description stringlengths 2.98k 3.35M | abstract stringlengths 94 10.6k | cpc int64 0 8 |
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FIELD OF THE INVENTION
The present invention relates to structural members, and, more particularly, to such members that include an outer shell of fiberglass or a similar material and to a method of assembling such members.
BACKGROUND OF THE INVENTION
Structural members such as tower legs and other columns are frequently made of steel or other metal and sometimes of wood. These conventional materials have become increasingly costly but, to date, little use has been made of alternative materials, such as fiberglass. Fiberglass has sufficient strength for many applications and has the advantage of being light in weight, which reduces shipping costs and makes the material easier to handle when a structure is being erected. In addition, it can be fabricated in a large variety of sizes and configurations, short production runs being feasible. Moreover, the amount of fiberglass incorporated in a member and the resulting load bearing capacity can be varied considerably without changing external dimensions.
One reason that fiberglass members have not come into common use is that it has proven very difficult to attach such members to the surrounding structure. It can be equally difficult to attach any components of the member that are not formed by the fiberglass itself.
A primary objective of the present invention is to provide an improved fiberglass structural member which overcomes the attachment difficulties previously associated with this material. A further objective is to provide such a member of increased strength and rigidity.
SUMMARY OF THE INVENTION
The present invention resides in a structural member that accomplishes the above objectives and in a method for the assembly of such a member. It includes an elongated body shell formed of fibers and a bonding medium, the shell having an open interior extending throughout. A pair of end caps are disposed across the ends of the shell and pulled toward each other by one or more bands in tension. The caps are thus secured to the shell. Preferably, the bands are filament wound loops.
It is advantageous to arrange interior surfaces of the shell so that they contact the side edges of the loops. Since the bands are rigidified by the tension, they resist collapse of the shell. Preferably, the shell is a multi-sided, box-like enclosure.
While the body shell can advantageously be formed of fiberglass, it is desirable to use metal for the end caps. Preferably, the end caps carry external fastening means.
In a preferred embodiment, the bands are attached to the end caps by anchor pieces, one of the anchor pieces being movable to apply tension to the bands. A preferred arrangement employs a movable anchor piece threadedly engaged by a tensioning member.
The tensioning member, which has a head received by a recess in the corresponding end cap, can be rotated by a drive member attached in such a manner that it breaks away once a predetermined tension has been applied. In one embodiments, serrations on the head of the tensioning member can engage the end cap to prevent counter-rotation that would result in a loss of tension.
Other features and advantages of the present invention will become apparent from the following detailed description, taken in conjunction with the accompanying drawings, which illustrate, by way of example, the principles of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an exploded, three-dimensional view of a structural member constructed in accordance with the invention, part of the shell being broken away to expose the bands and part of one end cap being broken away to expose its interior;
FIG. 2 is an end view of an end cap taken as indicated by the line 2--2 in FIG. 1, a portion of the end cap being broken away to enclose its interior;
FIG. 3 is a fragmentary cross-sectional, side view of two attached structural members each similar to the member shown in FIG. 1;
FIG. 4 is an exploded, three-dimensional view of another structural member constructed in accordance with the invention; and
FIG. 5 is an end view of the structural member of FIG. 4 taken as indicated by the arrows 5.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
A column 10, shown in FIG. 1 of the accompanying drawings, is suitable for use as, for example, a tower leg. It is exemplary of the many structural members that can be constructed in accordance with the present invention.
The beam 10 includes a four-sided, box-like, fiberglass body shell 12. The shell 12 is formed by an inner layer 12A that is filament wound parallel to the longitudinal axis of the column 10 and an outer layer 12B that is filament wound perpendicular to the longitudinal axis of the column. This technique for arranging the fibers within the resinous bonding material provides a shell 12 of superior strength. An alternative method of forming the shell 12 would utilize pulltrusion.
Within the shell 12 are four fiberglass bands 14 each of which is filament wound as a loop. Each of the bands 14 extends longitudinally throughout the open interior of the shell 12 and is oriented so that one of its two loop-shaped endless side edges is contiguous with the flat interior surface of a corresponding side of the shell 12. While this band construction is preferred, other types of band, such as woven steel cables, could be used.
Disposed across and covering the open ends of the shell 12 are steel end caps 16 and 18. The first end cap 16 is basically a steel plate that interlocks with one end of the shell 12. The inner layer 12A of the shell 12 projects slightly beyond the outer layer 12B and fits into the end cap to interlock and prevent transverse relative movement (note the right hand side of FIG. 3).
On the inside of the first end cap 16 is an internally formed anchor piece 20 that includes a rectangular support 22 projecting a short distance along the longitudinal axis of the shell 12 and four cylindrical lugs 24 that project radially from the support 22. Each of the lugs 24 is circled by an end of one of the bands 14, as shown in FIG. 3. On the outside of the first end cap 16 is a cross-shaped external fastener 26, the use of which will be explained below.
At the opposite end of the body shell 12, the second end cap 18 interlocks with the shell in the same manner as the first end cap 16. However, the second end cap 18 is of a different construction having two parallel plates 28 and 30 that define a cavity 31 between them. The inner plate 28 rests against the end of the shell 12.
The outer plate 30 is provided with a cross-shaped opening 32 that serves as an external fastener. This opening 32 is of the same configuration as the male fastener 26 at the opposite end of the column 10, but is rotationally displaced 45 degrees with respect to the male fastener. Accordingly, two similar columns 10 can be interlocked by inserting the male fastener 26 in the opening 32 and then rotating the flat sides of one column until they are aligned (see FIG. 3).
Just inside the second end cap 18 is a movable anchor piece 34 that includes a large four-sided nut 36 having a threaded opening 38 aligned with the longitudinal axis of the column 10. Four radially projecting cylindrical lugs 40 extend from the nut 36 to engage the ends of the bands 14. Thus, the bands 14 extend between the two anchors 20 and 34.
To retain and position the movable anchor 34 is a function of a tensioning member 42 that includes a threaded shank 44 and an enlarged convex head 46 at its outer end. The shank 44 extends through a central aperture 48 in the inner plate 28 and is received by the threaded opening 38 of the anchor 34. A concave, counter-sunk recess 50 in the outer surface of the inner plate 28 surrounds the aperture 48 and receives the head 46 of the tensioning member 42. Serrations 52 on the head 46 engage the surface of the recess 50 to prevent undesired rotation of the tensioning member 42.
To assemble the column 10, the bands 14 are placed within the body shell 12 so that they protrude from the open end where the second end cap 18 is to be positioned. The protruding ends can then be looped over the lugs 40 of the movable anchor piece 34. The free ends of the bands 14 are then withdrawn from the opposite end of the shell 12 so that the movable anchor piece 34 is pulled into the shell. It is then possible to connect the bands 14 to the lugs 24 of the fixed anchor piece 20. The bands 14 and movable anchor piece 34 are then moved back toward the second end cap 18 until the first end cap 16 interlocks with the body shell 12 as explained above.
The second end cap 18 is then interlocked with the opposite end of the body shell 12 to close the column 10. At this point, the bands 14 are only losely held. Next, the tensioning member 42 is inserted through the aperture 48 of the second end cap 18 so that the shank 42 engages the threads of the movable end anchor 34.
At this stage in the assembly of the column 10, the tensioning member 42 carries a break away drive piece 54 that, along with the head 46 to which it is attached, passes through the center of the cross-shaped opening 32 of the second end cap 18. The drive piece 54 (hexagonal in this example) is engaged by a suitable tool to rotate the tensioning member 42. Rotation in the proper direction causes the movable anchor 34 to be pulled toward the second end cap 18. In this manner, the bands 14 are stretched between the two anchors 20 and 34. After a predetermined tension has been applied to the bands 14, the drive piece 54 breaks off and can be extracted from the second end piece 18 through the cross-shaped opening 32. The serrations 52 do not interfere with rotation of the tensioning member 42 in the direction that increases the tension on the bands 14. They do, however, bite into the surface of the recess 50 to prevent tension reducing counter-rotation.
It will be noted that the metal end caps 16 and 18 are thus firmly and permanently secured to the body shell 12 by the tension of the bands 14. It is not necessary to use glue or other mechanical fasteners that would necessarily depend on the strength and integrity of a relatively small portion of the fiberglass shell 12 at the point of attachment. In addition, the bands 14 strengthen and rigidify the column 10 to inhibit any type of twisting or bowing since at least one of the bands 14, which are in tension, would resist the elongation that would necessarily accompany any such deflection. Another function of the bands 14 is to strengthen the sidewalls of the shell 12 which are in contact with the endless loop-shaped side edges of the bands tact, thereby preventing the shell from collapsing.
Another column 60, as shown in FIGS. 4 & 5, is also constructed in accordance with the invention but omits the more complex tensioning arrangement of the column 10 described above. It has a multi-directionally wound fiberglass body shell 62 formed by two elongated channel-shaped members 63 that come together to form a four-sided, box-like structure wrapped by a decorative outer layer 64. It is closed at the ends by first and second end caps 65 and 66 that are similar to the end caps 16 and 18 of the beam 10. The two columns 10 and 60 differ, however, in that the end caps 65 and 66 of the second column 60 each carry two relatively large plate-like projections 68 that fit into the shell 62. Instead of having four cylindrical lugs like the lugs 24 of the column 10, the end caps 65 and 66 of the column 60 each carry an anchor piece 70 that forms only two such lugs. Each of these anchor pieces 70 is intergrally formed with one of the end caps 65, 66 and thus as a fixed position once a corresponding end cap is in place. There are only two filament wound fiberglass bands 72 that engage the lugs 70 and pull the end caps 65 and 66 toward each other so that the shell 62 is firmly held in compression between the two end caps. The inside of the shell 62 can be in contact with the side edges of the bands 72.
To assemble the column 60, the bands 72 are looped over the anchor 70 and the two end caps 65 and 66 are pulled apart, gripping them by two external fasteners 74 and 76 similar to the fasteners 26 and 32 of the column 10. The channel shaped members 63 are then positioned between the end caps 64 and 66 and the tension of the bands 72 is allowed to pull the end caps toward each other. The column 60 can, if desired, be disassembled by reversing these steps.
Like the first column 10, the second column 60 retains the advantages of light weight and high strength associated with fiberglass. In addition, the parameters of the columns 10 and 60 can be varied with relative ease during the manufacturing process by changing the thickness of the fiberglass or varying the materials used without changing external dimensions significantly. The rigidity of the columns 10 and 60 can be altered by changing the tension of the bands 14 and 72.
While a particular form of the invention has been illustrated and described, it will be apparent that various modifications can be made without departing from the spirit and scope of the invention. | A structural member having an enlongated body shell, which may be fiberglass, and a pair of end caps enclosing the ends of the shell. A plurality of bands extend through the shell connecting the caps and pulling them toward each other, thus rigidifying the member and securing the caps. Contact between the interior surfaces of the shell and the side edges of the bands causes the shell to resist collapse. At one end of the member, the bands are secured to the end cap by movable anchor piece. A tensioning member threadedly engages the anchor piece so that tension can be applied to the bands by rotating the tensioning member. At a predetermined tension, a drive piece connected to the tensioning member breaks away and serrations on the head of the tensioning member prevent it from counter-rotating to release the tension. | 4 |
This application is a continuation of application Ser. No. 07/854.293, Mar. 19, 1992, now abandoned
BACKGROUND OF THE INVENTION
The present invention concerns an explosive device with a hollow charge designed for penetrating armor protected by active primary armor.
It is stated, as a reminder, that a hollow charge is basically made up of a rotationally symmetric explosive charge, provided with an open cavity covered by a metallic liner, and a priming device also having rotational symmetry. When detonated by the priming device, the metallic liner of the cavity is projected onto the rotational axis of the charge producing a jet of molten metal, which travels at very high speed along this axis, and a metal slug, travelling more slowly along the same axis, in the same direction as the preceding jet or in the opposite direction.
It is also reminded that, active primary armor is generally an auxiliary armor positioned in front of a conventional armor, referred to as the main armor; this auxiliary armor comprises two plates, usually made of steel a few millimetres thick with a relatively thin layer of explosive sandwiched between them. The primary armor may be multi-layered, that is, it may include several such sandwiches. The primary armor is provided so that when it is hit by a projectile, the head of the latter detonates the explosive layer on penetrating it. The explosion then projects the steel plates towards the projectile, perturbing it and reducing its lethality. In particular, in the case of a hollow charge projectile, the steel plates of the primary armor interfere with the jet of the hollow charge to such an extent that it loses most of its penetrating power against the main armor.
Such active primary armors are frequently used for the protection of armored vehicles, such as combat tanks.
The problem which faces designers of anti-tank munitions is therefore the following: in order to penetrate the main armor, it is preferable to use a very powerful hollow charge capable of penetrating the main armor which is usually very thick, yet, as stated above, hollow charges are particularly vulnerable to the action of active primary armor.
Different solutions are known for resolving this problem.
A first solution consists of greatly increasing the nominal penetrating power of the hollow charge so that its residual penetrating power (after interference by the primary armor) is sufficient. This process is simple but very expensive in terms of hollow charge calibres.
A second solution is the two-stage hollow charge (often referred to as a tandem warhead). The function of the charge which operates first, referred to as the primary warhead, is to neutralize the primary armor:
either by initiating it soon enough before the detonation of the second, or main, warhead, and thus facilitating the elimination of the primary armor plates before the arrival of the jet of the main warhead;
or by penetrating it without igniting it.
In the first case, adjustment of the process is difficult, in particular regarding the delay between the detonation of the two charges, and the implementation of this adjustment complicates the structure of the munitions, in particular those which, designed to be fired from cannons, must withstand very high acceleration. A solution corresponding to the second case is described notably in French patent application no. 2 583 156, which describes means of reducing the effect of the primary warhead. This embodiment, like the preceding one, has the disadvantage of increasing the bulk of the explosive device.
Furthermore, in order to improve the performance of a hollow charge, a known method consists of providing, between the priming device detonator and the explosive charge, a wave shaper, also known as a screen, whose function is to deflect the detonation wave and make it toric. This makes it possible, by varying the waveform and the shape of the cavity, to increase the velocity of the pentrating jet produced by the hollow charge, the explosive yield of the charge, etc.. The form of the screen is determined so that the detonation wave is deflected without substantial power loss, and so as to obtain the desired angle of incidence of this wave on the liner of the cavity. This leads to bulky screens whose length may be one third or one quarter of the length of the explosive charge, which again leads to an increase in bulk of the hollow charge and reduces its efficiency.
SUMMARY OF THE INVENTION
The purpose of the present invention is to reduce the longitudinal size of an explosive device with a hollow charge, of the type including a main warhead with a wave shaper and a primary warhead for the penetration of an active primary armor.
For this purpose, the primary warhead is a hollow charge placed at the apex of the main hollow charge and separated from the latter by wave transmission means, preferably comprising a third hollow charge inverted relative to the other two, the primary warhead also acting as a wave shaper for the main warhead.
BRIEF DESCRIPTION OF THE DRAWING
Other purposes, particular characteristics and results of the invention will become apparent from the following description, given as an example, but not limitative, and illustrated by the drawings, which represents in cross-section an embodiment of the explosive device with a hollow charge according to the invention in which:
FIG. 1 is a schematic cross-sectional view of an explosive device according to the invention;
FIG. 2 is a schematic view of the cavity of the main warhead section showing an alternative to the embodiment of FIG. 1;
FIG. 3 is a further alternative embodiment to that shown in FIG. 2.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The drawing represents an explosive device including an explosive charge 4 contained in a casing 1, and which is provided with an open cavity including three sections, marked 10, 20 and 30 from the explosive charge towards the opening respectively; the cavity is covered by a liner in three sections marked 13, 23, and 33 respectively. At the rear of the casing, which is at the opposite end from the opening of the cavity, a priming device 5 is provided, including, for example, a detonator 51 and an igniter charge 52, primed by the detonator 51 and having the function of detonating the charge 4. The assembly has rotational symmetry about a longitudinal axis XX.
The device therefore includes three sections, namely, starting from the rear of the device:
a section I, forming the primary warhead of a tandem-type warhead as described above. This primary warhead is a hollow charge, formed by cavity 10 open towards the front, for example in the approximate form of a cone, by section 13 of the liner and by the part of the explosive charge 4 surrounding it;
a second section II constituting a wave transmitter, formed by cavity 20 which is open at both ends but is more open at the rear of the device than at the front (for example in the form of a truncated cone), by section 23 of the liner and by the part of the explosive charge surrounding it;
a section II forming the main warhead of the tandem charge; it comprises a hollow charge formed by cavity 30, open at the front and not completely closed at its apex (for example in the approximate form of a cone, trumpet or tulip as shown in FIG. 2), by section 33 of the liner and by the part of the explosive charge 4 surrounding it.
When the detonator is triggered, it creates a detonation wave, by means of the igniter charge 52, in the explosive charge 4. The detonation wave is propagated in the primary warhead section (I) of the device, causing a very rapid jet and a slower slug to be formed from liner 13, and propagated on the axis XX. As stated earlier, the jet is intended to penetrate an active primary armor without igniting it.
Penetration without ignition is achieved by restricting the energy per unit area transmitted by the jet to the explosive of the primary armor, the energy of the jet depending mainly on the nature and weight of the liner and on the speed of the jet. For this reason, a material of low density is used for the liner, for example a plastic Nylon type material, along with a hollow charge designed to give the jet a relatively high velocity, so that there is no risk of collision between the jet of the primary warhead and that of the main warhead.
The form of the detonation wave arriving at base 11 of liner 13 is the same as one formed by a conventional wave shaper, this function being performed by the primary warhead I.
The wave transmitter II is designed to conduct the detonation wave to the apex 32 of the main warhead III. This transmitter functions like a hollow charge but with its priming device inverted, that is, it operates from its base 21. From liner 23, a jet is therefore formed, travelling on axis XX towards the rear of the device, a jet which is lost, and a slug whose effect is to close the apex 32 of the main hollow charge III. It must be noted that liner 23 is not essential; in fact, the closure of apex 32 itself is, in principle, not essential for the functioning of the main warhead; it does, however, have the advantage of opposing the passage of the slug of the primary warhead I, which, itself, would be liable to interfere with the formation of the jet of the main warhead. For this purpose, liner 23 may be made of metallic material, for example soft steel or copper. It must also be noted that the cavity 20 of the wave transmitter is represented in tapered form but that it may have other forms, for example that of a tulip or a trumpet; it can also have a larger or smaller angle at the apex, or even a cylindrical form, the angle depending on the diameters chosen for the base 11 of the primary warhead and the apex 32 of the main warhead.
The detonation wave then reaches the main hollow charge III, which then functions like a hollow charge equipped with a wave shaper. The liner 33 may conventionally be metallic, for example copper.
The explosive device described above therefore offers the advantages of a tandem-type structure and a hollow charge including a wave shaper, the entire assembly having reduced size, Moreover, the fact that the primary warhead penetrates an active primary armor without initiating it means that the action of the main warhead does not have to be delayed. The device according to the invention offers the following additional advantages:
elimination of possible inter-charge screens, as only a single explosive charge 4 is used;
elimination of the priming device of the primary warhead; according to the invention, a single device 5 assures the initiation of the whole assembly;
elimination of the risks of destruction of the main warhead before it functions; in fact, according to the invention, there is no possible back-firing of the primary warhead towards the main warhead;
large calibre of the primary warhead (equal to that of the main warhead);
reduction of the influence of the munition's sideslipping on the target, by reducing the overall functioning delay. | An explosive device with a hollow charge of the type including a main warhead with a wave shaper and a primary warhead for the penetration of active primary armor. The primary warhead comprises a hollow charge provided at the apex of the main warhead and separated from the latter by wave transmitting means in the form of a third hollow charge placed inverted relative to the other two hollow charges, the primary warhead also acting as a wave shaper for the main warhead. | 5 |
This application claims the benefit of U.S. provisional patent application Ser. No. 60/003,628, filed Sep. 14, 1995.
BACKGROUND OF THE INVENTION
The present invention relates to N-substituted derivatives of glutamic acid of pharmaceutical interest, to pharmaceutical compositions which include compounds of the invention and pharmaceutically acceptable carriers, to methods of their preparation, and to their use in purification of interleukin-1β converting enzyme (ICE). The novel compounds of the present invention are inhibitors of ICE and hence are useful in controlling human disorders associated with generation of interleukin-1β (IL-1β), including but not limited to rheumatoid arthritis, inflammatory bowel disease, stroke, Alzheimer's disease, septic shock, and acute myelogenous leukemia.
ICE acts on pro-interleukin-1β (pro-IL-1β) to generate interleukin-1β (IL-1β) which is an inflammatory cytokine. Cleavage occurs between aspartate 116 and alanine 117 of pro-IL-1β. The substrate specificity of ICE has been studied by P. R. Sleath, et al., in J. Biological Chem., 1990;265:14526-14528 and by D. K. Miller, et al., in Ann. N.Y. Acad. Sci., 1993;696:133-48, who found ICE to be highly specific for aspartic acid residues at the P-1 position. Substitution of even highly similar amino acids such as glutamate or asparagine for aspartic acid at the P-1 position of decapeptides which span the ICE cleavage site in pro-IL-1β were found to reduce the rate of cleavage to less than five percent of the native decapeptide with aspartic acid at P-1. This high substrate specificity allows ICE to recognize and cleave only pro-IL-1β in vivo and hence inhibition of ICE would reduce or eliminate inflammatory reactions associated with excess ICE activity by preventing the formation of IL-β. Conditions associated with excess ICE activity may include, but are not limited to joint inflammation such as in rheumatoid arthritis, gastrointestinal inflammation such as with inflammatory bowel disease, neuroinflammatory disorders such as seen in stroke and Alzheimer's disease, septic shock, and cancerous diseases such as acute myelogenous leukemia. ICE inhibitors have potential therapeutic utility in such conditions.
Many peptidic inhibitors of ICE have been described in the literature including tetrapeptide aldehydes such as Ac-Tyr-Val-Ala-Asp CHO! by Seq. ID NO.1 K. T. Chapman in Bioorganic & Medicinal Chemistry Letters, 1992;2:613-618, tripeptide aldehydes and derivatives such as Cbz-Val-Ala-Asp CHO! by T. L. Graybill, et al., in Int. J. Peptide Protein Res., 1994;44:173-182, peptidic acyloxymethyl ketone derivatives by R. E. Dolle, et al., in J. Medicinal Chemistry, 1994;37:563-564 and by C. V. C. Prasad, et al., in Bioorganic & Medicinal Chemistry Letters, 1995;5:315-318, and N-acyl-aspartic acid ketones by A. M. M. Mjalli, et al., in Bioorganic & Medicinal Chemistry Letters, 1995;5:1405-1408. In accordance with the substrate specificity of ICE, these previous disclosures focus on derivatives of aspartic acid as the preferred P-1 substituent. In the acyloxymethyl ketone papers by Dolle and Prasad, direct comparison of an acyloxymethyl ketone derived from aspartic acid to a similar compound derived from glutamic acid showed that, for ICE, the glutamic acid derived compound was "devoid of enzyme affinity" (quote from Dolle, et al., paper).
EP 0519748A discloses peptidyl derivatives as inhibitors of interleukin-1β converting enzyme
EP 0529713A discloses an affinity chromatography matrix useful in purifying interleukin-1β converting enzyme.
EP 0547699A discloses peptidyl derivatives as inhibitors of interleukin-1β converting enzyme.
However, the compounds disclosed in the above references do not disclose or suggest the ICE inhibitory activity of the compounds described hereinafter. On the contrary, they suggest that compounds of the present invention would be unlikely to contain significant ICE inhibitory activity.
SUMMARY OF THE INVENTION
One embodiment of the present invention is a compound of Formula I or a pharmaceutically acceptable ##STR1## salt thereof wherein: R is H, CH 3 , C 2 H 5 , or CH 2 O-alkyl;
R 1 is CHO, COCH 3 , COCF 3 , CH(OCH 3 ) 2 , or CN; and
R 2 is a tripeptide of the formula ##STR2## a dipeptide of the formula ##STR3## an amino acid derivative of the formula ##STR4## or an amide, carbamate, urea, or sulfonamide of the formula R 8 .
