform and mild crosslinking reaction can be expected. Particularly, in the present invention, divinylbenzene is most preferable. Divinylbenzene, since being easy to handle, since being good in compatibility with the crystalline polyolefin resin and the rubber which consitute the main component for crosslinking treatment, and since having a function of dissolving organic peroxides to work as dispersant thereof, produces the effect that the crosslinking by heat treatment is uniform to result in a thermoplastic elastomer composition balanced in flow and physical properties.
The compounds such as the above-mentioned crosslinking aids or polyfunctional vinyl monomers are used usually in a ratio of 0.1 to 2% by weight, preferably 0.3 to 1% by weight to the whole to be treated.
Here, the word “dynamic heat treatment” means a technical measure, in which a composition comprising each component mentioned above is melt-kneaded, namely, kneaded in a molten state. The dynamic heat treatment can be realized on a heretofore known kneading apparatus, for example, an open type apparatus such as mixing roll or a non-open type apparatus such as Bumbury's mixer, extruder, kneader and continuous mixer. Among these, a non-open type kneading apparatus is preferable and the kneading is preferably performed in an inert atmosphere, such as nitrogen gas and carbon dioxide gas.
The kneading may favorably be conducted at a temperature to make the half life of the organic peroxide to be used at a time shorter than one minute, usually in the range from 150 to 280° C., preferably from 170 to 240° C. for duration in the range usually from 1 to 20 minutes, preferably 3 to 10 minutes. The shearing force to be applied, in terms of the shearing velocity, is usually 100 sec −1 or more, preferably is determined in the range from 500 to 10,000 sec −1 .
The thermoplastic elastomer composition (C) preferably used in the present invention is one that has partial crosslinking. The word “partial crosslinking” means the case where the gel content determined according to the method described below is in the range from 20 to 98% by weight, while “perfect crosslinking” means the case where the gel content is over 98% by weight. The thermoplastic elastomer composition (C) may preferably have a gel content in the range from 40 to 98% by weight.
Measurement of Gel Content:
A thermoplastic elastomer composition sample 100 mg is weighed, cut into small pieces of 0.5 mm×0.5 mm×0.5 mm, immersed in 30 ml cyclohexane in a closed container at 23° C. for 48 hours, then taken out on a filter paper and dried at room temperature for 72 hours or more until a constant weight is obtained. From the weight of the residue after drying there are subtracted the weights of all the cyclohexane insoluble components (fibrous filler, filler, pigment, etc.) other than the polymer component and the weight of the crystalline polyolefin resin in the sample before cyclohexane immersion. The value obtained thus is named “corrected final weight (Y)”.
On the other hand, the weight of the rubber in the sample is named “corrected initial weight (X)”.
The gel content (cyclohexane insoluble components) is obtained by the following formula.
Gel content [% by weight]=[corrected final weight (Y)/corrected initial weight (X)]×100.
The olefinic thermoplastic elastomer composition (C) used in the present invention is used usually in an amount of 90 to 10 parts by weight, preferably 80 to 15 parts by weight to the total 100 parts by weight of the ultra high molecular weight polyolefin composition (B) and the olefinic thermoplastic elastomer composition (C). This olefinic thermoplastic elastomer composition (C) has good flexibility, so that, when it is incorporated in the ultra high molecular weight polyolefin composition (B) in the above-mentioned extent and the resulting product is laminated on the substratum layer comprising the olefinic thermoplastic elastomer composition (A), no wrinkle appears on the surface skin layer even if the laminate is twisted or bent. Further, since it has a good flow property, the appearance of the formed laminate product is superior.
Organopolysiloxane (D)
The organopolysiloxane (D) used in the present invention includes, concretely, dimethylpolysiloxane, methylphenylpolysiloxane, fluoropolysiloxane, tetramethyltetraphenylpolysiloxane, methylhydrogenpolysiloxane and modified polysiloxanes, such as epoxy-modified, alkyl-modified, amino-modified, carboxyl-modified, alcohol-modified, fluorine-modified, alkylaralkylpolyether-modified and epoxypolyether-modified polysiloxanes. Among these, dimethylpolysiloxane is preferably used.
The organopolysiloxane (D) may preferably have a viscosity, determined according to the prescription of JIS K2283 at 25° C. of 10 to 10 7 cSt. Those that have a viscosity [JIS K2283, 25° C.] of 10 6 cSt or more, being very viscous, may be in the form of a masterbatch with the crystalline polyolefin resin to facilitate the dispersion into the ultra high molecular weight polyolefin composition (B).
The organopolysiloxane (D) can either be used only in one kind or in a combination of two or more kinds, according to its viscosity. Particularly, when it is used in a combination of two or more kinds, preferred is a combination of a low viscous organopolysiloxane having a viscosity of 10 to 10 6 cSt and a high viscous organopolysiloxane having a viscosity of 10 6 to 10 7 cSt.
Such organopolysiloxanes (D) are used usually in the range from 0.1 to 25 parts by weight, preferably in the range from 1.5 to 20 parts by weight per the total 100 parts by weight of the ultra high molecular weight polyolefin composition (B) and/or the olefinic thermoplastic elastomer composition (C). Using the organopolysiloxane (D) in the above range can yield a product excellent in sliding property, abrasion resistance and scratch resistance.
The ultra high molecular weight polyolefin composition (B) permits the process of co-extrusion and lamination with the olefinic thermoplastic elastomer, and therefore, in manufacturing constructional gaskets of the present invention, it is possible to directly laminate the olefinic thermoplastic elastomer layer (substratum layer) and the ultra high molecular weight polyolefin layer, with elimination of the film (sheet) forming process, which produces a product economically.
Constructional Gasket and Glass-run Channel for Automobile Comprising Laminated Product
The constructional gasket and automobile glass-run channel comprising the laminated product according to the present invention is constituted by a layer (substratum layer) comprising the olefinic thermoplastic elastomer composition (A) and a layer (surface skin layer (slippery resin layer)) comprising the ultra high molecular weight polyolefin composition (B).
The above constructional gasket and glass-run channel for automobile can be obtained by laminating the both layers mentioned above.
The method of laminating the layer of the thermoplastic elastomer composition (A) (hereinafter referred to as “(A) layer”) and the layer of the ultra high molecular weight polyolefin composition (B) (hereinafter referred to as “(B) layer”) is different according to the shape, size and required performance of gasket, and there may be enumerated, for example, the following lamination methods, though these are no-way restrictive.
(1) Method of heat fusing the (A) layer and (B) layer, which have been formed in advance, at a temperature or higher at which temperature at least one of the layers is molten, using a compression molding machine
(2) Method of extruding the (A) layer and (B) layer simultaneously and heat fusing them, using a multi-layer extrusion molding machine (co-extrusion forming).
In the present invention, it is generally preferable that the thickness of the (A) layer is 0.1 to 50 mm and that of the (B) layer is 5 μm to 10 mm.
In the above-mentioned constructional gasket and automobile glass-run channel, the layer comprising the olefinic thermoplastic elastomer composition (A) comprises the polyethylene resin (a-1) and the ethylene-α-olefin-based copolymer (a-2), or the polypropylene resin (a-3) and α-olefin-based copolymer (a-4), so that it exhibits superior rubbery elasticity and moldability.
Further, in the constructional gasket of the present invention, the layer comprising the ultra high molecular weight polyolefin composition (B) is excellent in abrasion resistance, scratch resistance, sliding property and chemical resistance.
FIG. 1 shows an application example of the constructional gasket of the present invention. Between wall 1 and wall 2 there are two doors, door 3 and door 4 . Door 3 turns round toward the direction P-Q with hinge 5 being a supporting point and has gasket 6 on the contacting portion with door 4 . On the other hand, door 4 moves toward the direction R-S and can tightly come into contact with door 3 by means of gasket 6 and with wall 2 by means of two gaskets 7 .
FIG. 2 shows a transverse cross section of gasket 6 . Gasket 6 is constituted by substratum layers 8 and 9 comprising the thermoplastic elastomer composition (A) and surface skin layer (slippery resin layer) 10 comprising the ultra high molecular weight polyolefin composition (B), and the two layers are heat fused to have a sufficient strength. Of substratum layers 8 and 9 above, substratum layer 9 is a portion embedded in door 3 . Gasket 6 makes door 3 contact door 4 when door 3 is closed and can retain the tightness between door 3 and door 4 when the door is locked with the U-shaped portion of the gasket deformed by compression.
The U-shaped portion of gasket 6 is deformed at the time of opening and closing of door 4 to retain the tightness between door 3 and door 4 , and, since layer 10 comprising the ultra high molecular weight polyolefin composition (B) which has superior sliding property reduces significantly the power needed for the opening and closing, door 4 can be opened and closed lightly.
FIG. 3 shows a transverse cross section of gasket 7 . Gasket 7 is constituted by substratum layers 11 and 12 comprising the thermoplastic elastomer composition (A) and surface skin layer (slippery resin layer) 13 comprising the ultra high molecular weight polyolefin composition (B), and the two layers are heat fused to have a sufficient strength. Of substratum layers 11 and 12 above, layer 12 is a portion embedded in wall 2 . Gasket 7 is deformed at the fin portion of its tip when it comes into contact with door 4 , and retains the tightness between wall 2 and door 4 . For the fin portion of gasket 7 , there are required sliding property and durability along with flexibility. For the surface layer of this portion, there is used the surface skin layer (slippery resin layer) 13 comprising the ultra high molecular weight polyolefin composition (B)which has excellent sliding property and durability, so that door 4 can be opened and closed lightly.
FIG. 4 shows another application example of the constructional gasket of the present invention. Aluminum sash frame 14 is installed with gasket 15 at its lower portion. Aluminum sash frame 14 can move on rail 16 , and aluminum sash frame 14 and rail 16 can contact tightly by means of gasket 15 .
FIG. 5 shows a cross section of gasket 15 above. Gasket 15 is constituted by substratum layers 17 and 18 comprising the thermoplastic elastomer composition (A) and surface skin layer (slippery resin layer) 19 comprising the ultra high molecular weight polyolefin composition (B), and the two layers are heat fused to have a sufficient strength. Surface skin layer (slippery resin layer) 19 can retain the tightness between aluminum sash frame 14 and rail 16 at the slide-contact portion on the side of rail 16 .
Surface skin layer (slippery resin layer) 19 comprising the ultra high molecular weight polyolefin composition (B) which has excellent sliding property decreases significantly the force needed for movement of aluminum sash frame 14 , and so aluminum sash frame 14 can be moved lightly.
Constructional Gasket Comprising Olefinic Thermoplastic Elastomer Composition (A)
The present invention also provides constructional gaskets comprising the above-mentioned olefinic thermoplastic elastomer composition (A).
The olefinic thermoplastic elastomer composition (A) used for the constructional gasket comprises, preferably, a polyethylene resin (a-1) and an ethylene-α-olefin-based copolymer (a-2) having a Mooney viscosity ML 1+4 (100° C.) of 90 to 250 and an ethylene content of 60 to 95 mole %, or a polypropylene resin (a-3) and an α-olefin-based copolymer (a-4) having a Mooney viscosity ML 1+4 (100° C.) of 60 to 250.
For the polyethylene resin (a-1) used for the constructional gasket of the present invention, widely known polyethylene resins can be used without any restriction, such as high density polyethylene, medium density polyethylene, linear low density polyethylene and low density polyethylene.
It is favorable that the polyethylene resin (a-1) has a density of 0.90 to 0.98 g/cm 3 , preferably 0.90 to 0.95 g/cm 3 .