According to the description above:
R 3 and R 4 are each independently H, CH 3 , C 2 H 5 , n--C 3 H 7 , CH(CH 3 ) 2 , n--C 4 H 9 , CH 2 CH(CH 3 ) 2 , CH(CH 3 )C 2 H 5 , CH 2 OH, CH 2 SH, CH 2 CH 2 OH, CH 2 CH 2 SCH 3 , CH(OH)CH 3 , CH 2 CH═CH 2 , ##STR5## (CH 2 ) 4 NH 2 , (CH 2 ) 3 NHCOCH 3 , (CH 2 ) 4 NHCOCH 3 ,
(CH 2 ) 3 NHCOPh, (CH 2 ) 4 NHCOPh, (CH 2 ) 3 NHCO 2 CH 2 Ph,
(CH 2 ) 4 NHCO 2 CH 2 Ph, CH 2 CH 2 CO 2 H, CH 2 CH 2 CONH 2 , ##STR6## X 1 and X 2 are each independently H, or CH 3 ; R 5 is CH 2 Ph, CH 2 CH 2 Ph, CH 2 (4--HO--Ph), CH 2 CH 2 (4--HO--Ph), CH 2 -cyclohexyl, CH 2 CH 2 -cyclohexyl, CH 2 CH(CH 3 ) 2 , CHCH 2 -(2-naphthyl), or CH 2 -(3-indolyl);
R 6 is CH 3 CO, CH 3 CH 2 CO, CH 3 SO 2 , CH 3 CH 2 SO 2 , or ##STR7## R 7 is PhCH 2 OCO, PhCH 2 CH 2 OCO, PhCH 2 CH 2 CO, Ph(CH 2 ) 3 CO, PhCH 2 NHCO, PhCH 2 CH 2 NHCO, (2-naphthyl)-CH 2 CO, or (2-naphthyl)-CH 2 CH 2 CO; and
R 8 is R 9 CO, R 9 OCO, R 9 NHCO, or R 9 SO 2 where R 9 is alkyl, alkenyl, aryl, arylalkyl, cycloalkyl, (cycloalkyl)alkyl, heterocycle, or (heterocycle)alkyl.
A second embodiment of the invention is a method for preparation of compounds of Formula I by multiple, simultaneous synthesis. Additional embodiments of the invention are the uses of compounds of Formula I in treating rheumatoid arthritis, inflammatory bowel disease, stroke, Alzheimer's disease, septic shock, and acute myelogenous leukemia. A final embodiment of the invention is the use of selected compounds of Formula I in the purification of ICE.
DETAILED DESCRIPTION OF THE INVENTION
The following definitions apply to terms used in the description of Formula I:
"Alkyl" is a straight or branched chain of eight or fewer carbon atoms that is unsubstituted or substituted by one or two functional groups selected from OH, NH 2 , OCH 3 , CO 2 H, CO 2 CH 3 , CONH 2 , ═O, or CN.
"Alkenyl" is an alkyl group defined as above with one or two carbon double bonds.
"Cycloalkyl" is a ring of from three to eight carbon atoms that is unsubstituted or substituted by one or two functional groups selected from OH, NH 2 , OCH 3 , CO 2 H, CO 2 CH 3 , CONH 2 , ═O, or CN.
"(Cycloalkyl)alkyl" is a straight chain of from one to five carbon atoms which is substituted by a cycloalkyl group as described above.
"Aryl" is a benzene or naphthyl ring that is unsubstituted or substituted by one to three functional groups selected from CH 3 , CF 3 , F, Cl, Br, I, NO 2 , OH, NH 2 , OCH 3 , CHO, CH 2 OH, CO 2 H, CO 2 CH 3 , CONH 2 , or CN.
"Arylalkyl" is a straight chain of from one to five carbon atoms which is substituted by an aryl group as describe above.
"Heterocycle" is an aliphatic or aromatic five or six membered ring, or by an aromatic 5,6-fused or 6,6-fused bicyclic ring bearing one to four atoms selected from N, O, or S. The rings are unsubstituted or substituted by one to three functional groups selected from CH 3 , CF 3 , F, Cl, Br, I, NO 2 , OH, NH 2 , OCH 3 , CHO, CH 2 OH, CO 2 H, CO 2 CH 3 , CONH 2 , or CN.
"(Heterocycle)alkyl" is a straight chain of from one to five carbon atoms which is substituted by a heterocycle group as described above.
"Pharmaceutically acceptable salts" is as described by S. M. Berge, et al., in Journal of Pharmaceutical Science, 1977;66:1-19:
a) Acid addition salts--derived from nontoxic inorganic acids such as hydrochloric, nitric, phosphoric, sulfuric, hydrobromic, hydroiodic, phosphorous, and the like, as well as from nontoxic organic acids such as aliphatic mono- and dicarboxylic acids, phenyl-substituted alkanoic acids, hydroxy alkanoic acids, aromatic acids, aliphatic and aromatic sulfonic acids, and the like.
b) Base addition salts--derived from alkaline earth metals including sodium, potassium, magnesium, calcium, and the like, as well as from nontoxic organic amines such as N,N'-dibenzylethylenediamine, N-Methylglucamine, chloroprocaine, choline, diethanolamine, ethylenediamine, procaine, and the like.
Common abbreviations for natural amino acids, common protecting groups, common solvents, and common reagents are as accepted by the Journal of Organic Chemistry. Amino acid abbreviations beginning with a capital letter indicate the L-enantiomer and those beginning with a lower case letter indicate the D-enantiomer, e.g., Phe (-phenylalanine) and phe (D-Phenylalanine). Other abbreviations include: Aha (L-6-aminohexanoic acid), hPhe (L-homophenylalanine), hTyr (L-homotyrosine), Cha (L-cyclohexylalanine), hCha (L-homocyclohexylalanine), Nle (L-butylglycine, also known as L-norleucine), Glu CHO! (4-amino-4-formyl-butanoic acid), Glu CN! (4-amino-4-cyano-butanoic acid), DCC (dicyclohexylcarbodiimide), DIC (diisopropylcarbodiimide), EDAC (ethyldimethyl-aminopropylcarbodiimide hydrochloride), HOBT (1-hydroxybenzotriazole hydrate), AMC (7-amino-4-methylcoumarin), MBHA resin (methylbenzhydrylamine resin), BOP reagent (Benzotriazol-1-yloxy-tris(dimethylamino)-phosphonium hexafluorophosphate.
Compounds of the invention contain one or more chiral centers. Structures and compound names lacking a specific stereochemical definition define all possible stereoisomers.
Preferred compounds of the invention are those of Formula I wherein:
R is H, CH 3 , or CH 2 O-alkyl;
R 1 is CHO, or CN; and
R 2 is a tripeptide of the formula ##STR8## a dipeptide of the formula ##STR9## an amino acid derivative of the formula ##STR10## or an amide, carbamate, urea, or sulfonamide of the formula R 8 .
According to the preferred description above:
R 3 is CH 3 , C 2 H 5 , n--C 3 H 7 , n--C 4 H 9 CH(CH 3 ) 2 CH 2 CH 2 CO 2 H, CH 2 CH 2 CONH 2 , (CH 2 ) 4 NH 2 , ##STR11## R 4 is n--C 3 H 7 , CH(CH 3 ) 2 , n--C 4 H 9 , CH 2 CH(CH 3 ) 2 , CH(CH 3 )C 2 H 5 , CH(CH 3 )OH, CH 2 CH 2 CO 2 H, CH 2 CH 2 CONH 2 , or ##STR12## X 1 and X 2 are each independently H, or CH 3 ; R 5 is CH 2 Ph, CH 2 CH 2 Ph, CH 2 (4-HO-Ph), CH 2 CH 2 (4--HO--Ph);
R 6 is CH 3 CO, or ##STR13## R 7 is PhCH 2 OCO, PhCH 2 CH 2 OCO, PhCH 2 CH 2 CO, Ph(CH 2 ) 3 CO, PhCH 2 NHCO, PhCH 2 CH 2 NHCO, (2-naphthyl)--CH 2 CO, or (2-naphthyl)-CH 2 CH 2 CO; and
R 8 is R 9 CO, R 9 OCO, R 9 NHCO, or R 9 SO 2 where R 9 is aryl, arylalkyl, cycloalkyl, (cycloalkyl)alkyl, heterocycle, or (heterocycle)alkyl.
More preferred compounds of the invention are selected from the following list:
1) Ac-Tyr-Val-Ala-Glu CHO! Seq. ID No.2
2) Ac-Tyr-Nle-Ala-Glu CHO! Seq. ID No.3
3) Ac-hTyr-Val-Ala-Glu CHO! Seq. ID No.4
4) Ac-hTyr-Nle-Ala-Glu CHO! Seq. ID No.5
5) Ac-Tyr-Val-Ala-Glu CN! Seq. ID No.6
6) Ac-Tyr-Nle-Ala-Glu CN! Seq. ID No.7
7) Ac-hTyr-Val-Ala-Glu CN! Seq. ID No.8
8) Ac-hTyr-Nle-Ala-Glu CN! Seq. ID No.9
9) Cbz-Val-Ala-Glu CHO!
10) Cbz-Nle-Ala-Glu CHO!
11) Ph(CH 2 ) 3 CO-Val-Ala-Glu CHO!
12) Ph(CH 2 ) 3 CO-Nle-Ala-Glu CHO!
13) Cbz-Val-Ala-Glu CN!
14) Cbz-Nle-Ala-Glu CN!
15) Ph(CH 2 ) 3 CO-Val-Ala-Glu CN!
16) Ph(CH 2 ) 3 CO-Nle-Ala-Glu CN!
17) Ph(CH 2 ) 5 CO-Ala-Glu CHO!
18) Ph(CH 2 ) 5 CO-Ala-Glu CN!
19) Ac-Tyr-Glu-Val-Glu CHO! Seq. ID No.10
20) Ac-Tyr-Glu-Val-Glu CN! Seq. ID No.11
21) Ac-hTyr-Glu-Val-Glu CHO! Seq. ID No.12
22) Ac-hTyr-Glu-Val-Glu CN! Seq. ID No.13.
Any of the compounds of Formula I which contain a free amino group or a biotinoyl moiety may be utilized in the affinity purification of ICE. Preferred compounds for use in the affinity purification of ICE include compounds listed below:
1) Biotinoyl-Aha-Tyr-Val-Ala-Glu CHO! Seq. ID No.14
2) Ac-Tyr-Val-Lys(Aha-Biotinoyl)-Glu CHO! Seq. ID No.15
3) Ac-Tyr-Lys(Aha-Biotinoyl)-Glu CHO!.
These compounds serve as affinity ligands. They are first complexed to an immobilized avidin such as avidin-sepharose. A crude cell preparation is then equilibrated with the immobilized ligand and eluted with a suitable buffer to remove unbound cellular materials. The column-bound ICE is then equilibrated with an excess of soluble Ac-Tyr-Val-Ala-Glu CHO! and the purified ICE is eluted from the column in an inhibited form.
Compounds of Formula I are valuable inhibitors of ICE as demonstrated by measurement of K i and k on against ICE using the protocol described herein. ICE (0.24 nM) is added to 400 uL of HGDE buffer (100 mM HEPES, 20% glycerol, 5 mM DTT, and 0.5 mM EDTA) containing 250 μM substrate (Ac-Tyr-Val-Ala-Asp-AMC; Seq. ID No.16 Km=15 μM). Substrate hydrolysis is monitored by observing the fluorescence of released AMC using excitation at 380 nM and emission at 460 nM, After linearity of the assay is confirmed, a compound of Formula I is added to a final concentration of I!=2 or 4 μM, resulting in slow progressive decrease in the rate of substrate hydrolysis, with steady-state inhibition being achieved. The progress curves are fit to the equation F=F 0 +Vf.t+(V i -V f ) (1-exp(-k obs t))/k obs , where F 0 is the initial fluorescence, V i and V f are initial and final reaction velocities, and k obs is the pseudo first-order rate of inhibition. K i is calculated as K i =SPF. I!V f /(V i -V f ), where the substrate protection factor (SPF) is 1+ S!/K m =17.7. k on is calculated as SPF.k obs / I!.
Using these methods compounds of the invention can be shown to have K i values in the range of 0.5 nM to 50 μM and k on values in the range of 1×10 4 to 1×10 6 M -1 s -1 for inhibition of ICE. For example, one compound of the instant invention, Ac-Tyr-Val-Ala-Seq. ID No.2 Glu CHO!, gave K i =1.8 nM and k on =17,250 M -1 s -1 . Similar measurements applied to the reference ICE inhibitor, Ac-Tyr-Val-Ala-Asp CHO! gave K i =0.7 nM Seq. ID No.1 and k on =3×10 5 M -s -1 . The fact that these two molecules give similar K i values is unexpected based on the prior art since comparable substrates with Asp and Glu in the P-1 position show Glu to be detrimental to cleavage (P. R. Sleath, et al., J. Biological Chem., 1990;265:14526-14528 and D. K. Miller, et al., Ann. N.Y. Acad. Sci., 1993;696:133-148) and since other, structurally distinct inhibitors show a clear preference for Asp analogs over Glu analogs (R. E. Dolle, et al., J. Medicinal Chemistry, 1994;37:563-564 and C. V. C. Prasad, et al., Bioorganic & Medicinal Chemistry Letters, 1995;5:315-318).
Further evidence that compounds of Formula I are valuable inhibitors of ICE is provided by their ability to inhibit IL-1β production in human peripheral blood mononuclear cells (PBMCs) as described herein. PBMCs are isolated from heparinized blood by centrifugation over a ficoll cushion, then washed three times with phosphate-buffered saline. PBMCs are suspended in a medium containing RPMI 1640 with glutamine, penicillin, streptomycin and 2% human AB serum, then plated at 10 6 cells per well in 96-well flat bottom plates. PBMCs are stimulated overnight with 10 ng/mL of lipopolysaccharide (LPS, E. Coli strain 0111:B4; Calbiochem) in the presence or absence of a compound of Formula I. Medium is harvested and the level of mature IL-1β was determined using an ELISA kit from R & D Systems. Cells were cultured for an additional 4 hours in the presence of 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) to determine viability.
In this assay, the compound of Formula I, Ac-Tyr-Val-Ala-Glu CHO!, at a concentration of 100 μM, Seq. ID No.2 inhibited the production of mature IL-1β by 90% relative to the level from control PBMCs treated with LPS alone. Cell viability after treatment with 100 μM Ac-Tyr-Val-Ala-Glu CHO! was >95% as measured by the MTT assay. In similar experiments, the reference ICE inhibitor, Ac-Tyr-Val-Ala-Asp CHO!, at a concentration Seq. ID No.1 of 100 μM, also inhibited the production of mature IL-1β by 90% relative to control.
Compounds of Formula I may be prepared as outlined in Schemes 1 and 2. Although these schemes indicate only a limited range of structures, the methods apply widely to analogous compounds of Formula I, given appropriate consideration to the protection and deprotection of reactive functional groups by methods that are standard to the art of organic chemistry
According to Scheme 1, the synthesis starts from Nα-Fmoc-glutamic acid γ-t-butyl ester, 1, which is converted to a mixed anhydride by treatment with isobutylchloroformate and N-methylmorpholine and subsequently treated with O,N-dimethylamine to afford 2. Reduction of 2 with LAH in THF at -60° C., followed by a mild acid work-up affords the aldehyde 3 which is condensed with the semicarbazide, 4, to afford 5 and coupled to MBHA resin with the BOP reagent as described by A. M. Murphy, et al., in J. Am. Chem. Soc., 1992;114:3156-3157 to afford 6. Other common polymeric supports and coupling strategies may also be utilized, including those where the semicarbazide moiety is attached directly to the polymer or extended from the polymer by alternate linking groups. The remainder of the synthesis involves the sequential removal of the Fmoc group under standard conditions, such as 50% piperidine, morpholine, or piperazine in DCM or DMF, affording 7. Peptide and amide bonds may be formed by reacting 7 with a carboxylic acid halide or a mixed anhydride and a tertiary amine acid scavenger or alternatively by combining 7 and a carboxylic acid or protected amino acid with a wide variety of coupling reagents that are standard to the art of peptide chemistry. Sulfonamides are similarly prepared by reacting 7 with a sulfonyl chloride and tertiary amine. Cleavage of the t-butyl ester in 8 by treatment with TFA in DCM gives 9 which is subsequently cleaved from the resin by treatment with formaldehyde and dilute HCl to afford 10; a compound of Formula I. ##STR14##
According to Scheme 2, the synthesis may also start with Nα-Fmoc-glutamic α-carboxamide γ-t-butyl ester, 11, which is dehydrated to the nitrile through the use of a carbodiimide reagent such as DCC, DIC, or EDAC to afford 12. Removal of the t-butyl ester protecting group with TFA in DCM gives 13 which is subsequently coupled to a solid support using a mixed anhydride method such as 2,6-dichlorobenzoyl chloride/pyridine or isobutylchloroformate/N-methylmorpholine in DCM or dioxane solvent to afford 14. Solid supports are those common to solid phase peptide synthesis including, but not limited to, Wang resin, Merrifield resin, and 2-chlorotrityl resin. The remainder of the synthesis proceeds in a manner analogous to Scheme 1 to afford 17 which are compounds of Formula I. ##STR15##
While compounds of Formula I may be singly synthesized utilizing an automated peptide synthesizer, they are more rapidly prepared in a multiple parallel fashion utilizing a Diversomer apparatus as described by S. DeWitt, et al., in Proceedings of the National Academy of Science, USA, 1993;90:6909 and in U.S. Pat. No. 5,324,483.
The compounds of Formula I can be prepared and administered in a variety of oral and parenteral dosage forms. It will be obvious to those skilled in the art that the following dosage forms may comprise as the active component, either a compound of Formula I or a corresponding pharmaceutically acceptable salt of a compound of Formula I.
For preparing pharmaceutical compositions from the present invention, pharmaceutically acceptable carriers can be either solid or liquid. Solid for preparations include powders, tablets, pills, capsules, cachets, suppositories, and easily dispersed granules. A solid carrier can be one or more substances which may also act as diluents, flavoring agents or an encapsulating material.
In powders, the carrier is a finely divided solid which is in a mixture with the finely divided active component. In tablets, the active component is mixed with the carrier having the necessary binding properties in suitable proportions and compacted in the shape and size desired.
The powders and tablets preferably contain from five or ten to about seventy percent of the active compound. Suitable carriers are magnesium carbonate, magnesium stearate, talc, sugar, lactose, pectin, dextrin, starch, gelatin, tragacanth, methylcellulose, sodium carboxymethylcellulose, a low melting wax, cocoa butter and the like. The term "preparation" is intended to include the formulation of the active compound with or without carriers which is surrounded by an encapsulating material. Similarly cachets and lozenges are included. Tablets, powders, capsules, pills, cachets, and lozenges can be used a solid dosage forms suitable for oral administration.
For preparing suppositories, a low melting wax, such as a mixture of fatty acid glycerides or cocoa butter, is first melted, and the active component is dispersed homogeneously therein. The molten, homogeneous mixture in then poured into convenient sized molds, allowed to cool, and thereby to solidify.
Liquid for preparations include solutions, suspensions, and emulsions. For parenteral injection, liquid preparations can be formulated, for example, by dissolution of the active component in water or in aqueous polyethylene glycol. For oral use, the active component may be dissolved in water or aqueous ethanol and adding suitable colorants, flavors, stabilizing and thickening agents as desired. Also for oral use, suspensions can be made by dispersing finely divided active component in water with viscous material, such as natural or synthetic gums, resins, methylcellulose, sodium carboxymethylcellulose, and other well-known suspending agents.
Also included are solid for preparations which are intended to be converted, shortly before use, to liquid form preparations for oral administration. Such liquid forms include solutions, suspensions, and emulsions. These preparations may contain, in addition to the active component, colorants, flavors, stabilizers, buffers, artificial and natural sweeteners, thickeners, solubilizing agents, and the like.
The pharmaceutical preparation is preferably in unit dosage form. In such form the preparation is subdivided into unit doses containing appropriate quantities of the active component The unit dosage form can be a packaged preparation, the package containing discrete quantities of preparation, such as packeted tablets, capsules and powders in vials or ampoules. Also, the unit dosage form can be the capsules, tablet, cachet or lozenge itself, or it can be the appropriate number of any of these in packaged form. The quantity of active component in a unit dose preparation may be varied or adjusted from 0.1 mg to 100 mg according to the particular application and the potency of the active component. The composition can, if desired, also contain other compatible therapeutic agents.
In therapeutic use, the compounds utilized in the pharmaceutical method of this invention are administered at the initial dosage of about 0.1 mg to about 100 mg per kilogram daily. The dosage may be varied depending upon the requirements of the patient, the severity of the condition being treated, and the compound being employed. Determination of the proper dosage for a particular situation is within the skill of the art. Generally, treatment is initiated with smaller dosages which are less than the optimum dose of the compound. Thereafter, the dosage is increased by small increments until the optimum effect under the circumstances is reached. For convenience, the total daily dosage may be divided and administered in portions during the day, if desired.
The following examples illustrate methods for preparing intermediates and final products of the invention. They are not intended to limit the scope of the invention. Examples 1-6 describe in detail the methods outlined in Scheme 1.
EXAMPLE 1
Fmoc-Glu-(O-tBu)-N-Me(OMe) (1)
To a solution of Fmoc-glutamic acid γ-tBu ester (8.5 g, 20 mmol) and N-methylmorpholine (2.0 g, 20 mmol) in methylene chloride is added isobutylchloroformate (2.5 g, 20 mmol) at 0° C. under an atmosphereof dry nitrogen. The reaction mixture is stirred at 0° C. for 15 minutes followed by the dropwise addition of a solution of N-methyl-O-methylhydroxylamine hydrochloride (2.05 g, 21 mmol) and N-methylmorpholine (2 g, 20 mmol) in methylene chloride. The resulting solution is stirred at room temperature overnight and then evaporated under vacuum. The residue is partitioned between water and ethyl acetate and the organic layer washed successively with dilute aqueous sodium bicarbonate, 10% citric acid, and brine. The organic layer is dried over MgSO 4 and evaporated to give crude Fmoc-Glu-(O-tBu)-N-Me(OMe), 2, which is purified by flash chromatography.
EXAMPLE 2
Semicarbazone derivative (5)
To a solution of Fmoc-Glu-(O-tBu)-N-Me(OMe) (2.0 g, 4.3 mmol) in dry ether (450 mL) is added a solution of LAH (4.5 mL, 1M solution in THF) at -60° C. under an atmosphere of dry N 2 . The reaction mixture isstirred at -60° C. for 15 minutes and quenched at -60° C. by the dropwise addition of an aqueous solution of KHSO 4 (2 g) in water (6 mL). The reaction mixture is allowed to warm to room temperature, treated with an excess of MgSO 4 , and filtered through Celite. The filtrate is washed with 1N HCl, dried over MgSO 4 , and evaporated to give the crude aldehyde, 3, which is not purified, but used directly in the next reaction to avoid racemization. The crude aldehyde is dissolved in a solution of the semicarbazide, 4, (1.5 g), in ethanol (50 mL). The reaction mixture is stirred at room temperature for 30 minutes, and the ethanol is evaporated. The residue is partitioned between methylene chloride, and the organic layer is dried over MgSO 4 and evaporated togive crude semicarbazide which is purified by flash chromatography.
EXAMPLE 3
Coupling of 5 to MBHA resin
Compound 5 is coupled to the resin using the BOP reagent as described by A.M. Murphy, et al., in J. Am. Chem. Soc., 1992;114:3156-3157 to afford resinbound compound 6.
EXAMPLE 4
Removal of Fmoc protecting group
A mixture of 6 (100 mg) in DMF/piperidine was agitated for 1 hour at room temperature and filtered. The resin was successively washed with DMF, DCM,anhydrous EtOH, DCM, and DMF.
EXAMPLE 5
Acylation of 7
7 is added to a DMF solution containing a two-fold excess of Ac-Tyr-Val-Ala, EDAC and HOBT (in molar equivalent amounts). The resultingsuspension is agitated for 4 hours, the resin is then filtered, rinsed withDMF, and subsequently resubjected to the coupling reaction. Filtration and sequential rinsing with DMF, DCM, anhydrous EtOH, DCM, and DMF affords 8.
EXAMPLE 6
Deprotection and Cleavage From the Resin
8 is treated with a 1:1 mixture TFA in DCM and agitated for 2 hours at roomtemperature to give 9 which was treated with 1N HCl and 37% formaldehyde according to the procedure described by A. M. Murphy, et al., in J. Am. Chem. Soc., 1992;114:3156-3157 to liberate 10 from the resin. 10 is extracted into ethyl acetate, dried over MgSO 4 , and evaporated.