The content of the polyethylene resin (a-1) in the olefinic thermoplastic elastomer composition (A) used in the present invention is usually 5 to 60 parts by weight, preferably 10 to 40 parts by weight to the total sum 100 parts by weight of the polyethylene resin (a-1) and the ethylene-α-olefin-based copolymer (a-2).
The content of the polypropylene resin (a-3) in the olefinic thermoplastic elastomer composition (A) used in the present invention is usually 5 to 60 parts by weight, preferably 10 to 40 parts by weight to the total sum 100 parts by weight of the polypropylene resin (a-3) and the α-olefin-based copolymer (a-4).
The ethylene-α-olefin-based copolymer (a-2) used in the present invention is one having a Mooney viscosity ML 1+4 (100 c) of 90 to 250 usually, 100 to 200 preferably and an ethylene content of 60 to 95 mole % usually, 72 to 85 mole % preferably. Here, the ethylene content means an ethylene content to the total content of α-olefins (including ethylene).
Other than the above-mentioned, for the olefinic thermoplastic elastomer composition (A) used for the constructional gasket of the present invention, the same description holds good which has previously been made on the olefinic thermoplastic elastomer composition (A) in explaining the laminate of the invention.
The constructional gasket of the present invention is obtained by molding the olefinic thermoplastic elastomer composition (A). The molding method thereof is not particularly limited, and, for example, usual extrusion molding and injection molding can be adopted. It is possible to perform the molding in a combination of the olefinic thermoplastic elastomer composition (A) with a hard olefinic thermoplastic elastomer or an olefinic resin. Among the constructional gasket, the grazing channel type and grazing bead type are used to fix the sash and the glass of a window, so that they are required to be interceptive against rain and to be air-tight. FIG. 6 shows an application example of the grazing channel type of constructional gasket according to the present invention. FIG. 7 shows that of the grazing bead type for double glasses.
The laminate of the present invention has superior abrasion resistance, durability and sliding property and also has superior rubbery elasticity. The constructional gasket and glass-run channel for automobile comprising the above-mentioned laminate have excellent abrasion resistance and sliding property and besides have excellent rubbery elasticity and mechanical properties, so that there occurs no permanent set in fatigue after a prolonged use. Further, the laminate of the present invention and the constructional gasket and the automobile glass-run channel comprising the laminate can be produced easily, and they are economical because they can be put to recycled use.
The constructional gasket comprising the olefinic thermoplastic elastomer composition (A) of the present invention can be produced easily and is economically good because it uses an olefinic thermoplastic elastomer composition capable of being reclaimed. Further, since it has superior rubbery elasticity and mechanical properties, it affords superior sealing property and air-tightness, with no occurrence of permanent set in fatigue after a long use.
This specification includes part or all of the contents as disclosed in the specifications of Japanese Patent Applications Nos. 11(1999)-311589 and 11(1999)-311602, which are the bases of the priority claim of the present application.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic cross section to explain the application status of one example of the constructional gasket of the present invention.
FIG. 2 is a cross section of gasket 6 in FIG. 1 .
FIG. 3 is a cross section of gasket 7 in FIG. 1 .
FIG. 4 is a schematic longitudinal section to explain the application status of one example of the constructional gasket of the present invention.
FIG. 5 is a longitudinal section of gasket 15 in FIG. 4 .
Each numeral in FIGS. 1 to 5 means the following.
1 , 2 - - - wall
3 , 4 - - - door
5 - - - hinge
6 , 7 - - - gasket
8 , 9 - - - substratum layer comprising thermoplastic elastomer composition (A)
10 - - - surface skin layer (slippery resin layer) comprising ultra high molecular weight polyolefin composition (B)
11 , 12 - - - substratum layer comprising thermoplastic elastomer composition (A)
13 - - - surface skin layer (slippery resin layer) comprising ultra high molecular weight polyolefin composition (B)
14 - - - aluminum sash frame
15 - - - gasket
16 - - - rail
17 , 18 - - - substratum layer comprising thermoplastic composition (A)
19 - - - surface skin layer (slippery resin layer) comprising ultra high molecular weight polyolefin composition (B)
FIG. 6 is a drawing showing an application example of the grazing channel type of the constructional gasket of the present invention.
FIG. 7 is a drawing showing an application example of grazing bead type of the constructional gasket for double glasses of the present invention.
Each numeral in FIGS. 6 and 7 means the following.
20 - - - grazing channel
21 - - - sash
22 - - - glass
23 - - - thickness of glass plate
24 - - - surface clearance
25 - - - grazing bead set up previously
26 - - - grazing bead set up later
27 - - - setting block
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention will be explained hereinafter by way of examples, which, however, should not be construed as limiting the scope of the present invention.
EXAMPLE 1
There were mixed by a Henschel mixer 30 wt. % of a linear low density polyethylene (density; 0.920 g/cm 3 , MFR; 2.1 g/10 min., ethylene content; 97.0 mole %, 4-methyl-1-pentene content; 3.0 mole %) and 70 wt. % of an ethylene-propylene-dicyclopentadiene copolymer rubber (ethylene content; 77 mole %, Mooney viscosity ML 1+4 (100° C.); 145, iodine value; 12). The mixture was subjected to dynamic heat treatment, using a twin screw extruder having a L/D of 30 and a screw diameter of 50 mm, in the nitrogen atmosphere at 220° C. and extruded to produce pellets of an olefinic thermoplastic elastomer composition (A-1). The olefinic thermoplastic elastomer composition (A-1) and the ultra high molecular weight polyethylene composition (B-1) having an intrinsic viscosity [η], determined in decalin at 135° C., of 7.0 dl/g and a density of 0.965 g/cm 3 were subjected to co-extrusion molding at a temperature of 230° C. to obtain the gasket of the present invention.
Here, the ultra high molecular weight polyethylene composition (B-1) is composed of 23 wt. % of an ultra high molecular weight polyethylene having an intrinsic viscosity [η] measured in decalin at 135° C., of 28 dl/g and 77 wt. % of a low molecular weight polyethylene having an intrinsic viscosity [η] measured in decalin at 135° C., of 0.73 dl/g.
The shape of the obtained gasket is shown in FIG. 2, the size of the gasket being 9.0 mm for w 1 , 1.5 mm each for w 2 and w 3 , 1.0 mm for t, 8.0 mm for h, 0.8 mm for the thickness of U-shaped portion and average 30 μm for the thickness of the ultra high molecular weight polyethylene layer.
The obtained gasket was installed as gasket 6 for door 3 shown in FIG. 1, and an endurance test was conducted by repeated openings and closings of door 4 made of 8 mm thick glass. As a result, the gasket endured the repeat test of 50,000 times and maintained the function as gasket.
EXAMPLE 2
Using 30 wt. parts of the linear low density polyethylene used in Example 1, 70 wt. parts of the ethylene-propylene-dicyclopentadiene copolymer rubber used in Example 1 and 40 wt. parts of a mineral oil type softening agent (paraffinic process oil made by Idemitsu Kosan Co. Ltd., trade name; Diana Process PW-380), an olefinic thermoplastic elastomer composition (A-2) was obtained in the same way as Example 1. Then, using the above composition and the ultra high molecular weight polyethylene composition (B-1) used in Example 1, a gasket was manufactured in the same way as Example land subjected to the endurance test.
As a result, the gasket endured the repeat test of 50,000 times and was maintaining the function as gasket.
EXAMPLE 3
Using 15 wt. parts of the linear low density polyethylene used in Example 1, 85 wt. parts of the ethylene-propylene-dicyclopentadiene copolymer rubber used in Example 1 and 20 wt. parts of a propylene homopolymer (MFR; 1.5 g/10 min.), an olefinic thermoplastic elastomer composition (A-3) was obtained in the same manner as Example 1. Then, using the above composition together with the ultra high molecular weight polyethylene composition (B-1) used in Example 1, a gasket was manufactured in the same manner as Example 1 and subjected to the endurance test. As a result, the gasket endured the repeat test of 50,000 times and was maintaining the function as gasket.
EXAMPLE 4
Using 30 wt. parts of the linear low density polyethylene used in Example 1 and 110 wt. parts of an oil-extended ethylene-propylene-dicyclopentadiene copolymer rubber which is obtained by incorporating 40 wt. parts of an extending oil (paraffinic process oil made by Idemitsu Kosan Co. Ltd., trade name; Diana Process PW-380) in the ethylene-propylene-dicyclopentadiene copolymer rubber used in Example 1, an olefinic thermoplastic elastomer composition (A-4) was obtained in the same way as Example 1. Then, using the above composition and the ultra high molecular weight polyethylene composition (B-1) used in Example 1, a gasket was manufactured in the same way as Example land subjected to the endurance test. As a result, the gasket endured the repeat test of 50,000 times and was retaining the function as gasket.
EXAMPLE 5
Using the olefinic thermoplastic elastomer composition (A-1) obtained in Example 1 and an ultra high molecular weight polyolefin composition obtained by kneading with a twin screw extruder 75 wt. parts of the ultra high molecular weight polyethylene composition (B-1) used in Example 1 and 25 wt. parts of an olefinic thermoplastic elastomer composition (C-1) mentioned below, a gasket was manufactured in the same manner as Example 1 and subjected to the endurance test. As a result, the gasket endured the repeat test of 50,000 times and was retaining the function as gasket.
[Olefinic Thermoplastic Elastomer Composition (C-1)]
Eighty parts by weight of an ethylene-propylene-5-ethylidenenorbornene copolymer rubber having an ethylene content of 70 mole %, an iodine value of 12 and a Mooney viscosity ML 1+4 (100° C.) of 120 and twenty parts by weight of a polypropylene having a MFR of 13 g/10 min. and a density of 0.91 g/cm 3 were kneaded, using a Bumbury's mixer, in the nitrogen atmosphere at 180° C. for 5 minutes with a shearing velocity of 3,000 sec −1 . Then, the kneaded mass was formed into a sheet through a roll and cut with a sheet cutter to fabricate square pellets.
The pellets were blended with 0.3 wt. part of 1,3-bis(tert-butylperoxyisopropyl)benzene and 0.5 wt. part of divinylbenzene using a Henschel mixer.
The mixture was extruded, using a twin screw extruder having a L/D of 40 and a screw diameter of 50 mm, in the nitrogen atmosphere at 220° C. to obtain a thermoplastic elastomer composition (C-1).
The gel content of the obtained thermoplastic elastomer composition (c-1) was 85 wt. % according to the previously mentioned method.
EXAMPLE 6
Using the olefinic thermoplastic elastomer composition (A-1) obtained in Example 1 and an ultra high molecular weight polyolefin composition obtained by kneading with a twin screw extruder 75wt. parts of the ultra high molecular weight polyethylene composition (B-1) used in Example 1, 25 wt. parts of the olefinic thermoplastic elastomer composition (C-1) obtained in Example 5 and 2 wt. parts of an organopolysiloxane (D-1) (made by Dow Corning Toray Silicone Co., Ltd., trade name; Silicone Oil SH 200, viscosity; 3000 cSt), a gasket was manufactured in the same manner as Example 1 and subjected to the endurance test. As a result, the gasket endured the repeat test of 50,000 times and was retaining the function as gasket.