__________________________________________________________________________SEQUENCE LISTING(1) GENERAL INFORMATION:(iii) NUMBER OF SEQUENCES: 16(2) INFORMATION FOR SEQ ID NO:1:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 4 amino acids(B) TYPE: amino acid(C) STRANDEDNESS: single(D) TOPOLOGY: linear(ii) MOLECULE TYPE: peptide(xi) SEQUENCE DESCRIPTION: SEQ ID NO:1:TyrValAlaAsp(2) INFORMATION FOR SEQ ID NO:2:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 4 amino acids(B) TYPE: amino acid(C) STRANDEDNESS: single(D) TOPOLOGY: linear(ii) MOLECULE TYPE: peptide(xi) SEQUENCE DESCRIPTION: SEQ ID NO:2:TyrValAlaGlu1(2) INFORMATION FOR SEQ ID NO:3:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 4 amino acids(B) TYPE: amino acid(C) STRANDEDNESS: single(D) TOPOLOGY: linear(ii) MOLECULE TYPE: peptide(xi) SEQUENCE DESCRIPTION: SEQ ID NO:3:TyrXaaAlaGlu1(2) INFORMATION FOR SEQ ID NO:4:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 4 amino acids(B) TYPE: amino acid(C) STRANDEDNESS: single(D) TOPOLOGY: linear(ii) MOLECULE TYPE: peptide(xi) SEQUENCE DESCRIPTION: SEQ ID NO:4:XaaValAlaGlu1(2) INFORMATION FOR SEQ ID NO:5:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 4 amino acids(B) TYPE: amino acid(C) STRANDEDNESS: single(D) TOPOLOGY: linear(ii) MOLECULE TYPE: peptide(xi) SEQUENCE DESCRIPTION: SEQ ID NO:5:XaaXaaAlaGlu1(2) INFORMATION FOR SEQ ID NO:6:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 4 amino acids(B) TYPE: amino acid(C) STRANDEDNESS: single(D) TOPOLOGY: linear(ii) MOLECULE TYPE: peptide(xi) SEQUENCE DESCRIPTION: SEQ ID NO:6:TyrValAlaGlu1(2) INFORMATION FOR SEQ ID NO:7:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 4 amino acids(B) TYPE: amino acid(C) STRANDEDNESS: single(D) TOPOLOGY: linear(ii) MOLECULE TYPE: peptide(xi) SEQUENCE DESCRIPTION: SEQ ID NO:7:TyrXaaAlaGlu1(2) INFORMATION FOR SEQ ID NO:8:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 4 amino acids(B) TYPE: amino acid(C) STRANDEDNESS: single(D) TOPOLOGY: linear(ii) MOLECULE TYPE: peptide(xi) SEQUENCE DESCRIPTION: SEQ ID NO:8:XaaValAlaGlu1(2) INFORMATION FOR SEQ ID NO:9:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 4 amino acids(B) TYPE: amino acid(C) STRANDEDNESS: single(D) TOPOLOGY: linear(ii) MOLECULE TYPE: peptide(xi) SEQUENCE DESCRIPTION: SEQ ID NO:9:XaaXaaAlaGlu1(2) INFORMATION FOR SEQ ID NO:10:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 4 amino acids(B) TYPE: amino acid(C) STRANDEDNESS: single(D) TOPOLOGY: linear(ii) MOLECULE TYPE: peptide(xi) SEQUENCE DESCRIPTION: SEQ ID NO:10:TyrGluValGlu1(2) INFORMATION FOR SEQ ID NO:11:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 4 amino acids(B) TYPE: amino acid(C) STRANDEDNESS: single(D) TOPOLOGY: linear(ii) MOLECULE TYPE: peptide(xi) SEQUENCE DESCRIPTION: SEQ ID NO:11:TyrGluValGlu1(2) INFORMATION FOR SEQ ID NO:12:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 4 amino acids(B) TYPE: amino acid(C) STRANDEDNESS: single(D) TOPOLOGY: linear(ii) MOLECULE TYPE: peptide(xi) SEQUENCE DESCRIPTION: SEQ ID NO:12:XaaGluValGlu1(2) INFORMATION FOR SEQ ID NO:13:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 4 amino acids(B) TYPE: amino acid(C) STRANDEDNESS: single(D) TOPOLOGY: linear(ii) MOLECULE TYPE: peptide(xi) SEQUENCE DESCRIPTION: SEQ ID NO:13:XaaGluValGlu1(2) INFORMATION FOR SEQ ID NO:14:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 4 amino acids(B) TYPE: amino acid(C) STRANDEDNESS: single(D) TOPOLOGY: linear(ii) MOLECULE TYPE: peptide(xi) SEQUENCE DESCRIPTION: SEQ ID NO:14:TyrValAlaGlu1(2) INFORMATION FOR SEQ ID NO:15:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 4 amino acids(B) TYPE: amino acid(C) STRANDEDNESS: single(D) TOPOLOGY: linear(ii) MOLECULE TYPE: peptide(xi) SEQUENCE DESCRIPTION: SEQ ID NO:15:TyrValXaaGlu1(2) INFORMATION FOR SEQ ID NO:16:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 4 amino acids(B) TYPE: amino acid(C) STRANDEDNESS: single(D) TOPOLOGY: linear(ii) MOLECULE TYPE: peptide(xi) SEQUENCE DESCRIPTION: SEQ ID NO:16:TyrValAlaAsp1__________________________________________________________________________ | The present invention relates to N-substituted derivatives of glutamic acid of pharmaceutical interest, to pharmaceutical compositions which include compounds of the invention and pharmaceutically acceptable carriers, to methods of their preparation, and to their use in purification of interleukin-1β converting enzyme (ICE). | 2 |
FIELD OF THE INVENTION
The present invention relates to a method of modifying data in an encoded data signal, comprising at least:
a decoding step for decoding said encoded data signal and providing a decoded data signal, a re-encoding step performed on a modified data signal and generating a coding error, a prediction step for providing a motion-compensated signal from said coding error and comprising at least a subtracting sub-step between an input data signal obtained at least from said decoded data signal and said motion-compensated signal for obtaining said modified data signal.
The invention also relates to video processing devices for carrying out said method. This invention, may be used, for example, when a broadcaster wants to introduce additional data into a sequence of coded pictures. This invention finds applications not just in the field of MPEG-2 compression, but more generally in any digital video data compression system.
BACKGROUND OF THE INVENTION
Modifying data in an encoded data signal has become a vital function in studio editing environments. A possible solution has been proposed in the international patent application WO 99/51033 (PHF98546). This patent application describes a method and its corresponding device for modifying data in an encoded data signal. This method allows an additional data signal insertion, e.g. a logo inserting, into an MPEG-2 bitstream thanks to bit rate transcoding. Logo insertion comes as an extension of the bit rate transcoder. The corresponding diagram, depicted in FIG. 1 , comprises a transcoding module 101 and a logo addition branch 102 . The general outline of the transcoding module 101 , well known to a person skilled in the art, comprises:
a residue decoding branch 118 for receiving the input signal 125 and providing a decoded data signal Error_I(n). This branch comprises in series a variable length decoding 107 , an inverse quantization 108 followed by an inverse discrete cosine transform 109 . a re-encoding/decoding branch 120 for providing the output signal 126 and its decoded version respectively. The re-encoding part, for providing said output signal, comprises in series a discrete cosine transform 110 , a quantization 111 , a variable length coding 112 followed by a buffer 113 , and regulation means 114 ensuring a constant picture quality of the output signal 126 , and a first subtracter 122 generating a coding error. The decoding part comprises in series an inverse quantization 115 followed by an inverse discrete cosine transform 116 . an intermediate branch 119 comprising a motion compensation 105 using motion vectors V(n) of the input signal, its associated memory 106 storing a previous signal, and a second subtracter 123 . This branch, also called prediction loop, avoids the quality drift in the output signal by applying a motion compensation to said coding error generated during the re-encoding step.
The logo addition branch 102 is implemented thanks to a residue addition to the decoded signal Error_I(n), by means of the adding sub-step 121 . This residue is formed by subtracting an additional data signal Logo(n) referenced 127 with a motion-compensated logo prediction referenced 129 , obtained by means of the motion compensation sub-step 103 , which is based on reference pictures containing logo previously stored in memory 104 and which uses the same vectors V(n) as the main input signal.
In the prior art diagram depicted in FIG. 1 , two motion compensations are performed: a first one 105 , well known and provided for correcting the quality drift on P and B pictures introduced by the quantization sub-step 111 , and a second one 103 on an additional data signal 127 . This motion compensation 103 generates said motion compensated signal PRED(Logo(n−1), V(n)) referenced 129 which is subtracted from said signal 127 . Said motion-compensated signal is indeed essential since it cancels undesired parts of the signal relative to signal 127 , previously motion-compensated by 105 , in the input signal of the re-encoding step. Moreover, as a motion compensation always requires a storage of a previous signal, two memories 104 and 106 are also needed. Then, with these two motion compensation operations and two memory blocks, this solution remains not only complex as regards the CPU burden, but also expensive as regards storage memory.
SUMMARY OF THE INVENTION
It is an object of the invention to provide a method of modifying data in an encoded data signal which requires less memory capacity and puts a lesser burden on central processing units (CPU).
The method of modifying data according to the invention is characterized in that it comprises:
a first sub-step for adding an additional data signal to said decoded data signal, for providing said input data signal, a second sub-step for adding said additional data signal to said coding error, said motion-compensated signal resulting from the motion compensation of the output signal of said second adding sub-step.
A variant of the previously characterized method is also proposed. It is characterized in that it comprises a sub-step for adding an additional data signal to said modified data signal, before said re-encoding step.
The corresponding diagrams, depicted in FIG. 2 and FIG. 3 respectively, are based on data addition in the pixel domain of the additional data signal 127 with the decoded data signal relative to the input data signal, or with signal situated in the transcoder drift correction loop, by means of said adding sub-steps.
According to the invention, in contrast to the prior art solution, no more separate motion compensation is applied to logo data since the motion compensation relative to logo data is merged with the motion compensation relative to the drift correction of the transcoder loop. The invention thus comprises a minimum number of functional sub-steps, leading to a cost-effective solution. Indeed, only one set of motion compensations and its associated memory storage is used, which simplification is possible in that advantage is taken of combinations between different sub-steps, and by using their own characteristics such as the linearity of the motion compensation.
Another object of the invention is to propose devices for carrying out the above-mentioned methods.
To this end, the invention relates in a first implementation, to a transcoding device for adding data to an encoded data signal, comprising:
a first means for adding an additional data signal to said decoded data signal for providing said input data signal, a second means for adding said additional data signal to said coding error, said motion-compensated signal resulting from the motion compensation of the output signal of said second means.
In a second implementation, the invention also relates to a transcoding device for adding data to an encoded data signal, characterized in that it comprises means for adding an additional data signal to said modified data signal, before re-encoding means.
Detailed explanations and other aspects of the invention are given below.
BRIEF DESCRIPTION OF THE DRAWINGS
The particular aspects of the invention will now be explained with reference to the embodiments described hereinafter and considered in connection with the accompanying drawings, in which identical parts or sub-steps are designated in the same manner:
FIG. 1 illustrates the outline, as known in the prior art, of a transcoder with its logo insertion branch,
FIG. 2 illustrates a first embodiment of the technical solution according to the present invention.
FIG. 3 illustrates a second embodiment of the technical solution according to the present invention.
DETAILED DESCRIPTION OF THE INVENTION
As was stated above, the present invention aims at reducing the cost of the prior art method for modifying data in an encoded data signal. Such an invention is well adapted to the case of MPEG-2 coded video signals as the input signal, but it will be apparent to a person skilled in the art that such a method is applicable to any coded signal that has been encoded with a block-based compression method such as, for example, the one described in MPEG-4, H.261 or H.263 standards. In the following, the invention will be detailed assuming that encoded video signals comply with the MPEG-2 international video standard (Moving Pictures Experts Group, ISO/IEC 13818-2).
FIG. 2 depicts the first cost-effective arrangement for data insertion into an encoded data signal, according to the present invention. This arrangement re-uses the aim of the transcoder described above, into which are inserted sub-steps aiming at modifying the input signal. Indeed, the input signal is modified by a pixel-based data signal 127 simultaneously introduced owing to two adding sub-steps:
the sub-step 121 placed at the output of the error residue decoding, more precisely on the output signal of the inverse discrete cosine transform 109 . The modification of the input signal, e.g. in the case of a logo insertion, is therefore first implemented by means of an addition between the inserted data signal 127 and the incoming data signal Error_I(n). This addition results in a signal corresponding to the positive input of the subtracting sub-step 123 . the sub-step 124 at the input of the memory 206 relative to the motion compensation 205 .
The modification of the input signal, e.g. in case of a logo addition, is therefore secondly implemented by means of an addition between the inserted data signal 127 and the output signal of the subtracting sub-step 122 . This addition results in a signal corresponding to the input signal of the memory 206 .
From an algorithmic point of view, this first arrangement proposed according to the invention is equivalent to the one described in the prior art of FIG. 1 , as it can be recursively demonstrated hereinafter. The following notations will be adopted for the demonstration:
V(n): vectors of picture number n, I(n): decoded input picture number n, Error_I(n): error residue of input picture number n, O 1 (n): decoded picture number n corresponding to the output signal of FIG. 1 , MEM 1 (n): picture number n stored in the frame memory 106 , O 2 (n): decoded picture number n corresponding to the output signal of FIG. 2 , MEM 2 (n): picture number n stored in the frame memory 206 , PRED(X(n), V(n+1)): motion compensation of picture X(n) using vectors V(n+1). It corresponds to a predicted version of picture X(n+1), T: transform defined by T(x)=IDCT(IQ(Q(DCT(x)))).
Note that the decoded pictures I(n), O 1 (n) and O 2 (n) are not represented by any figures since only compressed signals are accessible.
The equivalence between the prior art and the diagram of FIG. 2 will be demonstrated if for each n, the three following relations are valid:
O 1 ( n )= O 2 ( n ) 1)
MEM 1 ( n )= O 1 ( n )− I ( n )−Logo( n ) 2)
MEM 2 ( n )= O 2 ( n )− I ( n ) 3)
Obviously, the input signal and the inserted data signal 127 of FIG. 1 and FIG. 2 are supposed to be identical in this demonstration.
For the case where n=0, corresponding to an Intra-coded picture, it can be written:
Error — I ( 0 )= I ( 0 ) 4)
It can be deduced from FIG. 1 :
O 1 ( 0 )= T ( I ( 0 )+Logo( 0 )) 5)
MEM 1 ( 0 )= O 1 ( 0 )− I ( 0 )−Logo( 0 ) 6)
It can be deduced from FIG. 2 :
O 2 ( 0 )= T ( I ( 0 )+Logo( 0 )) 7)
MEM 2 ( 0 )= O 2 ( 0 )− I ( 0 ) 8)
It is possible to conclude from relations (5), (6), (7) and (8) that relations (1), (2) and (3) are valid for n=0. Let us suppose they are still valid at the rank n, and let us demonstrate that (1), (2) and (3) are also valid at the rank (n+1).
Let us now introduce the terms A(n+1) and B(n+1) as:
A ( n+ 1)=Error — I ( n+ 1)+Logo( n+ 1)−PRED(Logo( n ), V ( n+ 1))−PRED(MEM 1 ( n ), V ( n+ 1))
B ( n+ 1)=Error — I ( n+ 1)+Logo( n+ 1)−PRED(MEM 2 ( n ), V (n+1))
Since (2) and (3) are valid at the rank n, and since the motion compensation is linear, A(n+1) and B(n+1) become:
A ( n+ 1)=Error — I ( n+ 1)+PRED( I ( n ), V ( n+ 1)+Logo( n+ 1)−PRED( O 1 ( n ), V ( n+ 1)) 9)
A ( n+ 1)= I ( n+ 1)+Logo( n+ 1)−PRED( O 1 ( n ), V ( n+ 1)) 10)
B ( n+ 1)=Error — I ( n+ 1)+PRED( I ( n ), V ( n+ 1))+Logo( n+ 1)−PRED( O 2 ( n ), V ( n+ 1) 11)
B ( n+ 1)= I ( n+ 1)+Logo( n+ 1)−PRED( O 2 ( n ), V ( n+ 1)) 12)
Since (1) is valid for at the rank n, relations (10) and (12) become:
A ( n+ 1)= B ( n+ 1)= I ( n+ 1)+Logo( n+ 1)−PRED( O 1 ( n ), V ( n+ 1) 13)
It can be deduced from FIG. 1 and FIG. 2 :
O 1 ( n+ 1)= T ( A ( n+ 1))+PRED( O 1 ( n ), V ( n+ 1)) 14)
MEM 1 ( n+ 1)= T ( A ( n+ 1)− A ( n+ 1) 15)
O 2 ( n+ 1)= T ( B ( n+ 1))+PRED( O 2 ( n ), V ( n+ 1)) 16)
MEM 2 ( n+ 1)= T ( B ( n+ 1))− B ( n+ 1)+Logo( n+ 1) 17)
One can conclude from relations (13), (15) and (17) that:
MEM 1 ( n+ 1)= O 1 ( n+ 1)− I ( n+ 1)−Logo( n+ 1) 18)
MEM 2 ( n+ 1)= O 2 ( n+ 1)− I ( n+ 1) 19)
This means that relations (1), (2) and (3) are valid for the rank n+1, which proves the algorithmic equivalence between the arrangement of FIG. 1 of the prior art, and the first proposed arrangement depicted in FIG. 2 according to the invention. This proposed arrangement thus ensures that the modified output signal has the same quality as the one of the prior art but is obtained in a more cost-effective manner. Indeed, no more separate motion compensation and its associated memory is needed for the inserted data signal 127 , since said data can be directly inserted into the transcoding pseudo-prediction loop, this simplification being justified by the linearity of the motion compensation. This merging of the two motion compensations—if the insertion of the two adding sub-steps 121 and 124 , at no cost for most digital signal processors, is disregarded—represents a substantial gain in terms of CPU occupation as well as memory storage.
FIG. 3 depicts an alternative embodiment of the present invention. It is also based on a transcoder arrangement identical to the one previously described and depicted in FIG. 1 . Compared with a transcoder architecture such as the one depicted in FIG. 1 , only a few modifications are made to obtain a change in the input signal. Indeed, the input signal is modified by signal 127 introduced by means of only one adding sub-step 121 placed at the input of the re-encoding step, more precisely on the input signal of the discrete cosine transform 110 . The modification of the input signal, e.g. in the case of a logo addition, is therefore implemented by means of an addition between the inserted data signal 127 and the output signal of the subtracting sub-step 123 . This addition results in a signal corresponding to the input of the discrete cosine transform 110 . From an algorithmic point of view, this second arrangement is also equivalent to the prior art arrangement of FIG. 1 . The following notations will be used for the demonstration:
O 3 (n): decoded picture number n corresponding to the output signal of FIG. 3 , MEM 3 (n): picture number n stored in the frame memory 206 .
Note that the decoded pictures O 3 (n) is not represented by any figures since only compressed signals are accessible.
The same recursive demonstration can be made in proving for each n, the three following equations:
O 1 ( n )= O 3 ( n ) 20)
MEM 1 ( n )= O 1 ( n )− I ( n )−Logo( n ) (2)
(as demonstrated above)
MEM 3 ( n )= O 3 ( n )− I ( n ) 21)
Obviously, the input signal and the inserted data signal 127 of FIG. 1 and FIG. 3 are supposed to be identical in this demonstration.
For the case where n=0, corresponding to an Intra-coded picture, it can be written:
Error — I ( 0 )= I ( 0 ) 22)
It can be deduced from FIG. 3 :
O 3 ( 0 )= T ( I ( 0 )+Logo( 0 )) 23)
MEM 3 ( 0 )= O 3 ( 0 )− I ( 0 ) 24)
From relations (5), (6), (23) and (24), it is possible to conclude that relations (20) and (21) are valid for n=0. Let us suppose they are still valid at the rank n, and let us demonstrate that (20) and (21) are also valid at the rank (n+1).
Let us now introduce the terms C(n+1) as:
C ( n+ 1)=Error — I ( n+ 1)+Logo( n+ 1)−PRED(MEM 3 ( n ), V+ 1))
Since (21) are valid at the rank n, and since the motion compensation is linear, C(n+1) becomes:
C ( n+ 1)=Error — I ( n+ 1)+PRED( I ( n ), V ( n+ 1))+Logo( n+ 1)−PRED( O 3 ( n ), V ( n+ 1)) 25)
C ( n+ 1)= I ( n+ 1)+Logo( n+ 1)−PRED( O 3 ( n ), V ( n+ 1)) 26)
Since (20) is valid for the rank n, relation (26) becomes:
A ( n+ 1)= C ( n+ 1)= I ( n+ 1)+Logo( n+ 1)−PRED( O 1 ( n ), V ( n+ 1))
It can be deduced from FIG. 3 :
O 3 ( n+ 1)= T ( C ( n+ 1))+PRED( O 3 ( n ), V ( n+ 1)) 28)
MEM 3 ( n+ 1)= T ( C ( n+ 1))− C ( n+ 1)+Logo( n+ 1) 29)
It can be concluded from relations (15), (27) and (29), that:
MEM 3 ( n+ 1)= O 3 ( n+ 1)− I ( n+ 1) 30)
So relations (20) and (21) are valid for the rank n+1. This proposed scheme thus ensures that identical results will be obtained in the output signals of FIG. 1 and FIG. 3 . No more separate motion compensation and its associated memory on signal 127 are needed, and said pixel-based data signal 127 is introduced thanks to the only no-cost adding sub-step ADD. In terms of CPU occupation and memory storage, this solution in almost the same as the one of an isolated transcoder without data insertion, which is remarkable.
In FIG. 2 and FIG. 3 described above according to the invention, the input signal data is modified thanks to the insertion of the pixel-based data signal 127 by means of adding sub-steps. These inserted data may correspond to a logo, i.e. a single small picture, or a ticker, i.e. successive small different pictures. In both cases, each picture must be pixel-based, e.g. by being encoded according to the so-called bitmap format which corresponds to a rough digital image coding. Of course, before insertion by means of the adding sub-steps, said signal 127 may derive from an adapted pixel-based signal Logo_ori(n) referenced 328 in order to optimize the quality of the output signal, as it is only represented in FIG. 3 with step 317 , for example by changing the luminance or the chrominance levels, as far as their format is still compatible. It is obvious that such an adaptation does not restrict the scope and the degree of protection of the present invention.
This method of modifying data in an encoded data signal can be implemented in several manners, such as by means of wired electronic circuits or, alternatively, by means of a set of instructions stored in a computer-readable medium, said instructions replacing at least a portion of said circuits and being executable under the control of a computer or a digital processor in order to carry out the same functions as fulfilled in said replaced portions. The invention then also relates to a computer-readable medium comprising a software module that includes computer executable instructions for performing the steps, or some steps, of the method described above. | The invention relates to a method of modifying data in an encoded data signal 125 corresponding to successive pictures divided into sub-pictures, for providing an output modified data signal 126 . In particular, this invention can be used for the insertion of an additional data signal 127 into a compressed video signal 125 . The proposed schemes according to the invention are based on a transcoder arrangement including at least partial decoding means and partial re-encoding means. This method leads to a cost-effective solution compared to the prior art comprising a minimum number of functional sub-steps, in particular including a unique motion compensation sub-step 205 , taking advantage of simplifications and combinations between different sub-steps. | 7 |
CROSS-REFERENCE APPLICATIONS
This application is directed to an improved insualting material which is used to advantage to provide an improved insulative operating column of the type disclosed and claimed in commonly-assigned, co-pending Application Ser. No. 721,616 filed in the names of L. V. Chabala et al on Apr. 10, 1985.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an improved insulating material; the insulating material being a mixture of an insulating fluid and solid bodies.
2. Description of the Related Art
Various devices utilize gas-filled vessels such as interrupting units at high voltage. It is often required to actuate parts within the vessel by employing a ground-potential mechanism and an insulating actuating member that connects the ground potential mechanism to the parts within the vessel.
The actuating member often passes through a hollow insulating support column that is filled with the same gas as the vessel at top where the gas is able to communicate between the vessel and the support column. This arrangement includes the drawbacks that the support column has a number of joints that must be sealed against gas leakage. This requires special handling during manufacture. Field assembly is also complicated since gas is normally added at the time of installation and contamination must be avoided either as to the pressurized vessel or the support column. Additionally, while in service, the gas presure must be monitored by special monitoring equipment to ensure that no breach of insulating integrity has occurred in the column and the interrupting unit.
An insulating liquid can be used to overcome the drawbacks with pressurized gas columns. The liquid is easier to seal and contamination is more easily avoided. However, a desirable fluid is relatively expensive and if the fluid is lost through leakage, moisture can enter the column and collect on the internal surfaces thereof; the insulating properties of the column thereby being reduced.
A solid insulation can be utilized but it is difficult to provide movement of actuating members through solid insultion. Further, it is difficult to prevent air pockets that would lead to dielectric breakdown.
Prior arrangement have utilized an insulating fluid and sand where the sand settles to the bottom and packs densely or cakes. Movement of an actuating member through such an arrangement would also prove difficult due to the high viscous drag on the actuating member and the settling and packing of the sand.
While these arrangements are generally suitable for some purposes, it is always desirable to provide improved insulating materials and insulating opertor columns that exhibit fewer shortcomings in the areas of sealing problems, maintenance, thermal expansion problems, air pockets and uniformity.
SUMMARY OF THE INVENTION
Accordingly, it is a principal object of the present invention to provide an improved insulating material that avoids one or more drawbacks of the prior art.
It is another object of the present invention to provide an insulating material that is a mixture of an insulating fluid and solid insulative bodies; the insulating material providing desirable surface-coating characteristics while also exhibiting low-viscosity properties.