EXAMPLE 7
Using the olefinic thermoplastic elastomer composition (A-1) obtained in Example 1 and an ultra high molecular weight polyolefin composition obtained by kneading with a twin screw extruder 75 wt. parts of the ultra high molecular weight polyethylene composition (B-1) used in Example 1, 25 wt. parts of the olefinic thermoplastic elastomer composition (C-1) obtained in Example 5, 2 wt. parts of the organopolysiloxane (D-1) used in Example 6 and 20 wt. parts of an organopolysiloxane (D-2) (made by Dow Corning Toray Silicone Co., Ltd., trade name; Silicone oil-polypropylene masterbatch BY27-002, containing 50 wt. % of ultra high molecular weight silicone oil), a gasket was manufactured in the same manner as Example 1 and subjected to the endurance test. As a result, the gasket endured the repeat test of 50,000 times and was retaining the function as gasket.
COMPARATIVE EXAMPLE 1
Using the gasket made of a conventional soft vinyl chloride resin the endurance test was conducted in the same manner as mentioned above. As a result, the contacting surface with the door was destroyed at a repeat of 22,000 times, and the friction drag between the door and the surface became markedly high, causing the gasket to be unfit for use.
EXAMPLE 8
The olefinic thermoplastic elastomer composition (A-1) of Example 1 and the ultra high molecular weight polyethylene composition (B-1) used in Example 1 were subjected to co-extrusion molding at 230 t to obtain a gasket having a sectional shape shown in FIG. 5 . The average thickness of the surface skin layer (slippery resin layer) comprising the ultra high molecular weight polyethylene composition (B-1) was 0.1 mm. The obtained gasket was installed in an aluminum sash frame shown in FIG. 4, and the aluminum sash frame was made go and return repeatedly on a rail for the endurance test. As a result, the gasket endured the repeat test of 50,000 times and was maintaining the function as gasket.
COMPARATIVE EXAMPLE 2
Using the gasket made of a conventional hard vinyl chloride resin, the endurance test was conducted in the same manner as mentioned above. As a result, the gasket broke at the contacting surface with the rail at a repeat of 16,500 times, and the friction drag between the rail and the surface increased markedly, causing the gasket to be unfit for use.
EXAMPLE 9
There were mixed, with a Henschel mixer, 20 wt. % of a polypropylene having a MFR of 13 g/10 min. and a density of 0.91 g/cm 3 and 80 wt. % of a propylene-ethylene copolymer rubber having a propylene content of 68 mole % and a Mooney viscosity ML 1+4 (100° C.) of 75. Then, using a twin screw extruder having a L/D of 30 and a screw diameter of 50 mm, the mixture was subjected to dynamic heat treatment in the nitrogen atmosphere at 220° C. and extruded to obtain pellets of an olefinic thermoplastic elastomer composition (A-5).
Using this olefinic thermoplastic elastomer composition (A-5) and the ultra high molecular weight polyethylene composition (B-1) used in Example 1, a gasket was produced in the same manner as Example 1, and the endurance test was performed. The result was that the gasket endured the repeat test of 50,000 times and maintained the function as gasket.
Table 1 shows the conditions of the dynamic heat treatment in manufacturing the above olefinic thermoplastic elastomer compositions (A-1), (A-2), (A-3), (A-4) and (A-5), and the characteristics thereof.
TABLE 1
A-1
A-2
A-3
A-4
A-5
Components
PE
30
30
15
30
EPDM
70
70
85
PER
80
Oil - extended
110
EPDM
PP
20
20
Paraffinic oil
40
Manufacturing
Conditions
T
223
222
239
225
223
P
50
50
50
50
50
Q
2800
2800
2800
2800
2800
R
50
50
50
50
50
S
280
280
280
280
280
U
15.7
15.7
15.7
15.7
15.7
Value in
6.42
6.41
6.58
6.44
6.42
formula (2)
Physical
Properties
JIS A-
74
70
75
70
82
hardness
Compression
46
46
55
43
58
set (%)
Tensile
18
14
13
13
27
strength
(MPa)
Elongation
10
9
7
7
11
set (%)
Value in
14.2
15.9
22.8
12.9
22.7
formula (1)
PE: Linear low density polyethylene
EPDM: Ethylene-propylene-dicyclopentadiene copolymer rubber
PER: Propylene-ethylene copolymer rubber
PP: Propylene homopolymer
T: Resin temperature at die outlet of twin screw extruder (c)
P: Screw diameter of twin screw extruder (mm)
Q: Maximum shearing velocity occurring in twin screw
extruder (sec −1 )
R: Extrusion through-put of twin screw extruder (kg/h)
S: Screw revolution per second (rps)
U: Gap at narrowest portion between inner face of barrel wall and kneading segment of screw (mm)
[( T −130)/100]+2.2 log P +log Q −log R Formula (2)
Y −0.43 X Formula (1)
wherein X denotes the JIS A-hardness value (dimensionless value) of olefinic thermoplastic elastomer composition, determined according to the prescription of JIS K6301, and Y denotes the compression set value (unit; %)of olefinic thermoplastic elastomer composition, determined at a condition of 70° C.×22 hours according to the prescription of JIS K6301.
The raw materials used in the manufacture of the olefinic thermoplastic elastomer compositions in the under-mentioned Examples and Comparative Examples are as follows. The melt flow rate (MFR) values are ones determined, unless otherwise specified, at a condition of 190° C. and 2.16 kg load according to the prescription of ASTM D1238.
<<polyethylene resin (a-1)>>
(a-1-i) high density polyethylene
1) density; 0.954 g/cm 3
2) MFR; 0.8 g/10 min.
3) ethylene homopolymer
(a-1-ii) linear low density polyethylene
1) density; 0.920 g/cm 3
2) MFR; 2.1 g/10 min.
3) ethylene content; 97.0 mole %, 4-methyl-1-pentene content; 3.0 mole %
(a-1-iii) linear low density polyethylene
1) density; 0.920 g/cm 3
2) MFR; 18 g/10 min.
3) ethylene content; 96.8 mole %, 4-methyl-1-pentene content; 3.2 mole %
(a-1-iv) low density polyethylene
1) density; 0.927 g/cm 3
2) MFR; 3 g/10 min.
3) ethylene homopolymer
<<ethylene-α-olefin-based copolymer (a-2)>>
(a-2-i) ethylene-propylene-dicyclopentadiene copolymer rubber
1) ethylene content; 77 mole %
2) Mooney viscosity ML 1+4 (100° C.); 145
3) iodine value; 12
(a-2-ii) ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber
1) ethylene content; 82 mole %
2) Mooney viscosity ML 1+4 (100 t); 15
3) iodine value; 10
(a-2-iii) ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber
1) ethylene content; 68 mole %
2) Mooney viscosity ML 1+4 (100° C.); 69
3) iodine value; 13
(a-2-iv) mixture of 70 wt. parts of the above ethylene-propylene-dicyclopentadiene copolymer rubber (a-2-i) and 40 wt. parts of extending oil (paraffinic oil made by Idemitsu Kosan Co. Ltd., trade name; Diana Process PW-380)
<<polypropylene resin (a-3)>>
(a-3-i) propylene homopolymer
1) density; 0.91 g/cm 3
2) MFR (ASTM D1238, 230° C., 2.16 kg load); 13 g/10 min.
<<propylene-α-olefin-based copolymer (a-4a)>>
(a-4-i) propylene-ethylene copolymer rubber
1) propylene content; 68 mole %
2) Mooney viscosity ML 1+4 (100° C.); 75
<<polypropylene resin (a-5)>>
(a-5-i) propylene homopolymer
1) density; 0.91 cm 3
2) MFR (ASTM D1238, 230° C., 2.16 kg load); 1.5 g/10 min.
<<mineral oil type softening agent>>
paraffinic oil: made by Idemitsu Kosan Co. Ltd., trade name; Diana Process PW-380
EXAMPLES 10 to 19
Each of the components was put in a Henschel mixer according to the formulations shown in Table 2 and they were mixed. The mixtures was dynamically heat treated and extruded in the nitrogen atmosphere at 220° C., using a twin screw extruder having a L/D of 30 and a screw diameter of 50 mm, to produce pellets of the olefinic thermoplastic elastomer compositions. The manufacturing conditions are shown in Table 2.
The hardness, compression set (70° C.×22 hours), tensile strength and elongation set values of these olefinic thermoplastic elastomer compositions were determined according to the prescription of JIS K6301. The results are shown in Table 2. Further, the endurance test (100° C.×3 days) was carried out according to the prescription of JIS A5756 (1997), and by the following calculation formulas the changes in hardness values, the rates of change in tensile strength values and the rates of change in elongation values were determined. The results are shown in Table 2.
Change in hardness value:
Hr=H
1
−H
0
H 0 ; hardness value before aging, H 1 ; hardness value after aging
Rate of change in tensile strength value (%) (γF)
γ F =[( F 1 −F 0 )/ F 0 ]×100
F 0 ; tensile strength value before aging, F 0 ; tensile strength value after aging
Rate of change in elongation value at break (%) (γE):
γ E =[( E 1 −E 0 )/ E 0 ]×100
E 0 ; elongation value at break before aging, E 1 ; elongation value at break after aging
COMPARATIVE EXAMPLES 3 TO 6
Except for using the components shown in Table 2 according to the formulas shown in Table 2, the same procedures were followed as in Examples. The results are shown in Table 2.
TABLE 2
Example
10
11
12
13
14
15
16
Components
a-1-i
30
a-1-ii
30
30
10
50
a-1-iii
30
a-1-iv
30
a-2-i
70
70
70
70
70
90
50
a-2-ii
a-2-iii
a-2-iv
a-3-i
a-4-i
a-5-i
Paraffinic oil
40
Manufacturing
T
230
223
222
223
222
235
232
Conditions
P
50
50
50
50
50
50
50
Q
2800
2800
2800
2800
2800
2800
2800
R
50
50
50
50
50
50
50
S
280
280
280
280
280
280
280
U
15.7
15.7
15.7
15.7
15.7
15.7
15.7
Value in
6.49
6.42
6.41
6.42
6.41
6.54
6.51
formula (2)
Physical
JIS A-
81
74
74
76
70
62
88
Properties
hardness
Compression
49
46
55
51
46
43
58
set (%)
Tensile
12
18
15
14
14
10
29
str. (MPa)
Elongation
18
10
10
11
9
9
16
set (%)
Value in
14.2
14.2
23.2
18.3
15.9
16.3
20.2
formula (1)
Durability
Ratio of
−12
−11
−8
−10
−12
−9
−4
change in
tens. str. (%)
Ratio of
−8
−8
−11
−6
−10
−7
−6
change in
elong. (%)
Change in
−2
−3
−3
−4
−2
−2
−3
hardness
Example
Comparative Example
17
18
19
3
4
5
6
Components
a-1-i
a-1-ii
30
15
30
30
70
a-1-iii
a-1-iv
a-2-i
85
30
70
a-2-ii
70
a-2-iii
70
a-2-iv
110
a-3-i
20
a-4-i
80
a-5-i
20
30
Paraffinic oil
Manufacturing
T
225
238
223
222
225
230
235
Conditions
P
50
50
50
50
50
50
50
Q
2800
2800
2800
2800
2800
2800
2800
R
50
50
50
50
50
50
50
S
280
280
280
280
280
280
280
U
15.7
15.7
15.7
15.7
15.7
15.7
15.7
Value in
6.44
6.57
6.42
6.41
6.44
6.49
6.54
formula (2)
Physical
JIS A-
Properties
hardness
70
77
82
84
68
91
91
Compression
43
57
58
66
72
69
87
set (%)
Tensile
13
13
27
11
2
35
4
str. (MPa)
Elongation
7
11
11
19
20
29
32
set (%)
Value in
12.9
23.9
22.7
29.9
42.8
29.9
47.9
formula (1)
Durability
Ratio of
−11
−8
−10
−20
−12
−12
−10
change in
tens. str. (%)
Ratio of
−9
−8
−9
−18
−18
−11
−9
change in
elong. (%)
Change in
−2
−3
−2
−6
−4
−4
−6
hardness
T: Resin temperature at die outlet of twin screw extruder (C)
P: Screw diameter of twin screw extruder (mm)
Q: Maximum shearing velocity occurring in twin screw extruder (sec −1 )
R: Extrusion through-put of twin screw extruder (kg/h)
S: Screw revolution per second (rps)
U: Gap at narrowest portion between inner face of barrel wall and kneading segment of screw (mm)
[( T −130)/100]+2.2 log P +log Q −log R Formula (2)
Y −0.43 X Formula (1)
wherein X denotes the JIS A-hardness value (dimensionless value) of olefinic thermoplastic elastomer composition, determined according to the prescription of JIS K6301, and Y denotes the compression set value (unit; %) of olefinic thermoplastic elastomer composition, determined at a condition of 70° C.×22 hours according to the prescription of JIS K6301.