It is a further object of the present invention to provide an insulating material that includes an insulating fluid and solid bodies while remaining relatively free-flowing and having a desirable fluidity.
It is a further object of the present invention to provide an improved insulating material including an insulating fluid and solid insulative particles for use in a hollow insulating column, the insulating material exhibiting a desirable apparent viscosity to permit the movement of an operating member within the insulating material and preventing the deposition of moisture on the internal surfaces of the insulating column even if some of the insulating fluid is lost through leakage; the insulating material including an appropriate combination of particle geometry and population per unit volume to achieve the desired properties while permitting a desirably low ratio of fluid volume to particle volume.
Briefly, these and other objects and advantages of the present invention are achieved by a mixture of an insulating fluid and solid insulative bodies or pellets to provide an improved insulating material that is relatively free-flowing and of desirable fluidity. The size and geometry of the solid bodies are chosen to avoid caking or conglomerate packing, and to be relatively free of interlocking with each other. Generally spherical bodies possess these desired qualities. However, bodies of other geometries such as elongated or flattened, smoothly contoured bodies may also be suitable for various applications. For example, the geometry of the solid bodies can be generally described by an aspect ratio defined by the largest dimension divided by the smallest dimension. In this regard, an aspect ratio of 3 to 1 is generally suitable for many applications while an aspect ratio in the range of 5 to 10 to one may be suitable for some applications provided that the shapes are non-interlocking and the percentage by volume of the solid bodies is appropriate.
The insulating material exhibits desirable insulating, conformal coating, surface adhesion, and low apparent viscosity properties, while also providing desirable properties in the event that some of the fluid is lost through leakage. For example, the use of the insulating material of the present invention to fill the bore of an insulator provides the desirable properties of a fluid to coat the inside surfaces of the insulator and provides moisture-repellant properties. In the event that some of the insulating fluid is lost through leakage, the build-up of moisture of the inside surfaces of the insulator is substantially reduced as compared to the performance of an insulating fluid without the provision of the solid, insulative bodies. Further, the insulating material of the present invention reduces the amount of relatively expensive insulating liquid that would be required to fill the bore. The insulating material of the present invention also reduces the amount of material in the insulator that exhibits undesirable volumetric changes with temperature. Accordingly, this reduces the size of any volume compensator that would be required for an all-liquid filler.
In insulating columns that are required to allow movement of an actuating member within or through the column at relatively high speeds, the insulating material in the column must exhibit an appropriate density and apparent or effective viscosity. The term apparent or effective viscosity refers to the relatively low viscosity encountered by a moving object within the insulating material as will be explained in more detail hereinafter. The apparent viscosity is relatively low as compared to most solids and is substantially unchanged from that of an insulating fluid; e.g. not more than an order of magnitude in a specific application which is a relatively small change for viscosity parameters. The insulating material of the present invention provides these desirable characteristics through the provision of predetermined densities, sizes, shapes and population of the solid insulative bodies. Prior insulating arrangements that employed liquid and sand where the sand settles to the bottom and packs densely would not be acceptable for this application. The high-viscous drag on the actuating member resulting from the settling and packing of the prior insulating arrangements inhibits high-speed movement of an actuating member through a column.
BRIEF DESCRIPTION OF THE DRAWING
The invention, both as to its organization and method of operation, together with further objects and advantages thereof, will best be understood by reference to the specification taken in conjunction with the accompanying drawings in which:
FIG. 1 is a partial elevational view, partly in section, illustrating an application of the insulating material of the present invention within an insulator;
FIG. 2 is an elevational view, partly in section, of an insulating column fabricated and assembled in accordance with the present invention; the insulator column serving a support function and also internally carrying an operating member; and
FIG. 3 is an elevational view, partly in section and with parts cut away, of an insulating column fabricated and assembled in accordance with the present invention; the insulating column serving a support function, carrying an internl operating member, and being rotatable to provide an operating drive function.
DETAILED DESCRIPTION
The improved insulating material of the present invention is provided by a mixture of an insulating fluid and solid bodies, particles, or pellets of insulating material. The resulting mixture of the present invention provides desirable insulating, surface adhesion and low apparent or effective viscosity characteristics while providing an advantage over the insulating fluid for certain applications as will be explained in detail hereinafter. Additionally, the low coefficient of thermal expansion of the solid material provides an insulating material having significantly lower net thermal expansion properties than that of the insulator fluid per se. The solid particle density, size, geometry and population density can be suitably varied to provide various characteristics of the insulating material regarding apparent viscosity and the reduced volume of the insulating fluid. The geometry of the solid particles and the population density can be varied while still providing an insulating material that is relatively free-flowing and of desirable fluidity; desirable properties for many applications such as to fill the bore of an insulating support column that includes an operating member that is moved within the column. For example, the insulating material provides low apparent or effective viscosity to the moving operating member and provides coating the internal surfaces of the insulator support column to act as a moisture-repellant for preventing moisture build-up even if some of the insulating fluid is lost through leakage. The insulating material of the present invention also functions as a lubricated insulating material as to the solid material included in the mixture. Further, considering the geometry of the solid material, while generally spherical bodies are suitable to practice the present invention, various other geometries are also suitable. However, to achieve desirable reductions in the volume of insulating fluid in the insulating material, while maintaining a relatively free-flowing material, the geometry of the solid material should be chosen to avoid caking or conglomerate packing and interlocking.
While the insulating material for purposes of illustrative example is described in detail hereinafter to provide improved insulative columns having operating members movable therein and therethrough, it should be realized that the described features and characteristics are applicable to numerous other applications and varieties of apparatus, including both static and dynamic arrangements, as will be apparent to those skilled in the art.
For example, and referring now to FIG. 1, the insulating material 10 of the present invention in a typical application is provided to fill the longitudinal bore 12 of an insulator 14 fabricated and assembled in accordance with the present invention. The insulator 14 may be utilized to replace the insulating support member for the electrical switch or interrupting unit such as disclosed in U.S. Pat. No. 3,432,780. The insulator 14 may also be utilized to replace the rotating spport column, such as disclosed in U.S. Pat. No. 3,508,178. In any event, the insulating material 10 includes an insulating fluid 16 and solid bodies 18 of insulating material. While the bodies 18 are depicted as generally round in FIG. 1, for purposes of illustration, it should be realized that the shape of the bodies 18 can be various shapes, sizes and densities while still providing the insulating material 10 with the desired properties. For the purposes of a particular application, the insulating material 10 provides coating and adherence to the internal walls of the insulator 14 due to surface tension, surface adhesion and capillary attraction. Further, should a leak occur in the insulator 14 such that some of the insulating fluid 16 is lost, the insulating properties of the insulator 14 will decrease gradually as opposed to the more rapid decrease if the insulator were filled solely with an insulating fluid; the decline in insulating properties being caused by moisture entering the insulator and depositing on the walls. The insulating material 10 of the present invention inhibits moisture build-up since the solid bodies 18 provide a large surface area that retains the insulating fluid. Accordingly, the insulating material 10 aids in preventing moisture from coating the walls of the insulator 14 which may be drawn into the insulator 14 by pressure variations; desirably, the solid bodies 18 being an appreciable proportion by volume of the insulating material 10 to aid in retaining the insulating fluid 16 of the insulating material 10.
Referring now to FIG. 2, the use of insulating material 10 is advantageous in the fabrication and assembly of the insulating support column 30 of the present invention. The insulating support column 30 includes a longitudinal bore 12 formed through an insulator body 31 within which is disposed an elongated operating member 32. The elongated operating member 32 is mounted for sliding or rotation in insulating support column 30 by means of suitable bearings 34 and 36. The lower bearing 34 is mounted in a lower seal housing 38 through which the operating member 32 passes. An upper seal housing 40 carries the bearing 36. The upper seal housing 40 is affixed to a mounting flange 42 which in turn is fastened to the insulator body 31. Similarly, the lower seal housing 38 is affixed to a mounting flange 44 which in turn is fastened to the insulator body 31.
The insulating support column 30 is attached to a support beam or base via the lower seal housing 38. In one specific arrangement, the operating member 32 is driven at a lower end fitting 46 over a linear path referred to at 50. The linear movement of the operating member 32 is coupled via an upper end-connector 52 through suitable linkage to operate the specific apparatus attached thereto; e.g., an interrupter unit.
In accordance with the operation of the insulating support column 30 with the operating member 32, the insulating material 10 provides all the desirable characteristics as were utilized for use with the insulator 14. Additionally, the insulating material 10 functions in the insulating support insulator 30 to provide reduced seal requirements and leakage considerations than would be the case if an insulating fluid alone were utilized. Since the insulating material 10 exhibits relatively apparent or effective viscosity characteristics, the operating member 32 in specific applications is capable of rapid operation without detrimental viscous drag.
Considering other applications of the insulating material 10 and referring now to FIG. 3, the insulating material 10 is used to fill the bore 116 of the insulator 114 of the operating column 112, which may also be referred to as a rotatable support column. The insulative operating column 112 is arranged to be rotated and includes an operating member 142 longitudinally disposed therethrough to provide independent rotary and linear drive arrangements.
The insulating operating column 112 is mounted for rotation with respect to a base housing 120 by bearings 124,126 cooperating with a base member 122 of the insulating operating column 112. The base member 122 is fixedly fastened to the insulator 114 by means of suitable fasteners referred to generally at 128. The fasteners 128 sealingly interconnect a mounting flange 130 of the insulator 114 and the base member 122. In the specific illustration, the housing 120 is carried by a base beam 134 and rigidly attached thereto by fasteners 136. The insulating support column 112 is rotated by a drive linkage referred to at 138 via interconnection to a drive arm 132 of the base member 122. Accordingly, operation of the drive linkage 138 represents a rotary drive input as illustrated by the bidirectional at 140.
The elongated operating member 142 is disposed for rotation and reciprocation with respect to the base member 122 via bearing 144. The lower end of the elongated operating member 142 extends through the base member 122 and fixedly carries an end fitting 146. As illustrated in FIG. 3, the end fitting 146 is pivotally connected to a bell crank 148. Accordingly, clockwise and counterclockwise pivoting of the bell crank 148 causes linear movement of the operating member 142 in the directions illustrated at 150; the movement of the bell crank 148 representing a linear drive input.
The operating member 142 at the upper end thereof, as shown in FIG. 3, passes through the insulator 114 and a base flange 154 fastended to an upper seal housing 155. The upper seal housing 155 is fixedly attached and sealingly connected to an upper insulator mounting flange 153. In turn, the upper mounting flange 153 is affixed to the upper portion of the insulator 114. The operating member 142 passes through the apertured mounting flange 153. The seal housing 155 includes a bearing 151 for the operating member 142. In a specific arrangement, the operating member 142 is fabricated from glass-epoxy tubing or rod. For a more detailed discussion of the insulative operating column 112, reference may be made to co-pending, commonly assigned U.S. application Ser. No. 721,616 filed in the names of L. V. Chabala et al on Apr. 10, 1985.
In accordance with important aspects of the present invention, the insulating material 10 provides features in the insulative operating column 112 additional to those provided for the support insulator 14 of FIG. 1 and the support insulator 30 of FIG. 2. Specifically, the insulating material 10 efficiently allows for rotation of the insulative operating column 112 and rapid translational movement of the operating member 142. It should be understood that in another specific arrangement, the operating member 142 is rotated instead of translated. Further, in yet other specific arrangements, the operating member may be arranged for total internal operation within an enclosure.
Considering one specific illustrative example of the composition of the insulating material 10 for the insulative operating column 112, it has been found suitable to utilize Dow Corning Silicone Fluid available under the designation DC 561 or other suitable liquid having similar dielectric properties and viscosity within the range of 10 to 500 centistokes for the insulating fluid 16. It has also been found suitable to utilize, for the solid bodies 18, generally rounded polyethylene pellets or other suitable material approximately one-eighth of an inch in overall size with the quantity of fluid 16 being sufficient to completely submerge the pellets 18. The size, density and volume of the solid bodies 18 is chosen to decrease the volume of the liquid while not unduly raising the viscous drag effect on the operating member 142 when the member 142 is rapidly moved. A lower quantity of fluid also results in a cost savings as well as the other advantages discussed herein. The proportion of the solid bodies 18 by volume is approximately 60-70% with the densities or specific gravities of the pellets 18 and the dielectric fluid 16 being approximately equal to each other. For this specific example, the insulating material 10 exhibits an effective or apparent viscosity of approximately 500 centistokes if a fluid 16 having a viscosity of 50 centistokes is utilized. Accordingly, the increase of an order of magnitude of the viscosity represents a relatively small, substantially unchanged viscosity as compared to solids and to the relatively large variations of viscosity parameters with respect to temperature. With approximately equal densities, the bodies 18 neither float above the liquid 16 nor pack tightly at the bottom. The acceptably low coefficient of net thermal expansion of the insulating 10 material permits higher initial fill levels during manufacture. Accordingly, the insulating material 10 functions as a lubricated insulating material.
This mixture has been found to conformally coat the operating member 142 and the interior walls of the insulator 114, which in a specific embodiment is fabricated from porcelain. The use of the silicone fluid is preferred over petroleum-based liquid or transformer oil because the silicone liquid is less flammable, is odorless and has no toxic effects. The size of bodies 18 is chosen so that an individual body is not a significant factor of the dimension from the bore 116 to the operating member 142 in the insulator 114. While plastics and and other materials are suitable for the solid bodies 18, the mateial should not introduce abrasive powders that could damage any seals or operating members. Further, with this mixture, even should the lower housing be opened or develop a leak, which might ordinarily permit a nearly total loss of an all-fluid filler, an effective and therefore significant quantity of fluid 16 remains bound to the solid bodies 18, to the inner walls of the porcelain forming the bore 116, and to the operating member 142. Accordingly, the surfaces are sufficiently coated through capillary attraction, surface tension, and surface adhesion to maintain appropriate insulating characteristics to prevent electrical leakage paths within the insulator 112 and to prevent deposition of moisture. Further, the seals on the operating member 142 are required to withstand only the gravity head of the fluid 16 within the insulator 114. An aerator in the upper seal housing 155 vents the interior of the insulator 112 to the ambient for pressure equalization without the inspiration of moisture. Such an aerator is disclosed in U.S. Pat. No. 3,696,729 issued to L. V. Chabala et al on Oct. 10, 1972 which is hereby incorporated incorporated by reference.
While the solid bodies 18 have been discussed as being of generally uniform size, in other specific embodiments, the solid bodies 18 include bodies of two or more different sizes such that the interstices between the larger bodies will be generally filled by the smaller bodies; thus providing a further reduction in the volume of the insulating fluid 16 if this should be desired. Further, the solid bodies 18 in other specific embodiments are non-rigid bodies of elastomeric material.
While there has been illustrated and described various embodiments of the present invention, it will be apparent that various changes and modifications will occur to those skilled in the art. For example, while a specific illustrative example utilized a fluid 16 having a viscosity of 50 centistokes to provide an insulating material having a viscosity of 500 centistokes, it should also be realized that the present invention may be practiced using a fluid 16 of various viscosity parameters; a fluid 16 having a lower viscosity value will provide an insulating material 10 exhibiting lower viscosity values. Further, while approximately equal densities are discussed, it should be understood that relative densities for the insulating fluid 16 and the solid bodies 18 within the range of 0.7 to 1.0 each other may also provide suitable results for particular applications. Additionally, the size of the solid bodies can also be widely varied for various applications; e.g. from 0.01 to 0.5 inch. As discussed hereinbefore, the shape or geometry of the solid bodies 18 may also be widely varied. It is intended in the appended claims to cover all such changes and modifications as fall within the true spirit and scope of the present invention. | An improved insulating material is provided. The insulating material is a mixture of an insulating fluid and solid insulative bodies. The insulating material exhibits desirable insulating, conformal coating, surface adhesion, and low-viscosity characteristics. For example, when the insulating material is used to fill the cavity of a hollow insulator, the insulating material prevents any moisture that enters the insulator from adhering to the walls that define the cavity; thus maintaining the insulating qualities of the insulator. In the event that some of the fluid is lost through leakage, the insulating material also aids in preserving the insulating qualities of the insulator. | 8 |
[0001] This application claims priority from U.S. Provisional Application Serial No. 60/174,714 filed Jan. 6, 2000. The entirety of that provisional application is incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The invention relates to a step system for providing a toehold/slide guard on inclined surfaces, such as a roof.
[0004] 2. Discussion of the Background
[0005] Providing a safe and secure foothold for workers working on an inclined surface, such as a roof, has been a concern in the construction industry for years. The most common method for providing a foothold on a roof today is by nailing a 2×4 (as used herein, 2″×4″refers to a 2 inch by 4 inch piece of lumber) directly to the roof. This method has several disadvantages. First, nailing a 2×4 to the roof creates holes in existing roofing materials. Second, because there is no protective material surrounding the 2×4, workers using the 2×4 as a toehold/slide guard will often dislodge granular material that is attached to roof shingles. Third, the lack of protective material around the roof step allows soil and other debris from workers' shoes to be deposited on the roof.
[0006] The above identified short comings associated with the use of a 2×4 for toeholds/slide guards has led to the development of a number of alternative systems. These alternative systems can generally be classified into one of two categories: 1) ladder-like roofing systems; and 2) platform systems. Ladder-like systems generally provide steps, similar to a ladder, that are intended to allow a worker to climb the roof. An example of a ladder-like system is the system described in UK Patent No. 2,131,475. Systems such as these provide a number of steps, spaced approximately the same distance as steps in a ladder. One drawback to the system proposed in UK Patent No. 2,131,475 is that the system is comprised of a rigid board, which makes the system cumbersome for use on a roof. Another example of a ladder-like system is disclosed in U.S. Pat. No. 2,708,543. This system discloses a number of triangular steps attached to a flexible rubber/foam backing board. Although this system has the advantage of providing a flexible backing, it still suffers from the relative disadvantage of being heavy and cumbersome for use on a roof. More importantly, both of these ladder-like systems do not provide toeholds that are spaced sufficiently far enough apart to allow a worker to kneel between successive, or neighboring, toeholds. Thus, while such ladder-like systems are useful for climbing a roof, such systems are not as useful for a roofer who needs to kneel while perched on a toehold to install roofing shingles.
[0007] The second type of alternative roofing systems are platform based roofing systems. An example of a platform based roofing system is disclosed in U.S. Pat. No. 4,946,123. This system consists of an angled bracket that holds a 2×4 at an angle with respect to the roof to provide toehold. This system suffers from many of the same drawbacks associated with using a single 2×4, including the necessity of driving nails through the bracket to secure the bracket to the roof. Several more complicated platform systems are also known in the art, including those described in U.S. Pat. Nos. 4,785,606; 5,908,083; and 5,624,006. These systems all provide good working surfaces, but are complicated and clumsy for use on a roof. Variations on the platform based systems are mobile platforms that can be attached to a worker's feet such as the platform described in U.S. Pat. No. 3,726,028 and UK Patent No. 2,131,475. Systems such as these are also cumbersome to use on a roof. What is needed is a light weight, easy to use system that provides a toehold/slide guard for a worker that will allow the worker to kneel on the roof in order to perform tasks such as installing shingles.
SUMMARY OF THE INVENTION
[0008] The present invention overcomes to a great extent the deficiencies found in the prior art discussed above by providing a step system comprising a number of spaced apart steps attached to a connecting material, wherein the steps are spaced sufficiently far apart to allow an adult to kneel between neighboring steps. In preferred embodiments, the connecting material is a light weight nylon and the steps are formed from high strength, light weight plastic. Highly preferred embodiments of the present invention employ a woven nylon material, approximately 900-1,000 denier. This type of fabric has been found to exhibit exceptional traction when used on asphalt shingles. The material is preferably solid. Besides providing traction on the roof surface, the use of a “solid” material also protects the roof both from dirt and other debris and from worker's shoe which tends to dislodge the granular material found on many asphalt shingles. The connecting material may be provided with a number of grommets, suitable for attaching the connecting material to the roof. In preferred embodiments of the invention, the step system is of sufficient length such that it can be draped over the entire roof and secured in sections to the roof. In preferred embodiments, the step includes a handle, which may also be used to secure a life line to the step. Preferably, the steps are separated by approximately 20 inches to approximately 36 inches, which is generally sufficient to provide room for a worker to kneel using one step as a toehold/slide guard. The step system may be any width, but as preferably between approximately 18 inches to approximately 50 inches wide, which is generally sufficiently wide to provide a toehold for both of a worker's feet.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] A more complete appreciation of the invention and many of the attendant features and advantages thereof will be readily obtained as the same becomes better understood by reference to the following detailed description when considered in connection the accompanying drawings, wherein:
[0010] [0010]FIG. 1 is a perspective view of a roof step system according to the present invention in use on a roof.
[0011] [0011]FIG. 2 is a bottom view of the roof step system of FIG. 1.
[0012] [0012]FIG. 3 is a top view of the roof step system of FIG. 1.
[0013] [0013]FIG. 4 is an enlarged top view of a portion of the roof step system of FIG. 1.
[0014] [0014]FIG. 5 is a front view of the roof step system of FIG. 1.
[0015] [0015]FIG. 6 is a side view of the roof step system of FIG. 1.
[0016] [0016]FIG. 7 is a perspective view of a preferred embodiment of the roof step according to the present invention.
[0017] [0017]FIG. 7A is a perspective view of a functional application of the preferred embodiment shown in FIG. 7.
[0018] [0018]FIG. 8 is a perspective view of another preferred embodiment of the roof step according to the present invention.
[0019] [0019]FIG. 9 is a perspective view of yet another preferred embodiment of the roof step according to the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0020] Referring now to the drawings wherein like reference numerals designate identical or corresponding parts throughout the several views, a perspective view of a roof step system 100 installed on the roof 10 of a building 20 is shown in FIG. 1. A worker 30 is using the roof step system 100 to install shingles 12 . As shown in FIG. 1, the roof step system 100 extends over the peak of the roof 10 . The roof step system may be attached to the other side of the roof before the shingles are attached to that side, or may extend entirely over the other side of the roof and be attached at a place on the house, thereby avoiding the necessity of creating holes in the roof 10 sheathing. The spacing between successive steps 130 on the roof system 100 allows the worker 30 to kneel between successive steps 130 . The step system 100 also protects installed shingles 12 from being scuffed and dirtied by the worker's feet.
[0021] [0021]FIG. 2 is a bottom view of the roof step system 100 . FIG. 2 illustrates the connecting material 110 . The connecting material 110 may be any material that is sufficiently strong to connect the step. In preferred embodiments, the material 110 is solid, or closed (as used herein, a solid or closed material is a material of a sufficiently dense weave such that dirt and other debris is prevented from passing through the material 110 ). However, other types of material may also be used. These other types of material may include open nets or meshes. It is also possible to use two thin strips of material spaced apart such that the strips of material are attached to opposite ends of a step 100 . In a highly preferred embodiment of the present invention, the connecting material is made from a heavy gauge (900 to 1,000 denier) nylon pack cloth. This material has been found to exhibit excellent traction on commonly used asphalt roof shingles. As can be seen with reference to FIG. 3, in an even more highly preferred embodiment of the invention, the fabric 110 is reenforced by thin nylon strips 120 , comprised of a 2 inch wide 6000 lb. break strength nylon/seat belt webbing for added strength.
[0022] Still referring to FIG. 3, a distance D separates the toehold 134 of one step 130 from the start of a successive step 130 . The distance D is chosen to allow a worker to kneel between successive steps 130 . Preferably, the distance D is between approximately 20 inches and approximately 36 inches.
[0023] Referring now to FIG. 4, it can be seen that the reenforcing strips 120 include grommets 140 . The grommets are used to secure the step system 100 to a nail, screw, or other object. Experience has shown that in many situations, a single grommet 140 on each side of the top of the step system 100 is sufficient to secure the step system 100 . This is partially due to the excellent traction provided by the connecting material 110 . However, a plurality of grommets 140 are provided to allow multiple screws or nails to be used to secure the step system 100 to the roof for the sake of safety; especially when the step system 100 is used on an uncovered plywood roof. The multiple grommets 140 also allow the roof step system 100 to be attached to a roof at a number of different points.
[0024] The step 130 is attached to the connecting material 110 by 6000 pounds of nylon seat belt webbing 120 . In the embodiment shown in FIG. 4, two slots 138 per side are used to attach the step 130 to the connecting material 110 through the reenforcing strip 120 . Any number of fasteners other than nylon seat belt webbing 138 could be used to secure the step 130 to the connecting material 110 , but nylon seat belt webbing is preferred because the nylon webbing 120 has low profile on the opposite side of the material 110 .
[0025] The step 130 includes a base 132 having a width W. The width W is chosen to prevent the step 130 from tipping over when used as a toehold/slide guard. In preferred embodiments, the width W is approximately 8 inches. The width W of the connecting material is approximately 10 inches to approximately 30 inches wide. More preferably still, the step 134 may be comprised of an textured plastic, which has been shown to provide surprisingly good traction, especially when sneakers are worn.