All the publications, patents and patent applications cited herein are incorporated herein by reference in their entirety. | The present invention relates to a laminate comprising an olefinic thermoplastic elastomer which comprises:
(a) a substratum layer comprising an olefinic thermoplastic elastomer composition (A) having the following characteristics {circle around (1)} to {circle around (3)}:
{circle around (1)}
9≦ Y −0.43 X ≦27 (1)
wherein X denotes the JIS A-hardness value (a dimensionless value) of the olefinic thermoplastic elastomer composition determined according to the prescription of JIS K6301 and Y represents the compression set value (expressed by %) of the olefinic thermoplastic elastomer composition determined according to the prescription of JIS K6301 under a condition of 70° C. and 22 hours,
{circle around (2)} a tensile strength value in the range from 5 to 30 MPa determined according to the prescription of JIS K6301 and
{circle around (3)} an elongation set value of 18% or less determined according to the prescription of JIS K6301, and
(b) a surface skin layer comprising an ultra high molecular weight polyolefin composition (B) having an intrinsic viscosity [η] measured in decalin at 135° C. in the range from 3.5 to 8.3 dl/g; and a constructional gasket comprising the olefinic thermoplastic elastomer composition (A). | 1 |
FIELD OF THE INVENTION
The present invention relates to a process for inputting English pronunciation symbols.
BACKGROUND OF THE INVENTION
Upon developing a speech synthesis English dictionary or creating English phonetic text, an English pronunciation symbol string must be input. However, English pronunciation symbols cannot be intuitively input unlike Japanese reading.
As conventional methods of inputting English pronunciation symbols (about 40 symbols), a method of registering pronunciation symbols as external characters and selecting them from an external character symbol table, a method of setting each of pronunciation symbols in correspondence with one or two alphabets and inputting symbols like normal text, and the like are known (for example, see Japanese Patent Laid-Open No. 7-78133).
However, with the method of registering pronunciation symbols as external characters, the user must display the external character symbol table and select a symbol from it every time he or she inputs one pronunciation symbol, resulting in an inefficient input process. Also, since external characters are used, compatibility with other systems is poor.
Furthermore, with the method of setting each pronunciation symbol in correspondence with one or two alphabets, it is difficult for the user to intuitively recognize the correspondence between an alphabet string and pronunciation symbol and to accurately input symbols.
SUMMARY OF THE INVENTION
The present invention has been made in consideration of the above problems, and has as its object to provide a processing technique that allows the user to efficiently and accurately input pronunciation symbols.
In order to achieve the above object, an information processing apparatus according to the present invention comprises the following arrangement. That is, an information processing apparatus for inputting a pronunciation symbol corresponding to an English notation, comprising: pronunciation symbol information holding means for holding pronunciation symbol information indicating a relationship between a predetermined alphabet and a pronunciation symbol that starts from the predetermined alphabet; pronunciation symbol statistical information holding means for holding statistical information associated with a probability of occurrence of each pronunciation symbol immediately after a predetermined pronunciation symbol; display means for extracting pronunciation symbols corresponding to an input alphabet from the pronunciation symbol information, and displaying the extracted pronunciation symbols while sorting them on the basis of the statistical information; and determination means for determining a pronunciation symbol corresponding to the English notation from the displayed pronunciation symbols.
The information processing apparatus of the present invention allows the user to efficiently and accurately input pronunciation symbols.
Other features and advantages of the present invention will be apparent from the following description taken in conjunction with the accompanying drawings, in which like reference characters designate the same or similar parts throughout the figures thereof.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention.
FIG. 1 is a block diagram showing the arrangement of an information processing apparatus according to an embodiment of the present invention;
FIG. 2 is a flow chart showing the processing sequence of the information processing apparatus according to the embodiment of the present invention;
FIG. 3 shows a pronunciation symbol table 105 of the information processing apparatus according to the embodiment of the present invention;
FIG. 4 shows an associative pronunciation symbol table 106 of the information processing apparatus according to the embodiment of the present invention;
FIG. 5 shows pronunciation symbol statistical information 107 of the information processing apparatus according to the embodiment of the present invention;
FIG. 6 shows pronunciation symbol image data 108 of the information processing apparatus according to the embodiment of the present invention;
FIG. 7 shows pronunciation symbol auxiliary data 109 of the information processing apparatus according to the embodiment of the present invention;
FIG. 8 shows an edit result database 118 of the information processing apparatus according to the embodiment of the present invention; and
FIG. 9 shows an edit process of pronunciation symbols by the information processing apparatus according to the embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Preferred embodiments of the present invention will now be described in detail in accordance with the accompanying drawings.
FIG. 1 is a block diagram showing the arrangement of an information processing apparatus according to an embodiment of the present invention.
Reference numeral 101 denotes a notation processing unit that executes a process associated with English notations to which pronunciation symbols are to be given.
Reference numeral 102 denotes a pronunciation symbol candidate processing unit that executes a process associated with pronunciation symbol candidates. Reference numeral 103 denotes a pronunciation symbol candidate holding unit that holds pronunciation symbol candidates. Reference numeral 104 denotes a pronunciation symbol candidate presentation unit that presents pronunciation symbol candidates. Reference numeral 105 denotes a pronunciation symbol table that stores alphabets and pronunciation symbols each of which has a corresponding alphabet as its first character. FIG. 3 shows an example of the pronunciation symbol table.
Reference numeral 106 denotes an associative pronunciation symbol table that stores alphabets, and pronunciation symbols each of which is associable as the pronunciation of a given alphabet when that alphabet forms a part of an arbitrary English notion. FIG. 4 shows an example of the associative pronunciation symbol table. For example, pronunciation symbols of an English notation “able” is “EY1 B AH0 L,” and “EY” is associable as the pronunciation of alphabet “a.”
Reference numeral 107 denotes pronunciation symbol statistical information used to determine a presentation order of pronunciation symbol candidates. FIG. 5 shows an example of the pronunciation symbol statistical information. In this case, a statistical value is generated by multiplying by −1 the logarithm of the probability of occurrence of a pronunciation symbol of interest immediately after a forward pronunciation symbol, and normalizing the product to an integer by multiplying that product by an appropriate value. Symbol Φ indicates a case wherein no forward pronunciation symbol is present (i.e., a case wherein the pronunciation symbol of interest is located at the head of an English notation). The probability of occurrence of a pronunciation symbol of interest immediately after a forward pronunciation symbol can be generated based on a dictionary and the like.
Reference numeral 108 denotes pronunciation symbol image data as pairs of pronunciation symbols expressed by alphabets and image symbols (symbols generally used in a dictionary and the like) corresponding to these pronunciation symbols. FIG. 6 shows an example of the pronunciation symbol image data. Reference numeral 109 denotes pronunciation symbol auxiliary data as pairs of pronunciation symbols expressed by alphabets, and auxiliary data of these pronunciation symbols. FIG. 7 shows an example of the pronunciation symbol auxiliary data. “odd: AA D” indicates that the pronunciation symbol “AA” is a pronunciation of “AA” of “odd.”
Reference numeral 110 denotes a key input processing unit that processes key operations input by the user upon editing pronunciation symbols. Reference numeral 111 denotes an input alphabet holding unit that holds alphabets input by the user.
Reference numeral 112 denotes an input mode change unit that changes an input mode between two input modes (i.e., a direct input mode and associative input mode). In the direct input mode, the user directly inputs and edits the first alphabet of a pronunciation symbol. In the associative input mode, the user inputs and edits some alphabets of an English notation to which pronunciation symbols are to be given. Reference numeral 113 denotes an input mode holding unit that holds the current input mode.
Reference numeral 114 denotes a pronunciation symbol determination unit that processes a pronunciation symbol determination operation. Reference numeral 115 denotes a pronunciation symbol speech generation unit for generating speech of pronunciation symbols. Reference numeral 116 denotes a phonemic symbol dictionary as acoustic data used to generate speech of pronunciation symbols. Reference numeral 117 denotes an edit result save unit that saves the edit results of pronunciation-symbols. Reference numeral 118 denotes an edit result database that holds the edit results of pronunciation symbols. FIG. 8 shows an example of the edit result database. In this case, the database holds pairs of English notations and pronunciation symbols.
FIG. 2 is a flow chart showing the processing sequence in the information processing apparatus according to the embodiment of the present invention.
In step S 201 , the user inputs an English notation to which pronunciation symbols are to be given. In step S 202 , the notation processing unit 101 displays the English notation input in step S 201 . A of FIG. 9 shows a display example (note that FIG. 9 shows display examples in the direct input mode). In this example, assume that pronunciation symbols corresponding to an English notation “that” are input.
In step S 203 , the user presses a given key, and the key input processing unit 110 detects the key pressed by the user.
The key input processing unit 110 checks in step S 204 whether or not the key pressed by the user in step S 203 is an “end key.” If the pressed key is an “end key,” the flow advances to step S 223 ; otherwise, the flow advances to step S 205 .
The key input processing unit 110 checks in step S 205 whether or not the key pressed by the user in step S 203 is an “alphabet key.” If the pressed key is an “alphabet key,” the key input processing unit 110 stores that value in the input alphabet holding unit 111 , and displays the input alphabet in an edit frame (A of FIG. 9 ). The flow then advances to step S 206 . If the pressed key is not an “alphabet key,” the flow advances to step S 212 .
The pronunciation symbol candidate processing unit 102 checks in step S 206 whether or not an alphabet is held in the input alphabet holding unit 111 . If an alphabet is held, the flow advances to step S 207 ; otherwise, the flow returns to step S 203 .
The pronunciation symbol candidate processing unit 102 determines with reference to the input mode holding unit 113 in step S 207 whether or not the current input mode is the direct input mode. If the current input mode is the direct input mode, the flow advances to step S 208 ; otherwise (i.e., the associative input mode), the flow-advances to step S 209 .
If the current input mode is the direct input mode, the pronunciation symbol candidate processing unit 102 reads out, from the pronunciation symbol table 105 , pronunciation symbol candidates corresponding to the alphabet held in the input alphabet holding unit 111 in step S 208 . For example, if the alphabet is “a,” the corresponding pronunciation symbol candidates are “AA, AE, AH, AO, AW, AY.” Note that pronunciation symbols of the English notation “that” in this example ( FIG. 9 ) include a pronunciation symbol starting from alphabet “d,” that starting from alphabet “a,” and that starting from alphabet “t.” Hence, the user inputs alphabet “d” initially, and “D, DH” are read out as candidates of pronunciation symbols that start from “d.”
On the other hand, if the current input mode is the associative input mode, the pronunciation symbol candidate processing unit 102 reads out, from the associative pronunciation symbol table 105 , pronunciation symbol candidates corresponding to the alphabet held in the input alphabet holding unit 111 , and holds them in the pronunciation symbol candidate holding unit 103 in step S 209 . For example, when the alphabet is “a,” corresponding pronunciation symbol candidates are “AA, AE, AH, AO, AW, AY, EH, ER, EY, IH, IY, OW.” In case of the English notation “that” in this example ( FIG. 9 ), the user inputs alphabet “t,” and “CH, DH, SH, T, TH” are read out as pronunciation symbol candidates.
In step S 210 , the pronunciation symbol candidate processing unit 102 gives statistical values to the pronunciation symbol candidates held in the pronunciation symbol candidate holding unit 103 with reference to the pronunciation symbol statistical information 107 . Furthermore, the unit 102 sorts the pronunciation symbol candidates in ascending order of statistical value.
In step S 211 , the pronunciation symbol candidate presentation unit 104 assigns image data to the pronunciation symbol candidates held in the pronunciation symbol candidate holding unit 103 with reference to the pronunciation symbol image data 108 . Furthermore, the unit 104 presents the pronunciation symbol candidates assigned with the image data to the user. B of FIG. 9 shows a display example. In this case, pronunciation symbol candidates “D[d] DH[δ]” corresponding to user's input “d” are presented. Also, the first candidate “D[d]” is presented in an active state.
In this example, the unit 104 presents pronunciation symbol candidates assigned with the pronunciation symbol image data 108 to the user. Alternatively, the unit 104 may present pronunciation symbol candidates assigned with the pronunciation symbol auxiliary data 109 to the user. In this case, “D[dee: D IY] DH[thee: DH IY]” are presented to the user.
The key input processing unit 110 checks in step S 212 whether or not the key pressed by the user in step S 203 is an “input mode change key.” If the pressed key is an “input mode change key,” the flow advances to step S 213 ; otherwise, the flow advances to step S 214 .
In step S 213 , the input mode change unit 112 refers to the input mode held in the input mode holding unit 113 . If the input mode is the “direct input mode” it is changed to the “associative input mode,” or vice versa, and the flow advances to step S 206 .
The key input processing unit 110 checks in step S 214 if the key pressed by the user in step S 203 is a “select key.” If the pressed key is a select key, the flow advances to step S 215 ; otherwise, the flow advances to step S 218 .
The pronunciation symbol candidate presentation unit 104 checks in step S 215 if pronunciation symbol candidates are presented to the user. If pronunciation symbol candidates are presented, the flow advances to step S 216 ; otherwise, the flow returns to step S 203 .
In step S 216 , the pronunciation symbol presentation unit 104 changes an active one of the pronunciation symbol candidates presented to the user to the next candidate. The active candidate is, for example, underlined. C of FIG. 9 shows an example.
In step S 217 , the pronunciation symbol speech generation unit 115 reads out speech data of the pronunciation symbol which is newly activated in step S 216 from the phonemic symbol dictionary 116 and generates that speech data. The flow then returns to step S 203 .
The key input processing unit 110 checks in step S 218 if the key pressed by the user in step S 203 is an “enter key.” If the pressed key is an “enter key,” the flow advances to step S 219 ; otherwise, the flow returns to step S 203 .
The pronunciation symbol candidate presentation unit 104 checks in step S 219 if pronunciation symbol candidates are presented to the user. If pronunciation symbol candidates are presented, the flow advances to step S 220 ; otherwise, the flow returns to step S 203 .
In step S 220 , the pronunciation symbol candidate presentation unit 104 presents the active pronunciation symbol in place of the alphabet in the edit frame. D of FIG. 9 shows an example.
In step S 221 , the pronunciation symbol candidate presentation unit 104 clears the presented candidates. E of FIG. 9 shows an example. The pronunciation symbol candidate processing unit 102 clears the pronunciation symbol candidates held in the pronunciation symbol candidate holding unit 103 , and the flow advances to step S 222 .
In step S 222 , the key input processing unit 110 clears the alphabet held in the input alphabet holding unit 111 , and the flow returns to step S 203 . The aforementioned processes are repeated for the next pronunciation symbol (F of FIG. 9 ), thus finally inputting pronunciation symbols shown in G of FIG. 9 .
In step S 223 , the edit result save unit 117 saves a pair of the input English notation and the edited pronunciation symbols in the edit result database 118 .
As can be seen from the above description, according to this embodiment, in the direct input mode, the user need only input the first alphabet of a pronunciation symbol to display pronunciation symbols that start from the input alphabet and are sorted in descending order of predetermined probability of occurrence. Hence, compared to selection from an external character symbol table (about 40 symbols), the input efficiency can be greatly improved. In the associative input mode, pronunciation symbols when an alphabet forms a part of an arbitrary English notation are stored as associative pronunciation symbol information for respective alphabets. Every time the user inputs each alphabet that forms an English notation, pronunciation symbols corresponding to the input alphabet are displayed while being sorted in descending order of predetermined probability of occurrence. Hence, compared to the conventional method (a method setting a pronunciation symbol in correspondence with one or two alphabets), the correspondence between alphabets and pronunciation symbols is clear, and an accurate input can be realized. As a result, pronunciation symbols can be efficiently and accurately input.
Another Embodiment
Note that the present invention may be applied to either a system constituted by a plurality of devices (e.g., a host computer, interface device, reader, printer, and the like), or an apparatus consisting of a single equipment (e.g., a copying machine, facsimile apparatus, or the like).
The objects of the present invention are also achieved by supplying a storage medium, which records a program code of a software program that can implement the functions of the above-mentioned embodiments to the system or apparatus, and reading out and executing the program code stored in the storage medium by a computer (or a CPU or MPU) of the system or apparatus.
In this case, the program code itself read out from the storage medium implements the functions of the above-mentioned embodiments, and the storage medium which stores the program code constitutes the present invention.
As the storage medium for supplying the program code, for example, a floppy® disk, hard disk, optical disk, magneto-optical disk, CD-ROM, CD-R, magnetic tape, nonvolatile memory card, ROM, and the like may be used.
The functions of the above-mentioned embodiments may be implemented not only by executing the readout program code by the computer but also by some or all of actual processing operations executed by an OS (operating system) running on the computer on the basis of an instruction of the program code.
Furthermore, the functions of the above-mentioned embodiments may be implemented by some or all of actual processing operations executed by a CPU or the like arranged in a function extension board or a function extension unit, which is inserted in or connected to the computer, after the program code read out from the storage medium is written in a memory of the extension board or unit.
The present invention is not limited to the above embodiments and various changes and modifications can be made within the spirit and scope of the present invention. Therefore to apprise the public of the scope of the present invention, the following claims are made. | An information processing apparatus for inputting a pronunciation symbol corresponding to an English notation includes pronunciation symbol information holding means for holding pronunciation symbol information indicating a relationship between a predetermined alphabet and a pronunciation symbol that starts from the predetermined alphabet, pronunciation symbol statistical information holding means for holding statistical information associated with the probability of occurrence of each pronunciation symbol immediately after a predetermined pronunciation symbol, display means for extracting pronunciation symbols corresponding to an input alphabet from the pronunciation symbol information, and displaying the extracted pronunciation symbols while sorting them on the basis of the statistical information, and determination means for determining a pronunciation symbol corresponding to the English notation from the displayed pronunciation symbols. | 6 |
TECHNICAL FIELD
[0001] The present invention relates to a magnetometer that measures a strength of a magnetic field. Specifically, the present invention relates to a gradiometer and a magnetic sensing method, which use an optically pumped magnetometer.
BACKGROUND ART
[0002] In many cases, for measuring a weak magnetic field, a magnetic gradiometer (hereinafter also simply referred to as “gradiometer”) is formed using measurement data obtained by magnetometers for two or more magnetic field measurement regions. As an example of such gradiometer, a gradiometer using an optically pumped magnetometer is known. An optically pumped magnetometer applies a pump beam to a magnetic field measurement region with a group of gaseous atoms encapsulated therein to cause spin polarization and obtain a rotation of a polarization plane occurring when a probe beam for reading is made to pass through the region, as a signal according to a magnetic flux density of the region. Use of optically pumped magnetometers to obtain a difference between signals obtained in two respective magnetic field measurement regions when a probe beam has sequentially passed through the magnetic field measurement regions enables formation of a gradiometer. As an example of a high-sensitivity optically pumped magnetometer that can be used to form a gradiometer, U.S. Pat. No. 7,038,450 proposes an atomic magnetic sensor using a circularly-polarized beam as a pump beam and a linearly-polarized beam of light as a probe beam, for a cell in which alkali metal vapor is present.
[0003] However, for such gradiometer using optically pumped magnetometers, there have been no discussions ever before on an optimum geometric arrangement of a signal source and two magnetic field measurement regions and an optimum direction of a magnetic field to which the magnetometers respond in the two magnetic field measurement regions.
CITATION LIST
Patent Literature
[0004] PTL 1: U.S. Pat. No. 7,038,450
SUMMARY OF INVENTION
[0005] The present invention is directed to a gradiometer enabling higher sensitivity measurement of a magnetic field and S/N ratio improvement, which has been obtained as a result of studies on effects of an geometric arrangement of a signal source and two magnetic field measurement regions and a direction of a magnetic field to which the magnetometer respond in the two magnetic field measurement regions imposed on a gradiometer.
[0006] In a gradiometer using an optically pumped magnetometer according to the present invention, the gradiometer using the optically pumped magnetometer includes: a cell containing a group of atoms in a gaseous state, including an alkali metal, encapsulated therein; a pump beam source that applies a first pump beam and a second pump beam to the cell to spin-polarize the group of atoms, the first pump beam and the second pump beam being parallel to each other; a probe beam source that applies a probe beam to the cell; a detector for detecting a rotation of a polarization plane of the probe beam that has passed through the cell in a state in which the group of atoms is spin-polarized, wherein the first pump beam and the probe beam cross each other at a first measurement position, the second pump beam and the probe beam crosses each other at a second measurement position, the first measurement position and the second measurement position are arranged along a first direction that is linear with respect to a signal source, and the probe beam sequentially passes through the first measurement region and the second measurement region; wherein an alkali metal density, a measurement position length, a pump beam intensity and a spin polarization ratio for the first measurement position are the same as those of the second measurement position; and wherein each of a direction of a magnetic field measured at the first measurement position and a direction of a magnetic field measured at the second measurement position is the same as the first direction, a sign of spin polarization caused by optical pumping is different between the first measurement region and the second measurement region; and an angle of rotation of the polarization plane of the probe beam that has sequentially passed through each of the first measurement position and the second measurement position is obtained, thereby obtaining a difference in magnetic flux density between the first measurement position and the second measurement position.
[0007] According to the present invention, a gradiometer enabling high sensitivity measurement of a magnetic field from a magnetic moment, which is a signal source, and S/N ratio improvement can be formed.
[0008] Further features of the present invention will become apparent from the following description of exemplary embodiments with reference to the attached drawings.
BRIEF DESCRIPTION OF DRAWINGS
[0009] FIG. 1 is a schematic diagram illustrating a gradiometer according to a first example of the present invention.
[0010] FIGS. 2A and 2B are schematic diagrams illustrating a mirror used in a variation of the first example of the present invention.
[0011] FIGS. 3A and 3B are schematic diagrams illustrating a total reflection prism used in a variation of the first example of the present invention.
[0012] FIG. 4 is a schematic diagram illustrating a gradiometer according to a second example of the present invention.
[0013] FIG. 5 is a schematic diagram illustrating a gradiometer according to a variation of the second example of the present invention.