[0026] Referring now to FIG. 5, it can be seen that the step 130 includes a toehold 134 of a height H. In preferred embodiments, the height H is equal to approximately 4 inches. Greater heights H are also possible, but the use of greater heights would require an increase in the width W of the base 132 of the step 130 . Also shown in FIG. 5 is a handle 136 , which is formed by removing portions of the toehold 134 . The handle 136 provides a convenient surface for a worker to grab. The handle 136 may also be used to provide a point at which a life line could be attached to the step system 100 . Such a life line is intended to be a short, e.g., 6 foot, life line. A short life line such as this prevents the step system 100 from being exposed to excessive force in the event that a worker should lose his footing. Another advantage of a short life line is convenience of use.
[0027] The step 130 is preferably comprised of a high strength, light weight plastic. Of course, other materials could also be used. For example, steps comprised of aluminum, steel and/or vulcanized rubber are also possible. It should also be noted that it is possible to use the solid nylon seat belt webbing 6000 pounds connecting material 110 without steps 130 . Used in this manner, the connecting material 110 provides good traction while keeping the roof 10 clean.
[0028] As shown in FIGS. 5 and 6, the toehold 134 is solid other than the cutout for the handle 136 . One advantage to this arrangement is that the toehold 134 can be used by a worker 30 as a tool rest as shown in FIG. 1.
[0029] Further as shown in FIG. 7, in a preferred embodiment of the step 130 , the base 132 includes keyhole-shaped sleeves 142 that are designed to permit passage of a nail, screw, or other fastener (not shown), in order to secure the step 130 to the roof surface. The keyhole shape allows the step 130 to be removed from the fastener without having to remove and reinstall the fastener, or without having to remove the fastener and patch or repair the hole left by the removed fastener. Furthermore, the keyhole-shaped sleeve 142 permits step 130 when installed to be anchored in place by sliding the step 130 so that the fastener passes through the narrow portion of keyhole-shaped sleeve 142 . In the example shown in FIG. 7, it is anticipated that 1.5 inch #10 Phillips head screws will be used, and upon removal of the step 130 , the screws are simply countersunk into the roofing material to maintain an impervious surface.
[0030] A further advantage to the preferred embodiment shown in FIG. 7 is that individual roof steps may be placed in irregular patterns as conditions require. As shown in FIG. 7A, at the discretion of the user, connecting material 110 may be used between individually placed steps 130 .
[0031] [0031]FIG. 8 displays another preferred embodiment of the step 130 , wherein the step is especially suitable for use on vertical or steeply pitched planes. In the preferred embodiment shown in FIG. 8, toehold 134 has non-skid surface 144 which permits the user to maintain stable footing while working on the vertical or steeply pitched plane. In the preferred embodiment shown in FIG. 8, the non-skid surface 144 is provided through a pattern of molded knurls, but the non-skid surface can also be provided through the use of applique, sand paint, or other techniques familiar to persons of ordinary skill in the art. Keyhole-shaped sleeves 142 are preferably placed relatively close to toehold 134 , to minimize the stress on the fasteners (not shown) that are used to attach step 130 to the roof or steeply pitched plane.
[0032] Turning to FIG. 9, a further preferred embodiment of the step 130 is shown, wherein the overall length of the step is increased, to permit extensive lateral movement by the user. The preferred embodiment shown includes multiple keyhole-shaped sleeves 142 , preferably placed at construction industry-relevant standardized intervals such as 16 inches and 24 inches. The embodiment depicted in FIG. 9 further includes non-skid surface 144 , and one edge of step 130 includes ruler demarcations 146 to indicate length from any point along step 130 . Multiple cutouts for handholds 136 permit one or more users conveniently and safely to carry the preferred embodiment shown. As shown in FIG. 9, it is anticipated that the preferred embodiment of the step will be formed from 14 gauge cold-rolled or cold-drawn steel, but any material of sufficient strength, resilience, resistance to corrosion and other desirable properties, which will be obvious to those of ordinary skill in the relevant art, may be used.
[0033] While the invention has been described in detail in connection with the preferred embodiments known at this time, it should be readily understood that the invention is not limited to such disclosed embodiments. Rather, the invention can be modified to incorporate any number of variations, alterations, substitutions or equivalent arrangements not heretofore described but which are commensurate with the spirit and scope of the invention. Accordingly, the invention is not to be seen as limited by the foregoing description, but is only limited by the scope of the appended claims. | A step system for providing a toehold/slide guard on inclined surfaces, such as a roof is disclosed. Individual steps including a toehold are connected at variable distances by flexible material permitting the steps to be spaced sufficiently far apart to allow an adult to kneel between neighboring steps. In preferred embodiments of the step system, individual steps include molded cutout handles, reenforced grommets for passage of fasteners, and non-skid surfaces for additional safety when the step system is employed in steeply pitched planes. | 4 |
FIELD OF THE INVENTION
The invention relates to a safety ski binding having a sole plate which is pivotally supported on a ski-fixed pivot pin and has a front jaw at one end and a heel holder at the other end.
BACKGROUND OF THE INVENTION
A known design of this type, as it is described in German OS No. 31 02 010, uses two pairs of toggle levers to lock the sole holder in the skiing position. However, these are difficult to mount. Furthermore, the known heel holder is relatively complicated in its construction.
The purpose of the invention is to overcome the disadvantages of the known construction and to provide a safety ski binding which can be easily manufactured and mounted.
Two constructions are available for attaining the mentioned purpose. A compact construction of the heel holder is thereby assured in both cases and its mounting is simplified. Furthermore, a separation of the functions of the spring is achieved.
A further characteristic of the invention permits that the piston, which is loaded by a spring for controlling the vertical release, can act directly onto the locking lever.
Further, the provision of two guide rods for the pressure springs, which control the release in a horizontal plane, are fixed to the control lever. The points of engagement of the two springs on the control lever are exactly defined.
Further, the invention is distinguished by the force of the spring, which is designated for controlling the pivoting of the sole holder in the vertical direction, being transmitted to both sides of the control lever and onto the locking lever. Thus, the spring can engage centrally on the control lever for controlling the release in a horizontal plane, which has advantages with respect to facilitating a symmetrical design.
A further feature of the invention locates the adjusting screw, which serves to adjust the initial tension of the pressure spring loading the roller controlling the release in a horizontal plane, so that it can be adjusted only by a trained mechanic. An adjusting of the adjusting screw by a layperson is thus practically impossible. With this accidents caused by incorrect adjustment of the spring can be prevented.
BRIEF DESCRIPTION OF THE DRAWINGS
Two exemplary embodiments of the subject matter of the invention are illustrated in the drawings, wherein:
FIG. 1 is a side view of the entire safety ski binding;
FIG. 2 is a vertical longitudinal cross-sectional view of the heel holder of the safety ski binding according to a first embodiment and in the skiing position;
FIGS. 3 to 5 are cross-sectional views similar to FIG. 2 but showing the cooperating structures on the sole holder and the release lever in a plane behind the cross-sectional view of FIG. 2;
FIG. 6 is a cross-sectional view taken along the line III--III of FIG. 2;
FIG. 7 is a vertical longitudinal cross-sectional view of the release lever of the heel holder; and
FIG. 8 shows a second exemplary embodiment of a heel holder, which is also in skiing position, in a vertical longitudinal cross-sectional view.
DETAILED DESCRIPTION
The safety ski binding illustrated in FIGS. 1 to 7 is a so-called plate binding. A base plate 2a, which carries a pivot pin 2b, is provided on a ski 2. A sole plate 1 is pivotally supported about the pivot pin 2b in a horizontal plane. A front jaw 2c is mounted on the front end of the sole plate 1 and is not the subject matter of the present invention. A heel holder is mounted on the sole plate 1 at the rear end thereof and is identified in its entirety by the reference numeral 3. The heel holder 3 has a housing 6. Furthermore a member 4 is secured to the base plate 2a. The member 4 has a cam surface 4a which is approximately V-shaped in the top view and on its side remote from the pivot pin 2b. A roller 7 is guided on the cam surface 4a. A groove 5, which is circular in the top view, is provided on the front facing side of the member 4. A rib 1a is provided on the sole plate 1 and slidingly extends into the groove 5.
A pair of laterally space and symmetrically oriented extensions 8 (only one being shown in FIG. 2) are secured to the upper surface of the rear end portion of the sole plate 1 and extend parallel rearwardly from the sole plate 1a. The housing 6 of the heel holder 3 is positioned between the extensions 8 and is fastened thereto by means of a rivet 8a. Two recesses 9a and 9b are furthermore provided in the housing 6. The recess 9a has a pressure spring 12 mounted therein whereas the recess 9b has two pressure springs 13 mounted therein. The pressure spring 12 acts onto a piston 10, which is reciprocally guided in the recess 9a. A pair of parallel rods 11 are provided in the recess 9b and are supported on the housing 6 for reciprocal movement. Each of the two pressure springs 13 encircle a rod 11 and is compressed between the head 11a of each rod 11 and the housing 6. In order to be able to adjust the initial tension of the three pressure springs 12 and 13, they both engage at one end thereof a spring washer 24a (spring 12) or a yoke 24b (springs 13), the longitudinal position of which elements can be adjusted by means of screws 25a and 25b in direction of the axis of the recesses 9a and 9b.
A transverse bore is provided in the housing 6 above the recess 9a, in which bore is supported an axle 14. A unit consisting of a sole holder 15 and a stepping spur 16 is hingedly secured to the axle 14. A cam surface 17 is provided on the inside of the unit. The axle 14 carries furthermore a control lever 20, at the lower end of which is supported an axle 20a for the roller 7. The control lever 20 has an approximate U-shape in cross-section (see FIG. 3), whereby the spacing between the laterally spaced legs thereof provides an opening through which the nose 10a on the piston 10 passes. The piston 10 is urged by the pressure spring 12 against the rear boundary surface of a locking lever 23, the pivot axle 24 for which is supported on and extends between the extensions 8. The front side of the locking lever 23 rests on the cam surface 17. Two bores or pockets 20b (only one of which is shown in FIG. 2) are furthermore provided in the control lever 20. The forward ends 11b of the rods 11 are received in the bores or pockets 20b.
An axle 31, on which is supported a release lever 18, is provided in the upper region of the locking lever 23. Details of the release lever 18 can be taken from FIG. 7. The release lever 18 is constructed approximately U-shaped, as viewed from the front, and has in the area of its two legs hooklike projections 18a, which are operatively received in conforming recesses in the sole holder 15. The release lever 18 also has on its two legs two laterally outwardly extending shoulders 18b which, during opening after exceeding the release point, cooperate with congruent surfaces 15a on the sole holder. Finally, two shoulders 18c are provided in the upper region of the two legs of the release lever 18 and are associated with counter surfaces 17c on the sole holder 15 for purposes of facilitating a closing of the sole holder 15 and, when the sole holder 15 is closed, of stabilizing the release lever 18. A large opening 18d is provided in each of the two legs of the release lever 18 in the center area, which opening facilitates a free positioning of the axle 14. The web 18e of the release lever 18 extending between the legs carries an indentation 18f, which is designated for the engagement of the tip of a ski pole. Axially aligned bores 18g are provided in the legs of the release lever 18 and receive therein the axle 31.
The sole holder 15 is urged by the pressure spring 12 to the skiing position illustrated in FIG. 2. The two pressure springs 13 cause the heel holder 3 to be yieldably locked against a pivoting movement in a plane parallel with respect to the upper side of the ski and about the axis of the pivot pin 2b.
If a frontal fall of the skier occurs during skiing the pressure spring 12 is compressed, and the unit of sole holder 15 and stepping spur 16 pivot clockwise in FIG. 2, which results in a release of the ski shoe. The free end of the locking lever 23 slides thereby along the cam surface 17 and moves the piston 10 back through its nose 10a against the urging of the spring 12.
If, however, a purely twisting fall occurs during skiing, then the roller 7 rolls along the cam surface 4a, which causes the control lever 20 to move the two rods 11 to the right in FIG. 2, which results in a compression of the two pressure springs 13. The ski shoe is not released during a purely twisting fall.
The two operations discussed above are superposed during a combined forward and twisting fall. Of course, all three pressure springs 12, 13 are thereby compressed.
The release lever 18 is pivoted clockwise in FIG. 2 during a voluntary release. The end 18a of the release lever 18, particularly a forward facing surface 18h thereon, biases a rearwardly facing cam surface 17b, which causes a lifting of the sole holder 15, thereby a sliding of the locking lever 23 along the cam surface 17 and a compressing of the pressure spring 12. As soon as the release point of the heel holder 3 is reached, the sole holder 15 is swung into the open position by the decompressing pressure spring 12 (see FIGS. 3-5). When the sole holder 15 has reached a certain opening angle its opening is further supported by the contact of the extending shoulders 18b of the release lever 18 with the congruent surfaces 15a of the sole holder 15.
To close the sole holder upon a reverse pivoting of the release lever 18 two shoulders 18c are provided in the upper region of the two legs of the release lever 18, which shoulders 18c are associated with countersurfaces 17c on the sole holder 15.
The release lever 18 illustrated in FIG. 7 is not limited in its use to the exemplary embodiment illustrated in FIG. 22, as it can also be used in the exemplary embodiment according to FIG. 8.
The embodiment of a heel holder 3' illustrated in FIG. 8 is similar to the first-described embodiment. However, only two pressure springs 12' and 13' are netted coaxially into one another in a single recess in the housing 6'. The inner pressure spring 13' is supported by means of a spring washer 24' and an adjusting screw 25' on the slightly bent control lever 20', which is hingedly secured to the housing 6' and carries the roller 7'. Whereas the other pressure spring 12' is supported through a pressure ring 26 connected between a two arm intermediate member 19, the arms of which are approximately triangularly shaped in the side view and carry a roller 27 straddled therebetween. The arms of the intermediate member 19 grip laterally around the control lever 20' and are also pivotally supported on the axle 14'. The roller 27 rolls along the back side of the upper region of the locking lever 23' adjacent the axle 31' which supports the release lever 18. Reference numeral 23'a identifies the frontwardly extending nose of the locking lever 23', which nose rests on the cam surface 17'.
An adjusting screw 25 is extended at 25'a toward the rear end of the ski. The extension 25'a is guided in an axially extending hollow sleeve 28 which has an external thread and is supported against the back wall of the housing 6'. A spring washer 29 is screwed onto the externally threaded part of the sleeve 28. A pressure ring 30 is provided between the spring washer 29 and the pressure spring 12'. The pressure ring 30 carries a mark 30a thereon. The position of this mark 30a and thus the initial tension of the pressure spring 12' can be read through a window 6'a in the housing 6', which window has a scale thereon.
During a frontal fall of the skier, only the outer pressure spring 12' is compressed and the sole holder 15' is pivoted about the axle 14'. Whereas if a twisting fall of the skier occurs, then the roller 7' moves along the cam surface 4'a, which results in a compression of the inner pressure spring 13'. The collar 25'b of the adjusting screw 25' rests then snugly with its lower half on the control lever 20'.
Only the spring 12' is compressed during a voluntary release of the binding. The functions of the two pressure springs 12' and 13 which are nested into one another are thus here also separate from one another.
Although a particular preferred embodiment of the invention has been disclosed in detail for illustrative purposes, it will be recognized that variations or modifications of the disclosed apparatus, including the rearrangement of parts, lie within the scope of the present invention. | A safety ski binding having a sole plate which is pivotally supported on a ski-fixed pivot pin in a horizontal plane, however, is secured against lifting off from the ski. The sole plate has a front jaw at its front end and a heel holder provided with a housing at its rear end. The heel holder has a sole holder which is pivotal upwardly about a transversely extending axle on the housing against the force of a pressure spring. The heel holder also carries a roller which is loaded by at least one further pressure spring on a control lever, with which roller is associated a cam surface arranged on a ski-fixed member. The pressure springs for controlling the vertical release and the ones for controlling the lateral release can thereby either be arranged among one another or nested into one another. | 0 |
This application is a continuation of application No. 07/868,688, filed Apr. 15, 1992, now U.S. Pat. No. 5,308,450.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a new and improved press section of a papermaking machine for pressing and dewatering a paper web.
Generally speaking, the press section of a papermaking machine for dewatering a paper web, as contemplated by the present development, is of the type comprising two separate successively arranged press locations. Each press location is formed between an upper extended press surface and a lower extended press surface forming extended or wide press nips. The press section contains at the first press location and at the second press location at least one respective separate felt guided in conjunction with the paper web through the press locations. The second press location contains a cylindrical counter roll or roller extending essentially beneath the second press location and an extended nip press roll extending essentially above the second press location. This extended nip press roll forms the extended nip of the second press location and is essentially accommodated to the contour of the counter roll.
2. Discussion of the Background and Material Information
Press sections or press arrangements of the aforementioned type for pressing and dewatering a paper web possess the decisive advantage that by using press structures which, as viewed in the direction of travel of the paper web, have an extended or wide press length, that is, an extended press nip, there is available a relatively large amount of time for expressing liquid out of the paper web. As a result, such a press section can operate with relatively few press locations and nonetheless can achieve a high dewatering effect or capacity even with relatively rapid throughpass or high speed travel of the paper web. The presently known press apparatuses or arrangements containing an extended press nip are frequently constructed such that there is provided a press roll equipped with a flexible shell or jacket which is pressed from internally of the press roll by means of an essentially only radially movable press element against a rigid counter roll, and the flexible shell or jacket, at the region of the extended press nip, can snugly bear against the rigid counter roll. However, other constructions are possible for achieving an extended press nip or press surface.
In order to obtain as great as possible operational reliability of the press section, at high speed papermaking machines it is strived to continuously maintain the paper web in contact with at least one felt, in order to thus avoid a so-called free or open draw where the paper web would be exposed to the danger of tearing. What is disadvantageous with such arrangements is especially that, following departure of the paper web from the press nip, there occurs remoistening or rewetting of the paper web by the water entrained by the felt.
In the commonly assigned German Published Patent Application No. 3,742,848, published Jun. 29, 1989, and the cognate U.S. Pat. No. 4,915,790, granted Apr. 10, 1990, there is disclosed an arrangement intended to solve the aforementioned problem, wherein special measures are undertaken in order to raise at least one felt very rapidly away from the paper web after the latter emerges from the press nip.
Furthermore, solutions have become known in the papermaking art where only a single felt is present in the second press nip. If this felt is located at the top of the paper web, then such paper web can drop off such felt much too easily prior to entering the second press location or press nip. On the other hand, if such felt is located at the bottom of the paper web, especially in the form of a continuous felt which spans both press locations or press nips, then the paper web co-travels throughout its full width, following exit from the second press location or press nip, upwardly together with the top or upper roll, and is then difficult to handle. Moreover, at this location there also exists a greater tendency of the paper web to again suck up water from the felt behind the press nip.
German Published Patent Application No. 3,815,278, published Nov. 16, 1989, discloses a press arrangement containing two successive roll presses each provided with an extended press nip. While here there exist favorable conditions for dewatering the paper web, on the other hand, the paper web is transported by one felt through both roll presses or press locations. It is not possible to condition the paper web between both of the roll presses.
SUMMARY OF THE INVENTION
Therefore, with the foregoing in mind, it is a primary object of the present invention to provide an improved press section or press arrangement of a papermaking machine for pressing and dewatering a paper web, which is not afflicted with the aforementioned limitations and drawbacks of the prior art.
Another and more specific object of the present invention aims at improving upon the dewatering effect or capacity of press sections containing two successively arranged extended or wide press nips, without impairing the operational reliability as concerns guiding the paper web through both extended or wide press nips.
Still a further noteworthy object of the present invention is directed to the provision of an improved press section or press arrangement of a papermaking machine for pressing and dewatering a paper web, which is relatively simple in construction and design and exceedingly reliable and efficient in operation.
Now in order to implement these and still further objects of the present invention, which will become more readily apparent as the description proceeds, the press section of the present development for dewatering a paper web is manifested, among other things, by the features that behind or downstream of the first press location, as viewed in the predetermined direction of travel of the paper web, the upper felt--to the extent present--of the first press location is removed or separated from the paper web located beneath such upper felt, thereafter the paper web is further guided from the first press location to a web removal or pickup device operated under vacuum conditions and contacted by the upper felt of the second press location, and the paper web can travel from such web removal or pickup device to the second press location.
A particular advantage which is realized with the solutions proposed by the present invention resides in the fact that different felts or felt belts are used in each case for both of the press locations. Therefore it is possible to newly condition each felt or felt belt following passage thereof through the associated press location, in other words, it is possible to make each such felt or felt belt available with a relatively low water content for accomplishing a new pressing operation at the paper web. The transfer of the paper web from the first lower felt to the second upper felt is performed with the aid of a felted and vacuum-operated web removal or pickup device. There is also ensured that the wet or moist paper web is positively guided between the first and second press locations and can be retained at the felt.
According to a further feature of the present invention, the at least one separate felt provided for the first press location and guided in conjunction With the paper web through the first press location defines a lower felt, and the paper web is transferred by the lower felt of the first press location to the vacuum-operated web removal device which is contacted by the upper felt of the second press location.
According to another aspect of the present invention, the web removal device is advantageously located between the first press location and the second press location, and the substantially cylindrical counter roll of the second press location defines a lower counter roll. The paper web is transferred by such web removal device, after moving through at most a substantially short travel distance, into contact with the lower counter roll of the second press location and then the paper web is guided in conjunction with the upper felt through the second press location.
Still further, there can be specifically provided an upper felt for the first press location, and the web removal device directly removes the paper web from the first press location. Also, in this regard there can be provided a lower counter roll for the first press location, and the web removal device directly removes the paper web from such lower counter roll.
Moreover, a vacuum-operated suction box can be located above the upper felt of the second press location for transferring the paper web between the web removal device and the lower counter roll of the second press location. The paper web is transferred by the web removal device located between the first press location and the second press location to the upper felt of the second press location and then to the lower counter roll of the second press location such that the suction box retains the paper web against the upper felt of the second press location.
According to a further embodiment, a transport wire is located beneath the upper felt of the second press location and the paper web for transferring the paper web between the web removal device and the lower counter roll of the second press location. The paper web is transferred by the web removal device located between the first press location and the second press location to the upper felt of the second press location and then to the lower counter roll of the second press location such that the transfer belt retains the paper web against the upper felt.
A further design envisions that a blow box is located above the paper web for transferring the paper web between the web removal device and the lower counter roll oft he second press location. This blow box directs an air current in a direction away from the upper felt of the second press location. The paper web is transferred by the web removal device located between the first press location and the second press location to the upper felt of the second press location and then to the lower counter roll of the second press location such that the blow box retains the paper web against the upper felt. This blow box can comprise slot means, and thus, constitutes a slotted blow box for producing an injector action which directs the air current in the direction away from the upper felt.
Another feature of the present invention contemplates arranging an additional web removal device downstream of the second press location with respect to the direction of travel of the paper web, and a further upper felt cooperates with the additional web removal device. A suction box operated under vacuum conditions is arranged above this further upper felt. The additional web removal device guides the paper web, following the second press location, at the further upper felt such that the suction box retains the paper web against the further upper felt.
According to a further modification of the present invention, a blow box is arranged above the further upper felt, this blow box directs an air current in a direction away from the further upper felt. The additional web removal device guides the paper web, following the second press location, at the further upper felt such that the blow box retains the paper web against the further upper felt. Once again, such blow box can comprise slot means to define a slotted blow box for producing an injector action which directs the air current in the direction away from the further upper felt.
Still further, the first press location can contain a substantially cylindrical counter roll extending beneath the first press location and an extended nip press roll extending above the first press location. This extended nip press roll forms the extended nip of the first press location and is essentially accommodated to the contour of the substantially cylindrical counter roll of the first press location.
Moreover, the successively arranged first press location and second press location can be positioned at substantially the same elevation or height.
According to a further embodiment, the substantially cylindrical counter roll of the second press location defines a lower counter roll, and an additional web removal device is arranged downstream of the second press location with respect to the direction of travel of the paper web. There also are provided means for providing a web drying section arranged downstream of the additional web removal device. A further upper felt cooperates with the additional web removal device. The upper felt of the second press location is guided, following passage through the second press location, such that it detaches from the paper web which remains adhering to the lower counter roll. Moreover, the additional web removal device removes the paper web from the lower counter roll and transfers the removed paper web to the drying section.
Furthermore, this additional web removal device which cooperates with the further upper felt can be advantageously mounted to be pivotable towards and adjustable in position with respect to the lower counter roll.
Still further, the drying section can be structured to provide a continuous closed guidance or closed draw guidance of the paper web through the drying section.
It is also possible to arrange a waste or broke pulper or the like beneath the second press location for collecting and forming a suspension therein from broke or paper web material formed upon tearing or transfer of the paper web.