[0014] FIG. 6 is a schematic diagram illustrating a gradiometer according to a third example of the present invention.
DESCRIPTION OF EMBODIMENTS
[0015] An exemplary mode for carrying out the present invention will be described below based on an embodiment.
Gradiometer
[0016] First, a relationship between a configuration of a gradiometer and strengths of a signal and noise obtained by such configuration will be discussed. Considering a magnetic field produced by a magnetic moment m S , a magnetic flux density vector B(d) at a position away from the magnetic moment m S , which is an attentioned magnetic signal source, by a distance vector d can be expressed by
[0000]
B
(
d
)
=
μ
0
4
π
[
3
n
(
n
·
m
S
)
-
m
S
d
3
]
(
1
)
[0000] wherein μ 0 is a vacuum magnetic permeability, a vector n is a unit vector pointing to a direction of the vector d. Based on expression (1), where the direction of the magnetic moment m S points to a direction from the signal source toward the magnetometer (direction of the vector n), a magnitude of the magnetic flux density vector at the position of the magnetometer can be expressed by
[0000] | B ( d )|=μ 0 ×|m S |/(2 ×d 3 ×π) (2).
[0000] This is also a maximum value of the magnetic flux density that can be detected by the magnetometer under the condition that the absolute value of d, i.e., |d|, is constant.
[0017] Then, another magnetometer is arranged to form a gradiometer of a simple model in which the two magnetometers are arranged on a straight line and the direction of the magnetic moment m S points to a direction from the signal source toward the two magnetometers. Where distances to two magnetometers are d 1 and d 2 (d 1 <d 2 ), if a signal measured at the position of the distance d 2 is subtracted from a signal measured at the position of the distance d 1 , a resulting signal S can be expressed by
[0000] S=μ 0 ×|m S |/(2×π)×( d 1 −3 −d 2 −3 )=μ 0 ×|m S |/(2 ×d 1 3 ×π)×[1−( d 1 /d 2 ) 3 ] (3).
[0000] For example, where d 2 =2×d 1 , it can be understood from expression (3) that the decrease of the signal remains at approximately ⅛. In other words, with this model, a strength of a magnetic signal from the vicinity of the sensor is substantially maintained.
[0018] Meanwhile, magnetic field noise from a position that is very farther than the attentioned signal source can also be considered as a magnetic field created by another magnetic moment m N . Where distances from the magnetic moment m N , which is a noise source, to the two magnetometers are R 1 and R 2 , a noise component N from the noise source can be obtained by a signal measured at the position of the distance R 2 is subtracted from a signal measured at the position of the distance R 1 , and can be expressed by
[0000] N=μ 0 ×|m N |/(2 ×R 1 3 ×π)×[1−( R 1 /R 2 ) 3 ] (4.
[0019] Since R 1 ≈R 2 in the case of a distant noise source, it can be understood that in this model, noise described by a distantly-arranged magnetic moment can substantially be reduced.
[0020] As described above, a configuration in which two magnetic field measurement regions are arranged to be linear with respect to a signal source and a direction of a magnetic moment m S points to a direction from the signal source toward the two magnetic field measurement regions enables reduction of noise from a distance position while maintaining the strength of a magnetic signal from the vicinity of the sensor.
Optically Pumped Magnetometer
[0021] Next, an optically pumped magnetometer used in a gradiometer according to the present invention for magnetic signal detection will be discussed.
[0022] A. Principle of Operation of an Optically Pumped Magnetometer
[0023] First, operation of an optically pumped magnetometer will be described according to three steps below.
[0024] 1) A pump beam is applied to an alkali metal gas encapsulated in a cell to orient spin of electrons in the atoms, thereby producing spin polarization. For the pump beam, a beam with a wavelength causing an optical transition from a ground level to an excited level, such as D1 transition of an alkali metal, is used. Where a circularly-polarized beam is used for the pump beam, the circularly-polarized beam is absorbed by the electrons in a particular spin state, providing an optical pumping effect, enabling provision of spin polarization for the alkali metal.
[0025] The spin polarization can be provided by circularly-polarized beam used as a pump beam because of conservation of angular momentum. A photon of circularly-polarized light has an angular momentum, and only a pair of a ground level and an excited level that can receive the angular momentum from the photon can be excited. For example, right-hand circularly-polarized light is selectively absorbed by a pair of a ground level and an excited level that increases an angular momentum of each electron by a quantum number of 1. The once excited atoms return to the ground state after emitting randomly-polarized light by means of spontaneous emission, or through, e.g., collision with quencher gas atoms. In this state, atoms with their angular momentums decreased by a quantum number of 1 and atoms returning to the ground state with their angular momentums conserved are mixed. Hence, repetition of a random excitation and relaxation process increases the ratio of atoms in which the ground state are not excited by the circularly-polarized light. As a result, the direction of the spin of atoms included in the group of atoms are oriented in the direction of travel of the circularly-polarized light as an axis of the quantization. In order to enhance the density of the alkali metal gas in the cell, the cell may be heated to a maximum of around 200° C.
[0026] 2) Spin polarization of the alkali metal rotates upon reception of a torque in a magnetic field. It is known that use of optical Bloch equation (5) including effects of pumping and relaxation of optically-pumped spin enables description of the behavior of a spin polarization vector P in a magnetic field
[0000]
P
t
=
γ
e
Q
B
×
P
-
Γ
eff
P
+
R
(
5
)
[0000] wherein γ e is a gyromagnetic ratio of an electron, Q is a slowdown factor depending on a spin polarization ratio, Γ eff is a spin relaxation rate, B is a magnetic field vector and R is a pumping vector.
[0027] 3) Information on the spin polarization in the magnetic field is read by means of a probe beam which is a linearly-polarized beam. Where spin polarization has a component in the direction of propagation of the probe beam, the magnitude of the spin polarization can be read as a rotation of a polarization plane caused by a magnetooptic effect. For the probe beam, also, a beam with a wavelength around a resonant wavelength of the alkali metal is used. Thus, the wavelength is made to be detuned from a center of the resonance, thereby reducing effects of the probe beam on the optical absorption and the spin polarization.
[0028] The probe beam, which is a linearly-polarized beam, can be described as superimposition of both a left-hand circularly-polarized beam and a right-hand circularly-polarized beam. As also mentioned in the description of the pump beam, a circularly-polarized beam of light is absorbed by electrons in a particular spin state, and thus, if polarization occurs in the atom group, a difference in absorption occurs between the left-hand circularly-polarized beam and the right-hand circularly-polarized beam depending on the polarization. A difference in absorption coefficient means an imaginary part of a complex refractive index, and thus, a difference occurs between the real parts of the refractive indexes sensed by the left-hand circularly-polarized beam and the right-hand circularly-polarized beam according to the Kramers-Kronig relation. Therefore, use of a linearly-polarized beam obtained by superimposition of both a left-hand circularly-polarized beam and a right-hand circularly-polarized beam causes a difference in length between the optical paths of the left-hand circularly-polarized beam and the right-hand circularly-polarized beam when the linearly-polarized beam passing through the atom group, and thus, a rotation of the polarization plane is observed.
[0029] Since the angle of such rotation depends on the magnitude of the magnetic field, measurement of the angle of rotation of the polarization plane enables detection of the magnitude of the magnetic field.
[0030] Next, a relationship between a direction of a magnetic field measured by a magnetometer and a strength of an obtained signal will be described for two operating modes of an optically pumped magnetometer: a zero-magnetic field magnetometer and a resonant operation of a magnetometer.
[0031] B. Zero-Magnetic Field Magnetometer
[0032] In a state of a zero-magnetic field magnetometer, a magnetic field of a magnetic field measurement region in which an alkali metal gas, to which a pump beam and a probe beam are applied, is placed so as to adjust a strength to be no more than about 1 nT (nanotesla). The gyromagnetic ratio of an alkali metal is, e.g., 7 GHz/T for K, 4.6 GHz/T for 85 Rb, 7 GHz/T for 87 Rb and 3.5 GHz/T for Cs. In any case, for a magnetic field of no more than 1 nT, an optically pumped magnetometer acts as a zero-magnetic field magnetometer with a Larmor frequency of no more than 10 Hz. In this condition, in solving optical Bloch equation (5), the behavior of spin polarization can well be descried according to a stationary solution that temporal change of the spin polarization is zero.
[0033] In the zero-magnetic field magnetometer, spin polarization in proportion to a magnetic field of a component orthogonal to the pump beam and the probe beam is induced in the direction of the probe beam. In other words, the magnetometer has substantive sensitivity to a magnetic field in the direction orthogonal to both the pump beam and the probe beam.
[0034] When measuring a biometric magnetic field resulting from activities of a brain and/or a heart, a direction of a magnetic moment m S is not a parameter that a measurement system can select. Nevertheless, in order to confirm the fact that the strength of an obtained signal varies depending on the direction of a magnetic field measured by the magnetometer, the magnitude of the magnetic flux density is figured out based on expression (1) for two cases below.
[0035] (i) A case where the magnetic moment m S points to the direction of the vector n
[0036] Since an n-direction component of a magnetic field is measured, a signal whose magnetic flux density has a magnitude of
[0000] μ 0 ×2|m S |/(4π×d 1 3 ) is measured.
[0037] (ii) A case where the magnetic moment m S points to a direction orthogonal to the vector n
[0038] Since a component parallel to the magnetic moment m S is measured, a signal whose magnetic flux density has a magnitude of
[0000] −μ 0 ×|m S |/(4π×d 1 3 ) is measured.
[0039] As can be seen from the above discussion, a larger signal can be observed in the case where the magnetic moment m S points to the direction of the vector n (case 1).
[0040] C. Resonant Operation of a Magnetometer
[0041] Also, a bias magnetic field of no less than 1 nT can be applied in the pump beam direction to make a magnetometer to perform a resonant operation. In this case, spin polarization resulting from optical pumping precesses at a Larmor frequency determined by the magnitude of the bias magnetic field with the direction of the bias magnetic field as a rotation axis. Motion of spin polarization with this magnetometer is described by means of, in particular, a stationary solution oscillating at a Larmor procession frequency from among the optical Bloch equation solutions.
[0042] This stationary solution is coupled with a magnetic field oscillating at a Larmor procession frequency, resulting in change in the direction of the spin polarization. From analysis of the optical Bloch equations, it is known that where a magnetometer performs a resonant operation, the magnetometer performs the resonant operation at a Larmor procession frequency for not only a magnetic field in the direction orthogonal to both the pump beam and the probe beam, but also a magnetic field in the probe direction.
[0043] A magnetic resonant signal is measured using such magnetometer. A state in which a magnetic moment m S , which is a signal source, rotates by means of magnetic resonance at an angular frequency ω will be considered. For measurement of a magnetic field as a magnetic resonant signal at a position a distance d 1 away, the bias magnetic field in the magnetometer is adjusted to make the resonant frequency correspond to a rotation frequency of the magnetic moment within a resonance width. In this case, the magnitude of the detected signal varies depending on the combination of the direction of the axis of rotation of the magnetic moment m S and the direction of the magnetic field measured by the magnetometer. Based on expression (1), the magnitude of a signal for magnetic flux density observed in each case will be figured out.
[0044] When considering a signal resulting from rotational motion of a magnetic moment, attention may be paid only on a time-variable component of the magnetic moment, that is, a magnitude orthogonal to the axis of the rotation. In the below description, the magnetic moment m S is described as one pointing to a direction orthogonal to the axis of the rotation. Furthermore, the wavelength of an electromagnetic wave at a resonant frequency is sufficiently longer than an attentioned scale, and thus, can be handled with quasi-static approximation. Furthermore, φ represents the phase of oscillation.
[0045] 1) A case where the axis of rotation in the magnetic resonance points to a direction pointing to the signal source viewed from the magnetometer
[0046] 1-A: Magnetic flux density in the direction pointing to the signal source viewed from the magnetometer
[0047] This direction is that of the axis of rotation, and thus, a magnetic flux density in this direction does not vary.
[0048] 1-B: Magnetic flux density in the direction orthogonal to the axis of rotation
[0049] Since the term of the inner product of the vector, n·m S , is zero in expression (1), a signal expressed by
[0000] B ( t )=[μ 0 ×m S /(4 π×d 1 3 )]× e (−iωt+φ) (6)
[0000] can be obtained.
[0050] 2) A case where the axis of rotation in the magnetic resonance is orthogonal to the direction pointing to the signal source viewed from the magnetometer
[0051] 2-A: Magnetic flux density in the direction pointing to the signal source viewed from the magnetometer (vector n direction)
[0052] Since the vector n(n·m S ) is observed for the second term within the square bracket in expression (1), a signal expressed by
[0000] B ( t )=[μ 0 ×2 m S /(4 π×d 1 3 )]× e (−iωt+φ) (7)
[0000] is measured.
[0053] 2-B: Magnetic flux density in the direction parallel to the axis of rotation
Since contribution from 3n(n·m S ) in the first term in the square bracket in expression (1) is zero, a signal expressed by
[0000] B ( t )=[μ 0 ×m S /(4 π×d 1 3 )]× e (−iωt++φ) (8)
[0000] can be obtained according to the rotation of the vector m S .
[0055] It can be understood from the above description that in observation of a magnetic resonant signal, where a magnetic field in the vector n direction is measured with an arrangement in which the axis of rotation in the magnetic resonance (direction of the pump beam) is orthogonal to the direction pointing to the signal source (vector n direction) viewed from the magnetometer (2-A), a signal with a magnitude twice those of the other cases can be observed.
[0056] In an optical gradiometer, also, provision of an arrangement in which the respective optically pumped magnetometers operate as described above according to each of a zero-magnetic field magnetometer and a resonant operation of a magnetometer enables extraction of a large signal, whereby higher sensitivity measurement can be made.
[0057] According to the knowledge described above, the present invention relates to a magnetometer using optically pumped magnetometers forming a configuration in which two magnetic field measurement regions are arranged so as to be linear with respect to a signal source, and a direction of a magnetic moment m S points a direction from the signal source to the two magnetic field measurement regions (vector n direction).
[0058] Furthermore, in the zero-magnetic field magnetometer, a magnetic force can be measured for a magnetic field in a direction orthogonal to both a pump beam and a probe beam.
[0059] Furthermore, in a resonant operation of the magnetometer, a magnetic force may be measured for not only a magnetic field in the direction orthogonal to both the pump beam and the probe beam but also a magnetic field in the probe direction.
[0060] Specific examples of a gradiometer according to the present invention, which has a configuration such as described above, will be indicated below. However, the present invention is not limited to the below examples.
Example 1
[0061] In FIG. 1 , laser beams 1 and 2 for pumping, which are circularly-polarized beams, are generated from non-illustrated pump beam sources. The laser beams 1 and 2 propagate in parallel to each other in a positive y axis direction. Both are circularly-polarized beams in a same direction. A laser beam 3 for probe is generated from a non-illustrated probe beam source, a cell 8 contains alkali metal encapsulated therein. Polarizing plates 4 and 5 form a crossed nicol arrangement that does not transmit light when no polarization plane rotation occurs in the glass cell. A photodetector 7 receives the probe beam. Mirrors 9 and 10 turn the pump beam back. It is desirable that the mirrors have a high reflectivity for an incident angle of 45 degrees and are dielectric multilayer mirrors designed to reduce the difference in complex reflectivity between p wave and s wave. A faraday modulator 6 is driven by a modulation signal with a frequency ω F from a non-illustrated signal source to modulate a polarization plane of the probe beam, which is a linearly-polarized beam, with an angle α and the frequency ω F . Where φ is the angle of rotation of the polarization plane caused by a magnetic field in the cell, an intensity I of the light passing through a pair of a polarizer and an analyzer in a crossed nicol arrangement can be expressed by
[0000]
I
=
I
0
sin
2
[
φ
+
α
sin
(
ω
F
t
)
]
≈
I
0
[
φ
2
+
2
φ
α
sin
(
ω
F
t
)
+
α
2
sin
2
(
ω
F
t
)
]
(
9
)
[0000] In other words, a frequency ω F component of the intensity of the light has an amount proportional to 2I 0 αω and the angle of rotation of the polarization plane.
[0062] An optical path of the laser beam for probe has a route starting from a lower left portion of the Figure and extending through a route from the polarizing plate 4 , the faraday modulator 6 , the cell 8 , the mirror 9 , the mirror 10 , the cell 8 , the polarizing plate 5 and the photodetector 7 in this order. Along this route, a region in which the first pump beam 1 and the probe beam 3 cross each other is a first measurement position, and a region in which the probe beam turned back by the mirrors 9 and 10 crosses the second pump beam 2 is a second measurement position. This configuration provides a configuration in which the first measurement position and the second measurement position are arranged along a direction linear with respect to a signal source (first direction). Here, the polarization plane of the probe beam rotates according to the value of B z1 , which is a z component of a magnetic flux density in the first measurement position, and the value of B z2 , which a z component of magnetic flux density in the second measurement position.
[0063] The cell 8 consists of a material transparent to the probe beam and the pump beams, such as glass. The cell contains K in a gaseous state, which is hermetically encapsulated. In the cell, a gas functioning as a buffer, such as He, and/or an N 2 gas can also be encapsulated in addition to the atom group. Since a buffer gas suppress diffusion of polarized alkali metal atoms, it is effective to suppress spin relaxation occurring due to collision with the cell walls, thereby enhancing the polarization ratio. Furthermore, an N 2 gas is a quencher gas that draws energy from K in an excited state to suppress light emission of K, and is effective for producing large spin polarization in the alkali metal gas by means of pumping.
[0064] A potassium metal is placed in a glass cell and heated to around 180° C., enabling the glass cell to be filled with potassium metal vapor with a number density of around 10 14 cm −3 . Here, the cell is placed in a non-illustrated oven for heating, and heated to a desired temperature by hot air circulating in the oven.
[0065] Furthermore, in the present example, a non-illustrated magnetic shield and a three-axis Helmholtz coil system are used to decrease geomagnetism and an environmental magnetic field around the cell 8 to no more than 1 nT.
[0066] In the first measurement position, y-direction spin polarization is produced by the first pump beam 1 , which is a circularly-polarized beam σ + . Where a z-direction magnetic field B z1 is positive, positive spin polarization occurs in the x direction. Here, since the probe beam 2 , which is a linearly-polarized beam, passing through the first measurement position, travels in the same direction as that of the spin polarization produced by the pump beam, and thus, the polarization plane makes right-hand rotation according to the magnitude of the spin polarization.
[0067] The optical path of the probe beam is turned back by the mirrors 9 and 10 to the cell 8 again. Similarly, in the second measurement position, y-direction spin polarization is produced by the second pump beam 2 , which is also a circularly-polarized beam σ + , and where a z-direction magnetic field B z2 is positive, positive spin polarization occurs in the x direction, too. Here, as opposed to the first measurement position, the probe beam 2 propagates in a direction opposite to the direction of the spin polarization, and thus, the polarization plane makes left-hand rotation according to the magnitude of the spin polarization.
[0068] Where a rotation angle φ of the polarization plane is represented by a mathematical expression, it can be expressed by
[0000] φ= cr e fnlP x Re[L (ν)] (10)
[0069] Here, ν is the frequency of the probe beam, n is an atomic density of an alkali metal, c is a speed of the light, and r e (=2.82×10 −15 m) is a classical electron radius. Furthermore, f is an oscillator strength of optical transition, l is a length of a measurement position, P x is a magnitude of the x-direction spin polarization (up to 1), L(ν) is a complex Lorenz function of a center wavelength ν 0 and a full width at half maximum Δν representing a shape of an absorption line. Here, when the probe beam is made to propagate in the opposite direction in the measurement position 2 , it should be noted that a negative sign is added further to expression (10).
[0070] A specific magnitude of the x-direction spin polarization P x can be figured out from optical Bloch equation (5). Considering a pumping vector R=(0, R, 0), which is y-direction pumping,
[0000]
P
x
=
R
(
γ
e
B
z
/
Q
)
Γ
eff
2
+
(
γ
e
B
z
/
Q
)
2
(
11
)
[0000] can be obtained as a stationary solution. Based on expression (11), it can be understood that if B z is so small that Γ eff >γ e B z /Q can be provided, a P x which is substantially proportional to B z can be obtained. Combining expressions (10) and (11), it is also clear that the rotation angle φ of the polarization plane is proportional to B x . If this relationship is represented by φ=αB z , the rotation angle of the polarization plane of the probe beam that has sequentially passed through the first measurement position and the second measurement position can be expressed by
[0000] φ=α A1 B z1 −α A2 B z2 =α( B z1 −B z2 ) (12),
[0000] and thus, the rotation angle of the polarization plane of the probe beam incident on the photodetector is an amount resulting from magnetic field subtraction as a gradiometer. The latter equal sign in expression (12) is provided where proportionality coefficients α A1 and α A2 of the rotation angles relative to the magnetic fields at the respective measurement positions are substantially equal to each other. Referring to expressions (10) and (11), it can be understood that examples of parameters to be uniformed to make α A1 and α A2 to be equal to each other include, e.g., the alkali metal density n, the length of the measurement position l the pumping vector R (the intensity of the pump beam), the spin polarization ratio (absolute value of the spin polarization vector P), and a slowdown factor Q, which will be determined later.
[0071] Under the condition that photon shot noise restricts the sensitivity, the gradiometer configured as described above provides signal/noise ratio improvement twice the gradiometer in which probe beams are made to pass through two independent measurement positions, respectively, to detect rotations of the respective polarization planes by means of photodetectors (comparison example). The principle will be described below.
[0072] Here, P 0 is the number of photons provided to each of the gradiometers according to comparative example and the present example per unit time. In comparative example, the photons to be provided are divided in half and used, and thus, the signal in each photodetector is proportional to P 0 /2. Furthermore, shot noise in each photodetector is proporational to (P 0 /2) 1/2 . For the signal, subtraction of the signals from each other results in obtainment of the strength proportional to P 0 /2. Meanwhile, even though “subtraction” is performed, random ones are added up for the noise, resulting in (P 0 /2+P 0 /2) 1/2 =P 0 1/2 . Accordingly, the S/N ratio in comparative example is proportional to an amount expressed by
[0000] P 0 1/2 /2 (13).
[0073] Meanwhile, in the present example, the signal in the photodetector is proportional to P 0 , and the shot noise in the photodetector is proportional to P 0 1/2 . Therefore, the S/N ratio is proportional to
[0000] P 0 1/2 ( 14 ).
[0074] Comparing expressions (13) and (14), it can be understood that the present example enables provision of a doubled S/N ratio in measurement using a same number of photons.
[0075] A magnetic moment, which is a signal source, is arranged in a negative direction on a z-axis in the Figure. As already described above, measurement of a z component of a magnetic field in each of the first measurement region and the second measurement region arranged to be linear with respect to the signal source results in measurement of relatively large magnetic signals, enabling provision of high sensitivity.