According to another aspect, the press section can be devoid of means upstream of the second press location for forming transfer tails, so that transfer of the paper web through the first press location and the second press location occurs throughout the full width of the paper web.
It is also possible to have means arranged downstream of the first press location for removing or separating the upper felt of the first press location from the paper web in order to prevent rewetting or remoistening of the paper web.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be better understood and objects other than those set forth above, will become apparent when consideration is given to the following detailed description thereof. Such description makes reference to the annexed drawings wherein there have been generally used throughout the different Figures the same reference characters to denote the same or analogous components or parts, and wherein:
FIG. 1 is a schematic side view of a first exemplary embodiment of a press section of a papermaking machine for pressing and dewatering a paper web, containing first and second press locations;
FIG. 2 is a schematic side view of a second exemplary embodiment of a press section of a papermaking machine for pressing and dewatering a paper web, likewise containing first and second press locations;
FIG. 3 is a schematic side view of a third exemplary embodiment of a press section of a papermaking machine for pressing and dewatering a paper web, again containing first and second press locations;
FIG. 4 is a schematic fragmentary side view of a fourth exemplary embodiment of a press section of a papermaking machine for pressing and dewatering a paper web, equally containing first and second press locations; and
FIG. 5 is a schematic fragmentary side view of a fifth exemplary embodiment of a press section of a papermaking machine for pressing and dewatering a paper web, once again containing first and second press locations.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Describing now the drawings, it is to be understood that only enough of the construction of the different exemplary embodiments of press sections of a papermaking machine for pressing and dewatering a paper web has been depicted therein, in order to simplify the illustration, as needed for those skilled in the art to readily understand- the underlying principles and concepts of the present invention.
Turning attention to the first exemplary embodiment of press section 100 of a papermaking machine as depicted in FIG. 1, it will be seen that a paper web, only generally indicated by reference character PW, is delivered, for instance, by a longitudinal wire 21 through a pickup roll 22, such as a suction roll 22a, into the press section 100. This press section 100 is here shown to comprise two successively arranged press locations 1 and 2, defining a first press location 1 and the downstream situated second press location 2 as viewed with respect to a predetermined direction of travel 102 of the paper web PW through the press section 100.
It will be seen that the first press location comprises press surfaces 3 and 4, and equally, the second press location 2 comprises press surfaces 5 and 6. It also will be recognized, as viewed in the direction of travel 102 of the paper web PW, the press surfaces 3 and 4 of the first press location 1 and the press surfaces 5 and 6 of the second press location 2 each have an extended shape, to thus define the respective extended or wide press nips 104 and 106. In the exemplary embodiment under discussion the first and second press locations 1 and 2 comprise the respective lower situated counter rolls 7 and 9 and the respective upper situated extended nip press rolls 8 and 10. Moreover, as depicted solely by way of example, the successively arranged first press location and the second press location 2 can be positioned at substantially the same elevation or height.
At the site of the first press location 1 there are here shown to be used two looped or endless felts or felt belts 11 and 12 which travel conjointly with the paper web W sandwiched therebetween through the first press location 1. It will be observed that the upper felt is trained about a displaceable deflection or turning roll 90. It is here also noted that under certain circumstances the upper felt 11 might even be omitted. Regarding the second press location 2, only a single looped or endless felt or felt belt 13 is guided through such second press location 2. The removal or pickup of the paper web PW from the lower felt 12 is undertaken by a web removal or pickup device 15, here constructed, for instance, as a suction or vacuum roll 15a about which partially wraps upper felt 13.
The paper web PW which is lifted or picked off from the lower felt 12 by the web removal device 15 is delivered through a short travel path or while in direct contact with the suction roll 15a to the lower counter roll 9 of the second press location 2, so that there is practically precluded dropping of the paper web PW due to its weight off of the upper felt 13 of the second press location 2. Behind or downstream of the extended or wide press nip 106, as viewed with respect to the direction of travel 102 of the paper web PW, such paper web PW remains adhering to the lower counter roll 9, whereas the upper felt 13 travels over a deflection or turning roll 92 and is raised away from the paper web.
By means of a further web removal or pickup device 18, here constructed, for instance, as a suction roll 18a which can be shifted or displaced towards the lower counter roll 9, the paper web PW is deposited at a further upper looped or endless felt or felt belt 14 and then moves in conjunction therewith to the starting region of a subsequently arranged web drying section, generally indicated by reference numeral 108, of the papermaking machine. In the event that the paper web tears or during transfer in the case of start-up of the papermaking machine, the not further transported paper web or paper web strips can be deposited with the assistance of doctor blades or scrapers 19 and 20 into the waste or broke pulper or receiver 23 or the like without any problems arising.
A further advantage can be realized if upon start-up of the press section 100 the paper web PW can be guided in its full width through the first and second press locations 1 and 2, because that measure serves to protect the sometimes sensitive structural parts of the extended nip press rolls 8 and 10. When the paper web PW then departs from the last extended nip press roll there can be formed a transfer tail or strip, for instance for the subsequently situated drying section. The thus formed waste or broke is deposited in the below situated waste or broke pulper 23. More specifically, in such waste or broke pulper 23 which is arranged beneath the second press location 2 there is formed a suspension from the collected broke or paper web material resulting during tearing or transfer of the paper web.
With respect to the modified exemplary embodiment of press section 100A depicted in FIG. 2, the operationally reliable transfer of the paper web PW between the first press location 1 and the second press location 2 is ensured by a suction box 16. This suction box 16 exerts a negative pressure or vacuum action from above the upper felt 13 upon such upper felt 13, and thus, retains the paper web PW situated therebelow against this upper felt 13. From the location of the suction box 16 the paper web PW arrives together with the upper felt 13 at the second press location 2. Instead of using the suction box 16, it would be possible to also provide a special, for instance, slotted blow box, schematically represented in broken lines by reference numeral 110. This slotted blow box 110 operates according to the injector principle and produces an air current or flow through narrow slots having a flow direction extending away from the upper felt 13, and thus, exerts a retaining force or adhering action upon the paper web PW. Such a slotted blow box 110 also can be provided for the suction box 16 cooperating with the further upper looped or endless felt or felt belt 14 with which coacts the web removal or pickup device 18.
Another possible construction of press section 100B is depicted in FIG. 3, where, instead of or in addition to the suction box 16 located upstream of the second press location 2, there is used a transport or transfer wire 17 or the like which presses the paper web PW from below against-the upper felt 13. This modified construction also affords an operationally reliable transfer of the paper web PW between the first press location 1 and the second press location 2. A further advantageous constructional possibility, useful for the same purpose, would entail the use of a blow box beneath the paper web PW, again schematically represented by the broken or dashed lines 110.
Apart from the different constructions of press sections 100, 100A and 100B, as respectively depicted and considered with respect to FIGS. 1 to 3, employing the upper situated extended nip press rolls 8 and 10 in the first press location 1 and the second press location 2, respectively, FIG. 4 depicts a variant construction of press section 100D employing an arrangement containing a lower situated extended nip press roll 8 arranged at the first press location 1 and on top of which there is arranged an upper counter roll 7. Similar to the previously considered embodiments, the paper web PW can be transferred by means of two looped or endless felts 11 and 12 from the first press location 1 and the upper looped or endless felt 11 can be raised or lifted away from the paper web PW. A suction roll 24 is mounted beneath the lower felt 12 to ensure for positive entrainment of the paper web PW. This solution can be advantageously combined with the different constructions previously discussed for transfer of the paper web PW to the second press location 2. In the depicted arrangement there is shown, by way of example and not limitation, a web transfer structure composed of the web removal device 15 like that considered with regard to the prior discussion of the embodiment of FIG. 1. Here also, the successively arranged first press location 1 and the second press location 2 are shown, by way of example, positioned at substantially the same elevation or height.
FIG. 5 depicts a further construction of press section 100E according to the present invention. There is illustrated therein an exceedingly compact arrangement of the entire press section 100E. The web removal device 15, operated under vacuum or suction conditions, directly transfers the paper web PW from the lower counter roll 7 belonging to the first press location 1 to the lower counter roll 9 belonging to the second press location 2. After travel through the second press location 2 the paper web PW remains at the lower counter roll 9 until reaching the further web removal or pickup device 18, here constructed, for instance, as a suction roll 18a, whereas the upper felt 13 is picked-off or removed from the paper web PW immediately after emerging from the extended press surfaces 5 and 6. This further web removal or pickup device 18 directly delivers or transfers the paper web PW to the subsequently situated drying section 108. Moreover, such additional web removal device 18, which cooperates with the further upper felt 14, is advantageously mounted to be pivotable towards and adjustable in position with respect to the lower counter roll 9, for which purpose there can be used any suitable roll pivot structure as schematically represented by reference numeral 112. Additionally, the drying section 108 can be structured to provide a continuous closed guidance or closed draw guidance of the paper web through such drying section. Once again, it is possible for the successively arranged first press location 1 and the second press location 2 to be positioned at substantially the same elevation or height.
While there are shown and described present preferred embodiments of the invention, it is distinctly to be understood the invention is not limited thereto, but may be otherwise variously embodied and practiced within the scope of the following claims. | The press section of a papermaking machine for dewatering a paper web comprises two separate, successively arranged extended nip press locations. Both of the extended nip press locations contain at least one respective felt which travels together with the paper web through the associated extended nip press location. The paper web is guided from the first extended nip press location to a web removal device contacted by an upper felt of the second extended nip press location, and from that location the paper web can move to the second extended nip press location. | 3 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims a benefit of priority under 35 USC § 119 based on patent application 60/939,944, filed May 24, 2007, the entire contents of which are hereby expressly incorporated by reference into the present application.
STATEMENT AS TO RIGHTS TO INVENTION(S) MADE UNDER FEDERALLY-SPONSORED RESEARCH AND DEVELOPMENT
[0002] The U.S. Government, through the National Institute of Standards and Testing, is the owner of this invention.
BACKGROUND OF THE INVENTION
[0003] 1. Field of the Invention
[0004] The present invention relates in general to the field of microfluidics. More particularly, the present invention relates to a three dimensional (3D) microfluidic device for the passive sorting and storage of liquid plugs using capillary force.
[0005] 2. Discussion of the Related Art
[0006] Sorting and storing microfluidic droplets is a subject of high importance for a number of different applications. One field is protein crystallization. For example, the group of Prof Ismagilov at the University of Chicago creates droplets with different contents of the reagents necessary to crystallize proteins. In this approach, the contents of each droplet are modified to enable screening through a large combinatorial set of reactions to determine the best combination of reagents for protein crystals. After production, the droplets need to be stored in a deterministic way so that the contents of each stored droplet are known. The initial solution to the problem of sequential storage was to introduce a glass capillary on a microchannel, fill it with a sequence of droplets, take it out, seal it with wax, and connect a second capillary to the outlet of the device. This operation proved cumbersome as the capillaries needed to be filled sequentially, labeled, and then stored many times. More recently, a simpler way to perform this operation by running the generation of droplets into very long tubing until it was filled was demonstrated.
[0007] Another method to store sequentially droplets for combinatorial experiments has also been published. This other method involves using external active valves to fill the side channels.
[0008] Despite recent advances, the methods discussed above are still too limited for a large number of applications.
[0009] Therefore, what is needed is a microfluidic device that does not need active valves and has no storage limitation because it has as many side microchannels as desired. Further, what is needed is a microfluidic device in which the microchannels are geometrically designed to allow filling flow using solely capillary force, i.e., by passive pumping.
[0010] What is also needed is a device that could be used in a remote location or in a lab that has a variety of applications and many degrees of freedom.
[0011] Fabrication techniques for the current invention are generally discussed in the article entitled “Using Pattern Homogenization of Binary Grayscale Masks to Fabricate Microfluidic Structures with 3D Topography,” Lab Chip, 2007, 7, 1567-1573, which was published in August of 2007 by the Royal Society of Chemistry, the entire contents of which are hereby expressly incorporated by reference into the present application.
SUMMARY AND OBJECTS OF THE INVENTION
[0012] By way of summary, the present invention is directed to microstructures with arbitrary topography. Preferably, the microstructures have modulated 3D topography over large areas (centimeters) and only require a single photolithographic step during fabrication. The device may further comprise at least one outlet in communication with the microchannel. The microchannel's topographic constrictions may be designed to stop priming flow through the main microchannel. These constrictions may further make use of capillary forces to move a liquid until a dead-end side channel is completely filled and a plug of liquid is stored therein. Any air (or gas) escapes through small orifices at the end of the side microchannels during this filling process. Subsequent plugs of liquid may be stored sequentially in the dead-end side channels of the device. In this way, the plugs of liquid may be used to create libraries of liquid plugs with arbitrary concentrations of chemicals. Additionally, the device may be designed to be primed passively with capillary forces.
[0013] The device may allow for complex chemical mixtures to be generated and stored for applications such as chemotaxis experiments under zero-flow conditions. The device may also allow for complex chemical mixtures to be dispersed in immiscible liquid forming droplets for combinatorial experiment or stored deterministically for subsequent analysis.
[0014] There are several possible applications of the device including the device being used in a remote location to sample water from a source. In such an application, this invention could be used for environmental sampling of liquids. For example, a person could bring one such device to a remote location and sample water from a source. The device could be designed to be primed passively with capillary forces (no external power would be required). This way the liquid sampled in the different side channels would correspond to samples acquired sequentially with a time lag between them.
[0015] This device could also be employed to realize combinatorial experiments in a lab. For example, droplets (or biological cells) could be introduced in different side channels according to a distinct property (e.g., different types of cells). The substrate could be functionalized with a gradient of proteins across the direction perpendicular to the channels, and/or with a gradient in temperature, light, etc. This device would work as a combinatorial platform with several degrees of freedom.
[0016] In another embodiment the invention is a microfluidic device without an actuator that is capable of sorting liquid plugs chronologically and storing them comprising: (1) a main microchannel with a multitude of topographic constrictions, (2) at least two inlets that merge into the main microchannel, (3) side channels with small orifices to allow any air (or gas) to escape that are associated with the topographic constrictions and alternate with the inlets, (4) and one outlet in communication with the main microchannel.
[0017] In another application of this embodiment, the device may provide for a gradient of proteins across a direction perpendicular to the channels. In another application possibly used in conjunction with the prior application, the device may also be used under zero gravity to handle liquid samples in space.
[0018] In yet another embodiment, the invention is a microfluidic device comprising a photoresist exposed to UV light through a binary transparency mask including an optical adhesive with low contrast γ≈0.55 to promote partial polymerization in areas subject to diffracted light and to facilitate the transfer of discrete patterns from the mask as homogeneous patterns (smooth surfaces) to the photoresist.
[0019] The device may comprise semicircular microchannels generated by using swatches of 5×1 pixels that are enlarged with graphic-design software to form lines. Additionally, complex curved surfaces in a microchannel may be created with graphic software operations such as stretching, rotating and skewing.
[0020] The device may further comprise a second microchannel of a smaller diameter that is semi-circular and includes a semi-spiral ridge inside. Microchannels may also have a zigzag structure that is modulated in an x, y and z direction.
[0021] These, and other aspects and objects of the present invention will be better appreciated and understood when considered in conjunction with the following description and the accompanying drawings. It should be understood, however, that the following description, while indicating preferred embodiments of the present invention, is 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 DRAWINGS
[0022] A clear conception of the advantages and features constituting the present invention, and of the construction and operation of typical mechanisms provided with the present invention, will become more readily apparent by referring to the exemplary, and therefore non-limiting, embodiments illustrated in the drawings accompanying and forming a part of this specification, wherein like reference numerals designate the same elements in the several views, and in which:
[0023] FIG. 1 is an illustration of morphology transition in an array of swatches of different pixels size and density;
[0024] FIG. 2 and the FIG. 3 illustrate various shapes produced;
[0025] FIG. 4 illustrates various grayscale tones in swatches which may be used;
[0026] FIG. 5 is a schematic illustrating fabrication of a master template;
[0027] FIG. 6 shows one embodiment of a microfluidic device of the present invention;
[0028] FIG. 7 is a close-up of a microchannel of the device shown in FIG. 6 ;
[0029] FIG. 8 is a grayscale pattern used to create the microchannel shown in FIG. 7 ;
[0030] FIG. 9 is a swatch used to create the grayscale pattern of FIG. 8 ;
[0031] FIGS. 10 and 11 are schematics of side channels of the device shown in FIG. 6 ;
[0032] FIGS. 12A and 12 B illustrate fluid flow in the device shown in FIG. 6 ;
[0033] FIG. 13 is a partial view of a grayscale pattern used to create a microfluidic device of the present invention;
[0034] FIG. 14 is a swatch used to create the grayscale pattern of FIG. 13 ;
[0035] FIG. 15 is a partial close-up view of microchannels of the device created using the grayscale shown in FIG. 13 ;
[0036] FIGS. 16A-17 B illustrate other grayscale patterns and the shapes may form;
[0037] FIG. 18 shows a partial view T-shaped microchannel of the present invention;
[0038] FIG. 19 shows a close up of a zigzag section of microchannel of the present invention;
[0039] FIG. 20 is a partial view of a grayscale used to create the microchannel of FIG. 19 ;
[0040] FIG. 21 is a swatch used to create the grayscale pattern of FIG. 20 ;
[0041] FIG. 22 shows a close-up of a concentric circle pattern of the present invention;
[0042] FIG. 23 is a pixelated grayscale pattern of FIG. 22 ;
[0043] FIG. 24 is a horn created using the pattern shown in the FIG. 23 ;
[0044] FIG. 25A is a master template of horns like the one shown in FIG. 24 ;
[0045] FIG. 25B shows a method of creating an ejector plate from the template shown in FIG. 25A ;
[0046] FIG. 26 shows an ejector device of the present invention;
[0047] FIG. 27A is an illustration showing an ejector device in operation;
[0048] FIG. 27B is a photograph showing that ejector device of the present invention in operation;
[0049] FIG. 28 is a diagram showing the various pixel patterns and swatches that may be used to develop various microstructures of the present invention;
[0050] FIG. 29 is another diagram showing the various masks with pixel patterns that may be used to develop various microstructures of the present invention;
[0051] FIGS. 30 and 31 show a master template of a microstructure of the present invention;
[0052] FIGS. 32 and 33 show replicas created from the template shown in FIGS. 30 and 31 ; and
[0053] FIG. 34 is a graph showing a calculation of the present invention.
[0054] In describing the preferred embodiment of the invention that is illustrated in the drawings, specific terminology will be resorted to for the sake of clarity. However, it is not intended that the invention be limited to the specific terms so selected and it is to be understood that each specific term includes all technical equivalents that operate in a similar manner to accomplish a similar purpose. For example, the words “connected”, “attached”, or terms similar thereto are often used. They are not limited to direct connection but include connection through other elements where such connection is recognized as being equivalent by those skilled in the art.
DESCRIPTION OF PREFERRED EMBODIMENTS
[0055] The present invention and the various features and advantageous details thereof are explained more fully with reference to the non-limiting embodiments described in detail in the following description.
1. System Overview
[0056] In the method of the present invention, first a glass slide is brought into contact with an optical adhesive of a photoresist chip. A mask with grayscale patterns is then used to block UV light selectively from the photoresist chip. This method promotes partial polymerization on the chip in areas subject to diffracted light. It also facilitates the transfer of discrete patterns from the mask to the photoresist chip as homogeneous patterns (smooth surfaces). Specifically, under an opaque pixel, there is an overlapping of the exponential decay in intensity from each edge (due to diffraction) that, in addition to the low contrast of the photoresist and the nonlinear interaction of photopolymerized features, can eventually trigger the emergence of a continuous polymerized structure.
[0057] To control this nonlinear collective phenomenon, tiling pattern units or “swatches” are used as repetitive motifs to define areas that transmit the same level of UV intensity. Each swatch is a distinct array of pixels where the relative density of transparent to opaque pixels determines the average UV light intensity transmitted (see, e.g., FIG. 28 ).
[0058] Preferably, the device created is a microfluidic device that has a main channel with several constrictions that alternate with dead-end side microchannels.
[0059] In another example, curved surfaces may also be created by designing incremental grayscale tones in adjacent small areas. This may be accomplished because after the first exposure to UV light, the polymer at the surface is in a compliant gel-like state that can stick to itself during cleaning, smoothing the transitions between surfaces of similar heights. Moreover, semicircular microchannels have been generated by using swatches of 5×1 pixels that are further enlarged with graphic-design software.
[0060] In yet another example, 8×4 pixel swatches are combined for multilevel flat surfaces with 5×1 swatches. These may produce a microchannel with a zigzag structure that is modulated in the three x, y, and z directions.
[0061] Similarly, swatches with different hierarchical levels may be used to design complex micro fluidic devices. Typically, the first level defines the grayscale tones for simple geometries such as the ones considered in the previous examples, and the subsequent levels increase the degree of complexity. An illustration of this is an array of polymerized “horns” that is fabricated and used as a master for a microfluidic device that ejects monodisperse liquid droplets into air.
[0062] It should be noted that all of the patterns described herein may be combined to form a single microfluidic device. Further, all of the microstructures described herein may be combined into one microfluidic device.
[0063] Some of the advantages of the inventive method include (i) ease of design; (ii) fast turn-around times both for mask design and fabrication based solely on exposure times; (iii) low cost of transparency masks, i.e., about 15 US Dollars; and (iv) patterning of large areas and single structures simultaneously with topographic resolutions of tens of microns.
2. Detailed Description of Preferred Embodiments
[0064] Specific embodiments of the present invention will now be further described by the following, non-limiting examples which will serve to illustrate various features of significance. The examples are intended merely to facilitate an understanding of ways in which the present invention may be practiced and to further enable those of skill in the art to practice the present invention. Accordingly, the examples should not be construed as limiting the scope of the present invention.
[0065] FIG. 1 shows a diagram of the morphology transition in an array of cylinders (2 mm diameter) that is created with masks patterned with variable pixel size and pixel density. A photoresistive adhesive polymerizes forming individual posts 4 a (Δ) and 2 as shown in FIG. 2 or homogeneous macro surfaces 4 c (□) and 3 as shown in FIG. 3 depending on the number of transparent pixels per unit area of the patterned mask (n) and the size of a pixel (a). The reference number 4 b (∘) denotes transition cases between homogenous and discrete patterns. For further details see also FIG. 29 . Interestingly, it was found that small individual posts (≈30 μm) generated with transparent pixels in swatches are vertical and form long threads, probably due to a lensing effect. Such complex geometries are useful for many applications such as to create tailored 3D flow patterns inside the microchannel to promote chaotic advection. Further, they may be used to create arbitrary cross sections in the microchannel that yield in plane velocity profiles different than Poiseuille flow for pressure driven systems. Finally, they may be used to modify the cross sectional distribution of the electric field in electro-osmotic flow to eliminate electric field constriction.
[0066] FIG. 4 shows a grayscale illustration 5 with corresponding pixel patterns or swatches 6 . It should be noted that experimental data shows the correlation between the height of macro-surfaces and grayscale tone in two experiments (see, e.g., FIGS. 28 and 29 , and graph shown in FIG. 34 ), with patterns at 600 ppi (pixels per inch) (•) and 2400 ppi (Δ) and in both cases at 3000 dpi (dots per inch) printing resolution. Pixels per inch, “ppi,” is used for pixel size when referring to the resolution of the pixilation process when converting theoretical grayscale into black and white pixels to distinguish it from the printing resolution or mask resolution that is given in “dpi” (dots per inch). The lines in FIG. 34 are a fit to guide the eye. The in-plane resolution is given by the size of the swatch used and by the minimum spacing required between features to avoid partial polymerization. Using 8×4 swatches at 2400 ppi (and 3000 dpi) the minimum area size that can be patterned is 42×84 μm 2 . Below 2400 ppi, the optical resolution of the experimental photolithographic setup interferes with the fidelity of the patterns. It was discovered empirically that the optical adhesive polymerizes forming vertical “threads” of 1 to 2 μm diameter, which sets the ultimate in-plane resolution of the fabrication process with this material if higher resolution masks are employed. Using ink masks printed at 3000 dpi and the optical adhesive, the smallest reproducible feature fabricated was a microchannel of constant height of 60 μm±3 μm along the symmetry axis.
[0067] FIG. 5 shows one a method of making some of the microstructures of the present invention. Using grayscale fabrication, a photoresist material 103 is exposed to UV light 102 through a binary transparency mask 105 . In between the mask 105 and the photoresist material 103 is preferably a glass slide 104 . The mask 105 preferably has a plurality of transparent and opaque pixels which form patterns used to fabricate microstructures with modulated topography over large areas. Large groups of pixels or “swatches” are needed for more complex shapes. The photoresist material used is an optical adhesive 107 with low contrast γ≈0.55. Contrast is a measure of the ability of a resist to distinguish between transparent and opaque areas of a mask and typical photoresists have a contrast of 2 to 3. At least partial polymerization of the material 103 occurs to create polymerized microstructures 108 . It should be noted that the photolithographic contrast is the maximum slope of the plot of development rate versus exposure dose on a logarithmic scale. The contrast of optical adhesion is calculated by collecting data on the following: 1) the calculation of the position of the polymerization front as a function of time; and 2) an accurate knowledge of the light intensity at the surface of the optical adhesive.