[0076] For the turns of the optical path via the mirrors 9 and 10 , it is desirable to employ a mirror configuration that reduces its effects on the polarization plane of the probe beam.
[0077] Fresnel reflection via a mirror exhibits different reflectivities for p-wave and s-wave. Here, a p-wave is a polarized wave of light whose electric field vector is present on an incident plane, and an s-wave is a polarized wave of light whose electric field vector is orthogonal to an incident plane. Use of dielectric multilayer mirrors enables suppression of the difference in reflectivity between p-wave and s-wave to no more than 1%, which is desirable as a method for turning an optical path; however, this case also requires the reflection phases to be taken into consideration.
[0078] For optical path turning in a gradiometer such as that in the present example, two examples of an optical configuration avoiding the effects of Fresnel reflectivity's dependency on the polarization plane are indicated below.
[0079] 1) There are known dielectric multilayer mirrors with a configuration exhibiting a high reflectivity for both p-wave and s-wave with a 45-degree incidence. In such high reflectivity mirrors, phases of reflection are not uniform but diffused depending on the wavelengths. Therefore, in order to enable precise measurement of the polarization plane, an optical system that turns an optical path through a reflection route including a plurality of reflective planes, such as illustrated in FIGS. 2A and 2B , is used. In this optical system, on a plane including an optical path for light to enter the optical system and an optical path for light to exit from the optical system, there are two reflections whose angle of incident on a mirror is 45 degree. Furthermore, on a plane perpendicular to the optical path for light to enter the optical system and the optical path for light to exit from the optical system, there are two reflections whose angle of incidence on respective mirrors is 45 degrees. As a result, in the reflection route of light with an e y polarized wave, the reflections occur for the p-wave, the s-wave, the s-wave and the p-wave in this order, while in the reflection route of light with an e z polarized wave, the reflections occurs for the s-wave, the p-wave, the p-wave and the s-wave in this order.
[0080] FIG. 2A is a perspective view of the mirrors, and FIG. 2B illustrates three planes of the mirrors using trigonometry. Consequently, a phase shift amount resulting from the reflections in the entire optical path turn is the same regardless of the p-wave incidence or the s-wave incidence, enable elimination of the effect of the optical path turn on measurement of the polarization plane.
[0081] 2) As a unit for substituting the reflections via the mirrors 9 and 10 , it is possible to turn the optical path by means of total reflection using a prism. In total reflection, there is a difference in phase shift amount due to reflection between p-waves and s-waves, hindering precise measurement of a rotation of the polarization plane. Therefore, use of a prism such as illustrated in FIGS. 3A and 3B enables provision of an optical system with an optical path turn in which in a route of the optical path turn, there are a sum of four total reflections, i.e., two total reflections for incidence of a p wave and two total reflections for incidence of a s wave. In other words, in the total reflection route of light with the e y polarized wave, the reflections occur for the p wave, the s wave, the s wave and the p wave in this order, while in the total reflection route for light with the e z polarized wave, reflections occur for the s-wave, the p-wave, the p-wave and the s-wave in this order.
[0082] FIG. 3A is a perspective view of the prism, and FIG. 3B illustrates three planes of the prism using trigonometry.
[0083] Although an example has been provided focusing on an operation of a zero-magnetic field magnetometer here, a resonant operation can be performed using the same configuration.
[0084] The resonant operation can be performed by adjusting a current flowing in the non-illustrated Helmholtz coil system to apply a bias magnetic field in the pump beam direction, thereby making the spinning of the alkali metal to precess at a frequency ω. The arrangement according to this example is particularly favorable for measurement of an oscillating magnetic field in the B z direction by resonant operation.
Example 2
[0085] FIG. 4 illustrates another configuration of a gradiometer using magnetometers using a resonant operation. The second example is different from the first example in that no optical turn using mirrors is provided on an optical path of probe beam.
[0086] The second example is characterized in an arrangement in which a first pump beam 1 and a second pump beam 2 , which correspond to two measurement regions, respectively, are circularly-polarized beams that rotate along a same direction but are incident on the cell 8 in directions opposite to each other, which is the difference from that of the first example. The circularly-polarized beams may have either right-hand rotation or left-hand rotation as long as the circularly-polarized beams rotate along the same direction. Furthermore, in the present example, there is a system that detects a rotation of a polarization plane by means of a balance photodetector including a polarization separation optical element 11 and photodetectors 12 and 13 .
[0087] A first measurement region is a region in which a probe beam 3 made to be a linearly-polarized beam by a polarizer 4 cross the first pump beam 1 , which is the circularly-polarized beam with right-handed rotation and is arranged inside a cell 8 . Here, a DC current is made to flow in a non-illustrated Helmholtz coil pair to apply a magnetostatic field to the entire cell in an x-direction. A magnetostaic field of around 0.7 μT is applied so that spin polarization of potassium excited in the cell precesses at a Larmor frequency of 5 kHz. The first pump beam 1 produces spin polarization in the x direction, and this spin polarization resonates with oscillating magnetic field components of around 5 kHz while preccessing at 5 kHz. Here, the magnetometer has sensitivity to, in particular, y-direction and z-direction magnetic fields. Consequently, according to B y and B z magnetic fields oscillating at the resonant frequency, a z-component of the spin polarization oscillating at that frequency occurs, and thus, an angle of rotation of the polarization plane of the probe beam passing through the first measurement region is one periodically modulated at a resonant frequency of 5 kHz.
[0088] Similarly, in the second measurement region in which the second pump beam 2 , which is a circularly-polarized beam with right-hand rotation, and the probe beam 3 cross each other in the cell 8 , spin polarization is produced by the pump beam, an x-component of the spin polarization is one having a sign that is the reverse of that of the spin polarization in the first measurement region. A bias magnetic field, which has already been described, is applied also to the second measurement region, and the spin polarizations have precession motion in a same direction (without depending on the signs of the respective polarizations). Furthermore, as with the resonance in the first measurement region, a z-direction component is generated in the spin polarization as a result of resonance with an oscillating magnetic field. Under the condition that resonant magnetic fields of a completely same magnitude and direction are measured in the first measurement region and the second measurement region (this is an assumed condition for description), the z-direction spin polarization has a sign opposite to that of the first measurement region, reflecting the reverse sign of the x-direction spin polarization. Therefore, an angle of rotation of the polarization plane of the probe beam passing through the second measurement region is one further periodically modulated at a resonant frequency of 5 kHz, contribution of the polarization plane rotation in the second region is one with a sign opposite to that of contribution in the first region.
[0089] Thus, it can be understood that the angle of rotation of the polarization plane of the probe beam sequentially passed through the first measurement position and the second measurement position can be expressed by
φ=α A1 B z1 −α A1 B z2 =α A1 ( B z1 −B z2 ),
[0090] which enables formation of a magnetic field gradiometer.
[0091] A direction of a polarizer 4 determining the polarization plane of the probe beam is adjusted so that when the angle of rotation of the polarization plane in the cell 8 is 0, an amount of reflected light and an amount of transmitted light in the polarized beam splitter 11 are equal to each other. In other words, an arrangement is made so that a polarizing axis of the polarized beam splitter 11 and a polarization plane of light passing through the polarizer 4 form an angle of 45 degrees. Obtainment of a difference between optical power received by the photodetector 12 and optical power received by the photodetector 13 enables extraction of an electric signal according to the angle of rotation of the polarization plane.
[0092] For a layout for obtaining a magnetic resonant signal, a magnetic moment, which is a signal source rotating by means of magnetic resonance, is arranged at a negative position on the z axis in the Figure. As already described, measurement of a z-component of a magnetic field in each of the first and second measurement regions arranged to be linear with respect to the signal source results in measurement of relatively large magnetic signals, enabling provision of high sensitivity. In such arrangement, in order to prevent the distance between the first measurement region and the signal source from being large, it is effective to bend an optical path of the probe beam entering the polarizer 4 in the Figure, using an optical path changing unit such as a non-illustrated mirror or a prism.
[0093] For magnetic field measurement using a resonant operation, not only rotation of a magnetic moment, which is a signal source, and rotation of spin polarization to have frequencies corresponding to each other or falling within a range of a resonance width, but also the rotation directions to be correspond to each other, is required. Therefore, it is necessary that a direction of the bias magnetic field B z applied to the cell 8 correspond to a direction of a x-component of a magnetostatic field B 0 in which the signal source is placed for generating magnetic resonance in the signal source. Furthermore, a magnitude of the magnetic field should be selected according to a gyromagnetic ratio of a nuclide used for the magnetic resonance.
[0094] In order to achieve a state in which signs of spin polarization generated in the first measurement region and in the second measurement region as a result of optical pumping are different from each other, another configuration can also be employed. In a variation of the present example, which is illustrated in FIG. 5 , a first pump beam 1 and a second pump beam 2 corresponding to two measurement regions are circularly-polarized beams propagating in a same direction, but directions of rotations of the circularly-polarized beams are different from each other, causing spin polarization to be generated in the first measurement region and the second measurement region in directions opposite to each other.
[0095] Operation of the magnetometer using a resonant operation is similar to that of the present example described, and thus, description thereof will be omitted.
Example 3
[0096] Another example in which rotations of a polarization plane of a probe beam by a magnetic field, which are measured in a first measurement region and a second measurement region, have directions opposite to each other will be described with reference to FIG. 6 . In FIG. 6 , a half-wave plate 14 is inserted between the first measurement region and the second measurement region along an optical path of the probe beam. A crystal axis direction of the half-wave plate 14 is made to correspond to a direction of a polarization plane of light passing through a polarizer 4 . Where φ is a rotation of the polarization plane in the first measurement region, an angle of rotation of the polarization plane of the probe beam passing through the half-wave plate 14 is −φ. This is because change of a polarization state when the probe beam passing through the half-wave plate arranged as described above can be expressed by the following matrix where a set of electric field vectors (e x , e y ) T is a base thereof.
[0000]
exp
(
ϕ
)
(
1
0
0
-
1
)
[0097] Although FIG. 6 illustrates that a cell 8 a and a cell 8 b are independent cells, it is necessary to make a first measurement position and a second measurement position correspond to each other in terms of, e.g., alkali metal density n, measurement position length l pumping vector R, spin polarization ratio and slowdown factor Q which will be determined later as in example 1. Thus, a configuration in which these cells are interconnected via a non-illustrated path may be employed. The interconnection of the cells as described above is effective to provide a common alkali metal density in the two measurement regions to make the two measurement regions in the gradiometer have equal parameters.
[0098] Although the polarization plane of the probe beam subsequently passing through the second measurement region further rotates, contribution of the polarization plane rotation in the second region has a sign opposite to that of contribution in the first region.
[0099] Furthermore, in the present example, as in the second example, a resonant operation of a magnetometer is performed on a y-direction bias magnetic field, providing sensitivity to B z , enabling a gradiometer that measures a large signal from a magnetic moment. While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. The scope of the following claims is to be accorded the broadest interpretation so as to encompass all such modifications and equivalent structures and functions.
[0100] While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. The scope of the following claims is to be accorded the broadest interpretation so as to encompass all such modifications and equivalent structures and functions.
[0101] This application claims the benefit of Japanese Patent Application No. 2010-181414, filed Aug. 13, 2010, which is hereby incorporated by reference herein in its entirety. | A gradiometer in which a probe beam for reading sequentially passes through two magnetic field measurement regions to obtain signals according to magnetic flux densities of the respective regions is formed using an optically pumped magnetometer. In particular, in a gradiometer using a high sensitivity optically pumped magnetometer, a geometric arrangement enabling obtainment of a large signal from a dipole moment as a signal source is defined. | 6 |
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