[0068] The transmittance of light through grayscale patterns becomes increasingly nonlinear as the pattern pixel size approaches the printing resolution of the mask. As will be discussed further below, the entire process needed to be calibrated instead of using higher resolution masks to increase pattern fidelity.
[0069] FIG. 6 shows an embodiment of the present invention including a multilevel microfluidic device 111 preferably used for the deterministic storage of liquid plugs using capillary forces. Replica molding is also used for the fabrication of this microfluidic device. First, a thiolene master or template 109 is created (see insert shown next to FIG. 6 ). This is done with grayscale transparency mask 105 as discussed above. However, the mask uses 8×4 swatches (see, e.g., FIGS. 8 and 9 ) of pixels. The swatches create in the device 111 at least one multilevel microchannel 114 that is able to harness capillarity forces and store fluid in a deterministic way (see, e.g., FIG. 12A ).
[0070] The preferred microfluidic device or chip 111 has four inlets 112 a - 112 d as shown in FIG. 6 . These inlets 112 a - d merge into the main microchannel 114 . The microchannel 114 preferably includes topographic constrictions 116 that alternate with dead-end side microchannels 118 . Preferably, at least one outlet 120 is provided on the chip 111 . As best shown in FIGS. 10 and 11 , each constriction 116 is designed to stop a priming flow through the main channel 114 , using capillary forces until the previous side channel 118 is completely filled and a plug of liquid is stored. Consequently, this device 111 may be used to create libraries of liquid plugs with arbitrary concentrations of liquids, e.g., dilute chemicals.
[0071] FIG. 7 shows a detail on a bottom of the device 111 including the main microchannel 114 . FIG. 8 is a grayscale pattern 5 used to construct the microchannel 114 . FIG. 9 is an 8×4 swatch 6 , e.g., a 70% grayscale pattern, used for the constrictions 116 .
[0072] FIG. 10 is a schematic showing the typical operation of the microfluidic device 111 . A liquid is introduced through an inlet and moves along the main microchannel. It then comes to an inlet 119 to the side channel 118 . The pressure that must be overcome by the moving the liquid front is higher at the constriction 116 than at the side microchannels 118 , and, therefore, the side channels 118 fill first before the liquid moves on. The quantity of liquid contained in a channel is often referred to as a plug of liquid 126 .
[0073] It should be noted that the maximum capillary force preventing a liquid front from wetting hydrophobic walls is proportional to the perimeter of the interface, and is given (if the microchannel is rectangular and all walls are hydrophobic) by F c =γ cos(θ)×2(w+h), where γ is the surface tension of the liquid, θ is the contact angle (we assume the same contact angle for all walls), w is the width of the channel and h is the height of the channel. If a pressure ΔP is applied to the liquid plug 126 in order to move it, the advancing interface will be subject to a force proportional to the area of the interface F ad =ΔP×(w×h). The plug starts moving when F ad >F c thus, F ad /F c >1, which can be expressed as: (w×h)/(w+h)>2γ cos(θ)/ΔP. If the height of the microchannel is reduced by a factor n, then
[0000] ( w×h/n )/( w+h/n )=( w×h )/( n×w+h )<( w×h )/( w+h ),∀ n> 1
[0000] and, therefore, the pressure threshold to start moving a liquid front in rectangular hydrophobic microchannels is higher in small channels or constrictions. Thus, as shown in FIG. 11 , the liquid enters a constriction 116 only after filling the previous side channel.
[0074] As shown in FIG. 12A , deterministic combinatorial storage of fluidic libraries 130 is illustrated by using two syringe pumps simultaneously to deliver two different color dyes and to store them in closed compartments (side channels 118 ) of the device 111 . The delivery rate of both dyes is ramped inversely, with 100% red and 0% blue at the beginning and 0% red and 100% blue at the end. The different combinatorial concentrations are stored passively in the different compartments. The external programmable syringe pumps introduce a red and blue dye through inlets 1 and 2 , respectively, in FIG. 12A . Both flow rates are ramped with the same slope and opposite sign, thus maintaining a constant total flow rate through the main channel 114 throughout priming. The liquid with variable dye concentrations is stored sequentially in the side channels 118 . This yielded an array 128 with a color gradient that varied within each side microchannel 118 and between microchannels. This illustration thus shows that it is possible for complex mixtures to be a) generated and stored in such a chip for applications such as chemotaxis experiments under zero-flow conditions, or b) dispersed in immiscible liquid forming droplets for combinatorial experiments and stored deterministically for subsequent analysis.
[0075] Referring now to FIGS. 13-15 another possible embodiment of the microfluidic device 111 is shown. As shown in FIG. 13 , a grayscale pattern on a mask 105 is created. The mask 105 preferably is constructed using 8×4 swatches 6 like the one shown in FIG. 14 . FIG. 15 shows a close-up of the device 111 created. The device 111 includes an inlet 112 , a main microchannel 114 , and a plurality of side channels 118 .
[0076] Referring to FIGS. 16A-17B , in this embodiment of the device 111 , curved surfaces are generated with a single grayscale mask. For example, as shown in FIG. 16A , the mask 105 is created with first-level 5×1 swatches (arrays of 5×1 transparent and opaque pixels) that are elongated along the length of the microchannel to form lines 227 . The complexity of the curved surface 227 is then increased with simple graphic operations such as stretching, rotating, and skewing (graphics software may be used here). For example, a second pattern of lines may be used to generate a microchannel of smaller diameter. Here, after a first pattern is created, a second pattern is created by skewing the first pattern by 30 degrees. Then, the second pattern is overlaid on top of the first pattern to obtain a semi-circular micro channel 219 with a semi-spiral ridge inside. The resulting two axis symmetric grayscale gradients end up defining curved sides of the microchannel as shown in FIG. 16B . In FIGS. 17A and 17B , the same type of patterns are then used to create a microchannel 223 of smaller diameter then the rest of the microchannel 221 . The original is first skewed and overlaid on top of the patterns of the previous panel, rendering a single semi-spiral ridge. In the embodiment shown in FIG. 18 , the patterns in FIGS. 16A-17B were repeated several times along the main channel to build a “T” main microchannel 251 with a semi-screw mixer 253 . This is accomplished with a single mask.
[0077] In the example seen in FIG. 19 , the mixing part of the “T” microchannel is modified to introduce simultaneous modulation in the x, y, and z directions (i.e., a so-called zigzag pattern 225 ). As shown by the inset cross-section, the channel 254 goes from a larger diameter to a smaller diameter. The minimum spacing between patterns necessary to generate such stepped flat surfaces is also the area required as a transition between steps, and can be calculated with the sidewall angle and the height difference between steps. A sidewall angle of approximately 85 degrees is created from medium-low grayscale tones. Grayscale tones close to the homogenization threshold generate surfaces with lower sidewall angles that may vary depending on the pattern.
[0078] FIG. 20 shows a pattern 205 that may be used to create such a channel 254 . FIG. 21 shows a detail of an 8×4 swatch 206 a (10%) and a 5×1 swatch 206 b (60%) used to make such a pattern master 205 . As mentioned, once the method of the present invention has created a three dimensional microfluidic device, the device may be used to create libraries of liquid plugs with arbitrary concentrations of chemicals, cells, etc.
[0079] The homogenization phenomenon is further enhanced by designing a mask with an array of circles filled with different patterns to fabricate a combinatorial set of polymerized structures. Each circle in the mask may be tiled with a different 8×4 swatch (swatch formed by 8×4 pixels), that differ in either average “grayscale tone” (the ratio of transparent to opaque pixels where 0% is completely transparent and 100% completely opaque) or in pixel size. Again as shown in FIG. 1 , it was discovered that there is a transition where binary patterns on the mask are transferred to the photoresist as homogeneous polymerized patterns, or discrete polymerized patterns where the pixel geometry is apparent (e.g., one post per pixel). Interestingly, this transition does not depend on pixel density but instead is found to occur for a critical value of the product of n×a, where n is the number of transparent pixels per unit area, and a is the side length of the pixel.
[0080] Specifically, if n×a>5500 μm per unit of patterned area (in mm 2 ), the pattern is transferred as a homogeneous smooth surface (this condition may be referred to as the “grayscale homogenization threshold”). Further, if n×a<3000 μm/mm 2 , it is transferred as a collection of discrete pixelated patterns ( FIG. 2 ). Thus, while the relation between grayscale tone and polymerized feature height is reproducible, it may be complex to predict. Nevertheless, as shown in FIG. 34 a simple calibration method may be used to empirically determine this relation for a set of swatches and design microfluidic devices a posteriori. For example, each swatch produces a specific photopolymerized structure of a distinct height, and, therefore, they may be used as building blocks in a hierarchical design approach for the creation of complex polymerized patterns within the device. In this way, multilevel flat features can be easily fabricated by designing adjacent large areas with swatches of different grayscale tones.
[0081] FIGS. 22-24 , show how another embodiment of the present invention may be formed utilizing hierarchical patterning. FIG. 22 shows a compound of concentric circles 209 of different grayscale tones in pattern 205 . The 8×4 swatches 206 below from left to right correspond to a 35%, 45%, 60%, and 65% grayscale tone. FIG. 23 shows a mask design 207 pixilated using first-level 8×4 swatches 206 . First, a horn 210 is constructed from concentric circles 209 patterned with different tonalities of first-level grayscale 8×4 swatches. Such a single horn 210 is shown in FIG. 24 . In any event, the circles 209 vary monotonically from black in the outer circle (1 mm outer diameter) to white in the inner circle (50 μm diameter), as shown in FIG. 22 . Next, this design is used to define a second-level swatch, and apply it to pattern a large rectangle with the same repetitive motif as shown in FIG. 25A to create a master. Additional first-level swatches may be added to the design to generate multilevel micro channels or other curved surfaces. Alternatively, the master horn pattern 256 may be used to construct microfluidic ejectors 270 , shown in FIG. 27A .
[0082] Fabrication of the ejectors 270 is as follows: an adhesive 262 is poured over the master 256 , next a glass slide 264 with a thick membrane of polydimethylsiloxan (PDMS) 266 is pressed against the master 256 and the adhesive 262 is exposed to a UV light 261 . When both sides are pressed together, the tips of the horns are inserted into the soft PDMS layer 266 to form an ejector plate 272 . Thus, the horn cavities 269 created on one side of the sandwiched membrane end up in orifices that surface on the other side of the membrane. Next the completed membrane or ejector plate 272 is released from the master. The membrane with the horn cavities 269 connecting both sides is used as an ejector plate.
[0083] A prototype of an atomizer 274 with an ejector plate 272 is shown in FIG. 26 . The plate 272 is mounted over a PDMS gasket 282 and piezoelectric actuator 284 . These are then assembled between pieces of aluminum and polycarbonate to form a sandwich structure 286 around a fluid cavity, as shown in FIG. 26 .
[0084] To operate the ejector, the fluid cavity is primed with water. A sinusoidal AC voltage signal is then generated by a function generator provided by Stanford Research Systems DS345 and an RF amplifier provided by T&C Power Conversion AG1020. When it is operated at a specific frequency (e.g. from 0.8 to 1.1 MHz), the piezoelectric transducer 276 produces standing acoustic waves that are focused by geometrical reflections within the horns, creating a pressure gradient that can be used for fluid jet ejection. The resulting micro fluidic device 274 may be used to eject liquids, such as water, through the thiolene nozzle orifices at ≈5 ml/min flow rate (see, e.g., FIGS. 27A and 27B ). Moreover, the diameter of the nozzle orifices (40 μm) is well suited to cell manipulation via focused mechanical forces to enable various biophysical effects such as the uptake of small molecules and gene delivery and transfection. Additionally, the grayscale mask here may be designed to create nozzle orifices of different sizes for application to areas as diverse as mass spectrometry, fuel processing, manufacture of multilayer parts and circuits, and photoresist deposition without spinning.
[0085] FIG. 25A illustrates the result when the design of a single horn shown in FIG. 24 is used as a second-level swatch to pattern a large rectangular area (20×20 mm 2 ). After fabrication, this swatch pattern may be used to generate an array of thiolene horns. As shown in FIG. 25B , these horns then may be used as a template to replicate repetitive cavities and form an ejector plate (see, e.g., FIG. 26 ).
[0086] FIG. 26 shows a microfluidic device including the ejector formed from the array of horns. FIG. 27A shows a schematic illustrating the operation of an ultrasonic atomizer created using a method of the present invention. Here fluid enters the chamber through a capillary. When the piezoelectric transducer is driven at a resonant frequency of the chamber, pressure wave focusing leads to ejection of jets of liquid. FIGS. 27A and 27B both show a demonstration of jet ejection with a microfluidic.
[0087] As shown in FIGS. 28 and 29 , various pixels of varying sizes may be used to create a wide variety of swatches and ultimately microstructures. FIG. 28 shows the results of various experiments that have been conducted to determine homogeneous/discrete patterns and their relation with the size and number of transparent pixels. Note that here first level swatches are used to pattern 32 pattern intensities (‘tonalities’). Further, an array of grayscale binary masks of 2 mm circles are shown patterned with several grayscale tones. Swatches are also shown in the panels at different pixel sizes and densities, e.g., pixels per inch or ppi. The examples of thiolene polymerized patterns created with such masks are also shown.
[0088] FIG. 29 shows examples of the determination of a discrete pattern 4 a , a transition case 4 b , and a homogeneous pattern 4 c in the case of 75% grayscale with varying ppi. It should be noted that n is the number of pixels per millimeter squared of pattern and a is the pixel size in micrometers.
[0089] FIGS. 30-33 , show yet another embodiment of a microfluidic device 111 of the present invention including various microstructures 281 . FIGS. 30 and 31 show a master template of a microstructure and FIGS. 32-33 show replicas created from the template shown in FIGS. 30 and 31 . The insert view in FIG. 31 shows a grayscale pattern 283 used to produce the microstructure 281 . FIG. 30 shows a detail of the thiolene master pattern 285 showing the array of side microchannels 281 . FIG. 31 shows a detail of an end of a side microchannel 281 . The post 291 at the end of the micro channel 281 is used to create a cavity 293 on the PDMS replica 295 . FIG. 32 shows a bottom view of a PDMS replica 295 created using the master 285 . FIG. 33 shows that the previously discussed cavity may be used as a guide to introduce a thin metal tubing 297 and punch a small hole all the way through the PDMS and out to the exterior.
[0090] There are virtually innumerable uses for the present invention, all of which need not be detailed here. Additionally, all the disclosed embodiments can be practiced without undue experimentation. Further, although the best mode contemplated by the inventors of carrying out the present invention is disclosed above, practice of the present invention is not limited thereto. It will be manifest that various additions, modifications, and rearrangements of the features of the present invention may be made without deviating from the spirit and scope of the underlying inventive concept.
[0091] In addition, the individual components of the present invention discussed herein need not be fabricated from the disclosed materials, but could be fabricated from virtually any suitable materials. Moreover, the individual components need not be formed in the disclosed shapes, or assembled in the disclosed configuration, but could be provided in virtually any shape, and assembled in virtually any configuration. Furthermore, all the disclosed features of each disclosed embodiment can be combined with, or substituted for, the disclosed features of every other disclosed embodiment except where such features are mutually exclusive.
[0092] Further, although the concept of pattern homogenization for the fabrication of 3D structures is shown and described here using masking opaque/transparent motifs and UV light, the same concept could easily be accomplished using infrared light (thermal radiation) and a thermal-resist instead of UV light and a photoresist. Another additional possibility would be to use conventional lithography to create the motifs on a photoresist covering a silicon or glass wafer. The photoresist with the motifs would work as a mechanical mask for the fabrication of 3D structures on the wafers using wet or dry etching.
[0093] It is intended that the appended claims cover all such additions, modifications, and rearrangements. Expedient embodiments of the present invention are differentiated by the appended claims. | A three dimensional microfluidic device for passive sorting and storing of liquid plugs is provided with homogeneous surfaces from the exposure of a photopolymer through binary masking motifs, i.e., arrays of opaque pixels on a transparency mask. The device includes sub-millimeter three-dimensional relief microstructures to aid in the channeling of fluids. The microstructures have topographically modulated features smaller than 100 micrometers. | 1 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a Continuation of PCT/DE2011/001165 filed Jun. 3, 2011, which in turn claims the priority of DE 10 2010 024 939.4 filed Jun. 24, 2010, the priority of both applications is hereby claimed and both applications are incorporated by reference herein.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to a method for gluing a friction lining to a support by means of an adhesive that develops its full adhesive effect under the influence of pressure and/or temperature. The invention further relates to a tool for sticking a friction lining to a support by means of an adhesive. The invention further relates to a tool for stacked gluing of supports comprising friction linings that have been stuck to the supports.
2. Description of Prior Art
It is known from German patent specification DE 44 31 642 B4 to connect a friction lining to a support when producing a preform. The support can be connected to the finished lining during the course of a hot pressing procedure or by means of a separate gluing process. The object of the invention is to improve the gluing of friction linings to supports by means of an adhesive.
With a method for gluing a friction lining to a support by means of an adhesive that develops its full adhesive effect under the influence of pressure and/or temperature, the object is achieved in that the friction lining and the support are pressed together along with the adhesive before the adhesive develops its full adhesive effect in order to stick the friction lining to the support. When affixing the friction lining to the support, the friction lining is pre-fixed to the support. The friction lining is then only ultimately fixed to the support when the glue develops its full adhesive effect. The glue develops its full adhesive effect in a subsequent crosslinking or curing process under the relatively prolonged influence of a higher temperature compared with during the affixation of the friction lining to the support. To affix the friction lining to the support, the adhesive is only subject over a short period to a high pressure and a lower temperature than when curing or crosslinking. The friction lining is preferably a clutch friction lining of a dry friction clutch, in particular a double clutch. The support is preferably a sheet metal support. The friction lining is preferably coated with adhesive.
A preferred exemplary embodiment of the method is characterized in that the adhesive is made to flow under the influence of pressure and/or temperature, before the adhesive develops its full adhesive effect. The flowing adhesive distributes optimally between the support and friction lining. The flowing adhesive particularly advantageously penetrates, in part, the preferably porous friction lining. During this process, the pressure and/or the temperature is/are set such that the adhesive does not yet crosslink or cure. The adhesive only crosslinks or cures after the affixing process, at a much higher temperature over a longer period of time.
A further preferred exemplary embodiment of the method is characterized in that the support and the friction lining are positioned and/or centered relative to one another before being pressed together. The support and friction lining are preferably positioned and/or centered in a special pressing tool. During the process, the support and friction lining are positioned relative to one another in particular in the circumferential direction.
A further preferred exemplary embodiment of the method is characterized in that a plurality of friction linings stuck to supports are pressed together in a stacked-gluing process, wherein the adhesive develops its full adhesive effect. In the case of stacked gluing, the friction linings already stuck to the supports are pressed together at a high temperature over a longer period of time than during the previous affixing process, such that the adhesive crosslinks or cures. The pressure during crosslinking or curing is lower than when affixing the friction linings.
With a tool for sticking a friction lining to a support by means of an adhesive, in particular by a method described above, the problem stated in the introduction is achieved in that the tool has a lower tool plate and an upper tool plate, between which the friction lining and the support are pressed together along with the adhesive. The terms “lower” and “upper” relate to the direction of action of the force of gravity. The friction lining is preferably coated with the adhesive. However, it is also possible to coat the support, or the support and the friction lining, with the adhesive. The two tool plates are preferably installed in a C-frame press, with which the required pressure for affixing the friction lining to the support can be applied. A heating plate is installed in the tool plate, which contacts the support, in order to introduce into the tool the heat required to affix the friction lining to the support.
A preferred exemplary embodiment of the tool is characterized in that the lower tool plate has centering pins for the friction lining and centering pins for the support. The centering pins are used to position and/or center the friction lining and the support relative to the tool and relative to one another.
A further preferred exemplary embodiment of the tool is characterized in that the centering pins taper conically at their free end. The centering and positioning of the friction lining and the support is thus facilitated, such that the process can be automated.
A further preferred exemplary embodiment of the tool is characterized in that the centering pins are guided movably in the lower tool plate in their longitudinal direction and are biased by a spring in the direction of the upper tool plate. The positioning and centering of the support and friction lining is thus further facilitated. The tool according to the invention is preferably combined with further tools in a round plate facility.
A further preferred exemplary embodiment of the tool is characterized in that the centering pins for the support have an outer diameter that is different from that of the centering pins for the friction lining. Corresponding through-holes for the centering pins are provided in the support and in the friction lining. The friction lining is preferably positioned and centered first on the lower tool plate. During this process, a through-hole in the friction lining for the centering pin of the support is left open.
With a tool for stacked gluing of supports comprising friction linings that have been affixed to the supports in particular by a method described above, in particular using a tool described above, the above-stated object is achieved in that the tool for stacked gluing has centering rods, which are arranged radially to the outside of the friction linings stuck to the supports in order to position and/or center these friction linings between two press plates. A total of four centering rods are preferably guided into the corner regions of the preferably square press plates. Further positioning pins, which extend through the supports or friction linings, can be omitted. In the case of stacked gluing, the previously affixed friction linings are connected fixedly to the friction linings by applying pressure and high temperature over a relatively long period of time, wherein the adhesive cures or crosslinks.
DESCRIPTION OF THE DRAWINGS
Further advantages, features and details of the invention will emerge from the following description, in which various exemplary embodiments are described in detail with reference to the drawing, in which:
FIG. 1 shows a sectional view of a tool for sticking according to the invention, taken along a line I-I in FIG. 2 ;
FIG. 2 shows a plan view of the tool from FIG. 1 ;
FIG. 3 shows a perspective illustration of the section from FIG. 1 ;
FIG. 4 shows an enlarged detail IV from FIG. 3 ;
FIG. 5 shows an enlarged detail V from FIG. 3 ;
FIG. 6 shows a sectional view of a tool for stacked gluing; and
FIG. 7 shows an enlarged detail VII from FIG. 6 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
A tool 1 for fastening, including an upper tool plate 2 and a lower tool plate 3 is illustrated in various views and details in FIGS. 1 to 5 . In the sectional views of FIGS. 1 and 3 , it can be seen that the upper tool plate 2 has a plurality of through-holes 5 , 6 , 7 , 8 . The through-holes 5 , 6 are used to receive the upper ends of centering pins 11 , 12 , which are guided movably to and fro in the lower tool plate 3 in the longitudinal direction. The through-holes 7 , 8 are used to fasten the upper tool plate 2 to a C-frame press (not illustrated).
The lower tool plate 3 likewise comprises a plurality of through-holes 9 , 10 . The through-holes 9 , 10 are used to fasten the lower tool plate 3 to the C-frame press. The centering pins 11 , 12 are guided movably to and fro in further through-holes.
In the plan view illustrated in FIG. 2 , it can be seen that the two tool plates 2 , 3 each have a total of five through-holes for fastening the tool plates to the frame press. In addition, it can be seen that the tool 1 comprises a total of eight centering pins 11 , 12 . The centering pins 11 are arranged alternately with the centering pins 12 in the circumferential direction. Each centering pin 11 is thus arranged between two centering pins 12 in the circumferential direction. Similarly, each centering pin 12 is arranged between two centering pins 11 in the circumferential direction. The centering pins 11 are assigned to a friction lining 15 . The centering pins 12 are assigned to a support 16 , which is designed as a sheet metal support. The friction lining 15 is coated with an adhesive, which is used to fasten the friction lining 15 to the support 16 .
In FIGS. 4 and 5 , it can be seen that the centering pins 11 , 12 each have a conical tapering 21 , 22 at their respective ends protruding from the tool plate 3 . At their ends arranged in the tool plate 3 , the centering pins 11 , 12 each have a collar 35 ; 25 , which constitutes an axial stop for the movement of the centering pins 11 , 12 upwardly from the tool plate 3 .
The centering pins 11 , 12 are each biased upwardly from the tool plate 3 by a spring 36 ; 26 , that is to say toward the upper tool plate 2 . The spring 36 ; 26 is arranged in each case with its upper end in the hollow centering pin 11 , 12 . With its lower end, the spring 36 ; 26 is supported on a spring cap 37 ; 27 , which is fastened to the underside of the lower tool plate 3 .
In FIG. 4 , it can be seen that the centering pin 12 extends both through the friction lining 15 and through the support 16 arranged thereabove. The conical tapering 22 at the free end of the centering pin 12 protrudes in part beyond the support 16 and into the through-hole 5 in the upper tool plate 2 arranged thereabove.
In FIG. 5 , it can be seen that the centering pin 11 for the friction lining 15 protrudes upwardly beyond the friction lining 15 . The support 16 has a through-hole 39 in the region of the centering pin 11 . The centering pin 11 can extend through the through-hole 39 and into the through-hole 6 in the upper tool plate 3 arranged thereabove.
The tool 1 for sticking illustrated in FIGS. 1 to 5 is also referred to as an affixing tool. The two tool plates 2 , 3 are fabricated for example from tool steel and are installed on the C-frame press via special guides. The friction lining 15 is centered and positioned on the lower tool plate 3 by the four centering pins 11 . The support 16 is then positioned and centered relative to the friction lining 15 via the four centering pins 12 .
The press is then closed and pre-fixes the support 16 on the friction lining 15 . The pre-fixing process is also referred to as sticking or affixing. During the pre-fixing process, the support 16 is stuck to the friction lining 15 . The friction lining 15 is, of course, also stuck to the support 16 during this process. In a variant of the tool 1 , the friction lining 15 may be inserted first, followed by the support 16 .
A heat-activatable, possibly solvent-containing, adhesive on the basis of nitrile rubber/phenol resin is preferably used as an adhesive. For the affixing process, a pressure of approximately 50 tons with an affixing time of approximately 10 seconds is preferably applied by the frame press. The affixing temperature is between 150 degrees Celsius and 205 degrees Celsius. At this affixing pressure and at this affixing temperature, the adhesive starts to flow, but does not yet cure.
In each case, a friction lining 15 is stuck to a support 16 , or vice versa, in the tool 1 . After the affixing process, the stuck friction lining/support composite is removed from the opened tool 1 . The friction lining/support composite parts stuck together are then subjected to stacked gluing in a tool 41 .
A tool 41 for stacked gluing is illustrated in FIGS. 6 and 7 in various views. The stacked-gluing tool 41 comprises two press plates 42 and 43 . The press plate 42 may be arranged above the press plate 43 based on the direction of action of the force of gravity. A total of three stacks 45 , 46 , 47 comprising friction lining/support composite parts glued together are arranged between the two press plates 42 and 43 . Each stack comprises twelve stuck composite parts, which each comprise a friction lining 15 , which is affixed to the respective support 16 . An intermediate plate 51 , 52 is arranged between the stacks 45 , 46 and between the stacks 46 , 47 .
In the outer circumferential edge region of the tool 41 , four centering rods 54 , 55 extend through the intermediate plates 51 , 52 and to the outside of the stacks 45 to 47 . In accordance with a preferred exemplary embodiment, the four centering rods 54 , 55 are arranged radially to the outside of the stacks 45 to 47 in the corner regions of the press plates 42 , 43 , such that the friction linings 15 glued to the supports 16 are centered radially to the inside of the centering rods 54 , 55 .
A central threaded rod 60 extends through the press plates 42 , 43 , the stacks 45 to 47 and the intermediate plates 51 , 52 . A first nut 61 is fastened at one end of the threaded rod 60 . A second nut 62 is screwed onto the other end of the threaded rod 60 . A bearing 64 , which is designed as an axial deep groove ball bearing, and a disk spring assembly 65 are arranged between the nut 62 and the press plate 42 .
A defined torque is introduced via the nut 62 and the central threaded rod 60 in order to tension the two press plates 42 and 43 against one another. In the case of stacked gluing, a sufficient pressure is applied to the tool 41 . During the process, the tool 41 is exposed to a temperature of approximately 205 degrees Celsius, for example in a furnace, for approximately six hours. In the case of stacked gluing, a much lower pressure of approximately three tons may possibly be sufficient with the component parts already stuck in order to cure or crosslink the adhesive.
With stacked gluing, the adhesive crosslinks fully. Before the stacks 45 to 47 are removed, they are cooled to room temperature. The pressure during stacked gluing is preferably maintained from the moment at which the press plates 42 , 43 are clamped, during the stacked gluing process in the furnace, until removal. Due to the combination according to the invention of the affixing process in the tool 1 illustrated in FIGS. 1 to 5 with the stacked gluing in the tool 41 illustrated in FIGS. 6 and 7 , extremely high requirements in terms of burst speed, in particular after thermal damage, can be met.
LIST OF REFERENCE SIGNS
1 tool
2 upper tool plate
3 lower tool plate
5 through-hole
6 through-hole
7 through-hole
8 through-hole
9 through-hole
10 through-hole
11 centering pin
12 centering pin
15 friction lining
16 support
21 conical tapering
22 conical tapering
25 collar
26 spring
27 spring cap
35 collar
36 spring
37 spring cap
39 through-hole
41 tool
42 upper press plate
43 lower press plate
45 stack
46 stack
47 stack
51 intermediate plate
52 intermediate plate
54 centering rod
55 centering rod
60 threaded rod
61 nut
62 nut
64 bearing
65 disk spring assembly | The invention relates to a method for gluing a friction lining to a support by means of adhesive that develops its full adhesive effect under the effect of pressure and/or temperature. The invention is characterized in that the friction lining and the support are pressed together along with the adhesive before the adhesive develops its full adhesive effect in order to glue the friction lining to the support. | 1 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This invention claims priority of the German patent application 101 03 253.6 which is incorporated by reference herein.
FIELD OF THE INVENTION
[0002] The invention relates to a method for transporting and inspecting semiconductor substrates. In addition, the invention relates to an arrangement for transporting and inspecting semiconductor substrates.
BACKGROUND OF THE INVENTION
[0003] U.S. Pat. No. 5,863,170 discloses a modular process system for semiconductors. This system, for handling wafers, is of modular construction and has a large number of process stations, which are loaded with wafers. The wafers are forwarded from process station to process station by a central carousel. In the process stations, various process steps are carried out on the wafers. This arrangement can be used only for treatment in various process stations. Monitoring and inspection of the wafers is not provided.
[0004] U.S. Pat. No. 5,807,062 discloses an arrangement for handling wafer-like objects. The wafers in the arrangement are transferred from and to magazines. In the arrangement itself there are arranged three workstations. In the first workstation, the wafer-like object is aligned with respect to a plane and an angle. The next workstation represents the x/y table of an inspection microscope. The third workstation is used for the visual monitoring of the wafer-like objects by an operator. The workstations are in each case arranged at an angle of 120° to one another. A changer sits between the workstations and, with its three arms, can feed the wafer-like objects to the individual workstations. The changer has three arms and additional means for the fine positioning of the wafer-like objects. To this end, there is on the shaft of the changer a gearwheel, in which jaws with identical toothing engage and thus permit fine adjustment of the changer. The drawback with this arrangement is that it cannot be used so universally, and fine positioning takes up a relatively long time.
SUMMARY OF THE INVENTION
[0005] It is the object of the present invention to provide a method with which wafer-like objects can be handled in a time-saving manner, and a high throughput of the wafer-like objects is achievable with this method.
[0006] The object is achieved by a method comprising the steps of:
[0007] providing at least three workstations arranged in a housing, wherein a changer being arranged in such a way that each of the workstations can be supplied with a semiconductor substrate;
[0008] lifting the changer and carrying out a rotational movement by a specific angular amount, in order to transfer al least one of the semiconductor substrates to another workstation;
[0009] lowering the changer and carrying out a rotational movement by the same angular amount in the opposite direction, without a semiconductor substrate resting on the changer; and
[0010] picking up a new semiconductor substrate from a substrate feed module.
[0011] It is a further object of the invention to provide an arrangement which permits wafer-like objects to be inspected visually and microscopically in a simple, time-saving manner. Added to this is the intention that the arrangement shall also be able to operate with inaccurately positioned wafer-like objects. Furthermore, wafer-like objects of different sizes are intended also to be processed with the invention.
[0012] The object is achieved by an arrangement for transporting and inspecting semiconductor substrates which comprises at least three workstations, a changer defining an axis of rotation, wherein the changer has at least three arms, and which is designed to load the at least three workstations with semiconductor substrates, the workstations being arranged coaxially around the axis of rotation of the changer, a measuring device is assigned to one workstation, wherein the measuring device determines the deviation of the current position of the semiconductor substrate from an intended position and makes it available to the arrangement for the further inspection of the semiconductor substrate and in that the changer is not equipped with means for moving the semiconductor substrates into the intended position.
[0013] It is advantageous to have an arrangement for transporting and inspecting semiconductor substrates. The arrangement comprises:
[0014] a first, second and third workstation,
[0015] a changer defining an axis of rotation, wherein the changer has three arms, and which is designed to load and unload the three workstations with semiconductor substrates,
[0016] the first workstation defines a transfer position, at which semiconductor substrates are introduced into the arrangement from a substrate feed module and can be transferred from the arrangement to the substrate feed module,
[0017] the second workstation is a measuring device, which determines the deviation of the current position of the semiconductor substrate from an intended position and makes it available to the arrangement for the further inspection of the semiconductor substrate, and
[0018] the third workstation defines a micro inspection and comprises an x/y table, which feeds the semiconductor substrate to a microscope.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] The subject of the invention is illustrated schematically in the drawing and will be described below using the figures, in which:
[0020] [0020]FIG. 1: shows a schematic view of the arrangement, which is connected to a substrate feed module for wafer-like objects;
[0021] [0021]FIG. 2: shows a further exemplary embodiment of a possible set-up of the arrangement and of the substrate feed module;
[0022] [0022]FIG. 3: shows a schematic illustration of the configuration of the workstation in side view in the area of the optical inspection microscope;
[0023] [0023]FIG. 4: shows a plan view of the arrangement to clarify the flow of the semiconductor substrates;
[0024] [0024]FIG. 5: shows an illustration of two cycles in a possible scenario of the flow of the semiconductor substrates in the arrangement, macro inspection by the user being dispensed with;
[0025] [0025]FIG. 6: shows an illustration of two cycles in a further scenario of the flow of the semiconductor substrates in the arrangement, a macro inspection additionally being carried out;
[0026] [0026]FIG. 7: shows an illustration of a cycle in which a poor semiconductor substrate has been found during the visual macro inspection; and
[0027] [0027]FIG. 8: shows an illustration of the handling of semiconductor substrates, in which only one semiconductor substrate per cycle is inspected in the arrangement, and no visual macro inspection is carried out.
DETAILED DESCRIPTION OF THE INVENTION
[0028] [0028]FIG. 1 shows, in schematic form, a lateral assignment of a substrate feed module 1 to an arrangement 3 having a plurality of workstations 8 , 10 , 12 . The substrate feed module 1 in this exemplary embodiment is oriented with respect to the arrangement 3 in such a way that it can be loaded with substrates from its front side 2 via one or more load ports 2 a, 2 b. Normally, two load ports 2 a, 2 b are provided. In this case, open or closed cassettes 4 are used, which are inserted manually, by the user, or by means of automation, for example by means of a robot, into the load ports 2 a, 2 b. The cassettes 4 can be filled with semiconductor substrates 6 or can also be empty, depending on the working sequence envisaged. For example, all the cassettes 4 can be filled and semiconductor substrates 6 are first removed from one cassette 4 , inserted into the arrangement 3 and, after treatment and monitoring there, are put back into the same cassette 4 again. This procedure is then repeated for the next cassette 4 , while the user retrieves the cassette 4 with the processed semiconductor substrates 6 and, in its place, inserts a new cassette 4 with semiconductor substrates 6 into the free load port 2 a, 2 b. Provided in the interior of the substrate feed module 1 is a transport robot 5 , which transfers the semiconductor substrates 6 into the arrangement 3 . The arrangement of the substrate feed module 1 in FIG. 1 is merely one of a plurality of possible configurations. Likewise, the substrate feed module 1 can be rotated through 90°, so that the cassettes point away from the arrangement 3 .
[0029] As already mentioned, a plurality of workstations 8 , 10 and 12 are provided in the arrangement 3 . At the workstations 8 , 10 and 12 , appropriate investigations, monitoring and inspections are carried out on the semiconductor substrates 6 . In the present exemplary embodiment, three workstations, a first, a second and a third workstation 8 , 10 and 12 , are provided in the arrangement. Arranged centrally between the workstations 8 , 10 and 12 is a changer 14 for the semiconductor substrates 6 . The changer 14 has three arms 14 a, 14 b and 14 c, with which the individual workstations 8 , 10 and 12 can be supplied simultaneously with the semiconductor substrates 6 . The first workstation 8 is used for acceptance from and transfer to the substrate feed module 1 . The second workstation 10 is used for the alignment, for the determination of the positioning and for the visual inspection of the semiconductor substrates 6 . In order to align the semiconductor substrates 6 , the second workstation 10 is assigned a measuring device 15 , which detects marks applied to the semiconductor substrate 6 and determines codings on the semiconductor substrates. Furthermore, the measuring device 15 determines the deviation from the accurately-positioned deposition of the semi-conductor substrate 6 in the second workstation 10 . The data determined in this way are forwarded to a central processing unit (not shown). The third workstation 12 is designed for the micro inspection of the semiconductor substrates 6 . The third workstation 12 has an x/y table 17 , which feeds the semiconductor substrate 6 to a microscope 16 for the micro inspection. A z displacement can also be made possible by the x/y table. The arrangement 3 is surrounded by a housing 18 , which shuts off the three workstations 8 , 10 and 12 and the microscope 16 with respect to the ambient air and provides the correspondingly required clean-room conditions. Added to this is the fact that the possibility of intervention by the user in the arrangement 3 is likewise prevented by the housing 18 , which additionally constitutes a security aspect. In the embodiment disclosed here, the microscope 16 is provided with an eyepiece 20 , which provides the user with the possibility of carrying out a visual micro inspection of the semiconductor substrates 6 to be examined. Of course, the semiconductor substrates 6 can be inspected automatically by the microscope 16 in the third workstation 12 . The housing 18 of the arrangement 3 and the substrate feed module 1 have docking elements 22 , which permit a variable association between substrate feed module 1 and arrangement 3 .
[0030] An exemplary embodiment of the this variable association is shown in FIG. 2 and shows a possible setup of the arrangement 3 and the substrate feed module 1 . The arrangement 3 defines a transfer position 24 , at which the semiconductor substrates 6 are introduced into the arrangement 3 by the substrate feed module 1 . For this purpose, the docking elements 22 are fitted in or on the housing 18 of the arrangement 3 in an appropriate way. From the cassettes 4 , the semiconductor substrates 6 pass via the load ports 2 a, 2 b into the substrate feed module 1 and, from there by means of the transport robot 5 , to the transfer position 24 of the arrangement 3 .
[0031] [0031]FIG. 3 shows a schematic illustration of the configuration of the workstation in side view in the area of the optical inspection microscope 16 . The changer 14 can be rotated freely about an axis of rotation 13 . In addition, the changer 14 can be moved up and down axially, in order in this way to pick up the semiconductor substrates 6 or set them down in the third workstation 12 . The axial movement of the changer 14 , which likewise corresponds to the movement in the z direction, is represented by a double arrow A-A. In the lifted position 14 up, the changer 14 is shown dashed. In the lifted position 14 up of the changer 14 , the changer is able to move with its arms above a plane 19 which is defined by a wafer set down in the workstation 12 . The plane 19 is illustrated in FIG. 3 by a thick dashed line. In addition, the workstation 12 has a cutout 21 , through which the changer 14 can freely rotate its arms 14 a and 14 b. The cutout 21 makes it possible for the changer 14 to rotate freely in the forward and reverse directions when in the lowered position. The second workstation 10 , in the basic position in FIG. 3, is likewise represented by continuous lines. The second workstation 10 can be moved into a central position 10 m and into a lifted position 10 up. In the central position 10 m, the second workstation 10 is at the level of the plane 19 . As already mentioned in FIG. 1, the second and third workstations 10 and 12 are arranged physically in such a way that they can be supplied with semiconductor substrates 6 by the arms 14 a and 14 b of the changer 14 .
[0032] [0032]FIG. 4 shows a schematic plan view of the arrangement 3 to clarify the flow of the semiconductor substrates 6 . An arrow 26 in FIG. 4 marks the point at which the semiconductor substrates 6 are introduced into the arrangement 3 . In a preferred embodiment, the changer 14 has three arms 14 a, 14 b and 14 c, which are each arranged at an angle of 120°. The changer 14 guides the semiconductor substrates 6 to the individual workstations 8 , 10 and 12 . The first workstation 8 is the transfer position 8 a, the second workstation 10 is the macro inspection 10 a, and the third workstation 12 is the micro inspection 12 a. The transfer position 8 a, macro inspection 10 a and micro inspection 12 a define the position of the changer 14 at which the semiconductor substrates 6 are accepted by the workstations 8 , 10 and 12 or are transferred to the workstations 8 , 10 and 12 . Given optimum utilization, there are three semiconductor substrates in the arrangement 3 at the same time, simultaneous macro inspection 10 a and micro inspection 12 a being possible. The dashed circle in FIG. 4 defines an outer movement circle 28 of the changer 14 together with the semiconductor substrates 6 resting on the changer 14 . Each of the semiconductor substrates 6 has an identification 30 and a notch 32 . The identification 30 comprises, for example, a barcode, a numeric identification, an alphanumeric identification or combinations thereof. The notch 32 is used to determine the orientation of the semiconductor substrate 6 and, consequently, also for its precise spatial alignment.
[0033] [0033]FIG. 5 shows a graphical representation of two cycles n and n+1 in a possible scenario of the flow of the semiconductor substrates 6 in the arrangement 3 . The time t is plotted on the x-axis in FIG. 5 and in FIGS. 6 to 8 . The representations in FIGS. 5 to 8 are to be viewed as schematic, and the time intervals represent an approximate duration of the processing time of the semiconductor substrates at the workstations. In the exemplary embodiment illustrated in FIG. 5, three semiconductor substrates 6 are located simultaneously in the arrangement 3 . A visual macro inspection is not carried out by the operator in this exemplary embodiment. At the beginning of the flow of the semiconductor substrates 6 in the arrangement, the first semiconductor substrate 6 1 is at the transfer position 8 a, the second semiconductor substrate 6 2 is in the macro inspection 10 a, and the third semiconductor substrate 6 3 is in the micro inspection 12 a. The transfer position 8 a, the macro inspection 10 a and the micro inspection 12 a are illustrated as a dashed line in FIGS. 5 to 8 . The residence time of the semiconductor substrates is identified by vertical lines in FIGS. 5 to 8 , and the interspace is designated by the reference symbol of the semiconductor substrate just being processed.
[0034] The changer 14 makes a stroke in the axial direction (in each case represented by an upward arrow in FIGS. 5 to 8 ) and lifts the second and the third semiconductor substrates 6 2 and 6 3 off the macro inspection 10 a and the micro inspection 12 a, respectively. The changer 14 rotates, and in this way the first semiconductor substrate 6 1 reaches the macro inspection 10 a, the second semiconductor substrate 6 2 reaches the micro inspection 12 a and the third semiconductor substrate 6 3 is finally transported to the transfer position 8 a and transferred to the substrate feed module 1 . The changer 14 is then lowered (in each case represented by a downward arrow in FIGS. 5 to 8 ) and rotated back through −120° with empty arms. A fourth semiconductor substrate 6 4 is fed to the empty arm at the transfer position 8 a from the substrate feed module 1 . Before this exchange is carried out, the necessary inspection has been carried out on the first and second semiconductor substrates 6 1 and 6 2 at the second and third workstations 10 and 12 . After a certain time, the changer 14 again carries out an axial stroke, in order to initiate the cycle n+1. The changer 14 once again makes an axial stroke and carries out a rotation by +120°. The fourth semiconductor substrate 6 4 therefore reaches the macro inspection 10 a, and the first semiconductor substrate 6 1 is fed to the micro inspection 12 a. The movement sequence of the changer 14 is identical to that already mentioned above. At the transfer position 8 a, the second semiconductor substrate 6 2 is replaced by a fifth semiconductor substrate 6 5 . This fifth semiconductor substrate 6 5 then passes through the workstations 8 , 10 and 12 in the arrangement 3 in the following cycle.
[0035] A further embodiment of the handling of the semiconductor substrates 6 in the arrangement 3 is disclosed in FIG. 6. In this case, a macro inspection is additionally carried out by the user. Just as at the start of the flow of semiconductor substrates 6 disclosed in FIG. 5 in the arrangement 3 , the first semiconductor substrate 6 1 is at the transfer position 8 a, the second semiconductor substrate 6 2 is in the macro inspection 10 a and the third semiconductor substrate 6 3 is in the micro inspection 12 a. The changer 14 makes an axial stroke and lifts the second and the third semiconductor substrates 6 2 and 6 3 off the macro inspection 10 a and the micro inspection 12 a, respectively. The changer 14 rotates through +120° and, in this way, the first semiconductor substrate 6 1 reaches the macro inspection 10 a, the second semiconductor substrate 6 2 reaches the micro inspection 12 a and the third semiconductor substrate 6 3 is finally transported to the transfer position 8 a and transferred to the substrate feed module 1 . While the micro inspection 12 a is being carried out at the third workstation 12 , the changer 14 is lowered axially and is then rotated through −60°. The changer 14 is thus moved out of the working range of the second workstation 10 . This is necessary, since the semiconductor substrate 6 in the second workstation 10 is pivoted in the visual range of the operator and rotated, in order to detect possible macroscopic faults on the semiconductor substrate 6 . When the visual macro inspection has been completed, the changer 14 , which is still lowered, rotates through a further −60°. A fourth semiconductor substrate 6 4 is fed to the arm at the transfer position 8 a from the substrate feed module 1 . Before this exchange was carried out, the necessary inspection has been carried out on the first and second semiconductor substrates 6 1 and 6 2 at the second and third workstations 10 and 12 . After a certain time, the changer 14 again carries out an axial stroke, in order to initiate the cycle n+1. The changer 14 once more makes an axial stroke and a rotation through +120°. The fourth semiconductor substrate 6 4 thus reaches the macro inspection, and the first semiconductor substrate 6 1 is fed to the micro inspection 12 a. The movement sequence of the changer 14 is identical to that already mentioned above. At the transfer position 8 a, the second semiconductor substrate 6 2 is replaced by a fifth semiconductor substrate 6 5 . This fifth semiconductor 6 5 then passes through the workstations 8 , 10 and 12 in the arrangement 3 in the following cycle.
[0036] [0036]FIG. 7 shows a representation of a cycle in which a poor semiconductor substrate has been found during the visual macro inspection. Here, just as already shown in FIG. 6, a visual macro inspection is carried out by the user. Just as at the start of the flow of semiconductor substrates 6 disclosed in FIG. 5 in the arrangement 3 , the first semiconductor substrate 6 1 is at the transfer position 8 a, the second semiconductor substrate 6 2 is in the macro inspection 10 a and the third semiconductor substrate 6 3 is in the micro inspection 12 a. The changer 14 makes an axial stroke and lifts the second and the third semiconductor substrates 6 2 and 6 3 off the macro inspection 10 a and the micro inspection 12 a. The changer 14 rotates through +120° and, in this way, the first semiconductor substrate 6 1 reaches the macro inspection 10 a, the second semiconductor substrate 6 2 reaches the micro inspection 12 a, and the third semiconductor substrate 6 3 is finally transported to the transfer position 8 a and transferred to the substrate feed module 1 , the changer 14 being lowered axially. While the micro inspection 12 a is being carried out at the third workstation 12 , changer 14 is then rotated through −60°. Thus, as already mentioned in FIG. 6, the changer 14 is moved out of the working range of the second workstation 10 . During the visual macro inspection, the first semiconductor substrate 6 1 has been identified as faulty. A fourth semiconductor substrate 6 4 which may possibly already have been transferred to the changer 14 at the transfer position 8 a, is transported back into the substrate feed module 1 again. The changer 14 , lowered axially, rotates through a further +60°. One arm of the changer 14 accepts the first semiconductor substrate 6 1 by lowering the second workstation 10 into the basic position. It is necessary to lower the workstation 10 into the basic position in order that the changer 14 can rotate freely. The changer 14 rotates through −120° in the lowered state and thus brings the first semiconductor substrate 6 1 into the transfer position 8 a. The second semiconductor substrate 6 2 is still in the third workstation 12 or the micro inspection 12 a. At the transfer position 8 a, the first faulty semiconductor substrate 6 1 is transferred to the substrate feed module 1 , and a fourth semiconductor substrate 6 4 from the substrate feed module 1 is deposited on the changer 14 . Finally, the changer, lowered, rotates through +120° and brings the fourth semiconductor substrate 6 4 to the second workstation 10 . The fifth semiconductor substrate 6 5 is transferred to the changer 14 at the transfer position 8 a. The changer 14 , lowered, then rotates through −60°, in order to leave the active range of the second workstation 10 free. At the first workstation 10 , the visual macro inspection is carried out on the fourth semiconductor substrate 6 4 . After the visual macro inspection has been completed, the changer 14 again rotates through −60° and then the semiconductor substrates located in the arrangement 3 can be changed in accordance with the method already described in FIG. 5 and FIG. 6.
[0037] [0037]FIG. 8 shows an embodiment of the method for handling semiconductor substrates in which only one semiconductor substrate 6 per cycle is examined in the arrangement 3 . No visual macro inspection takes place. The first semiconductor substrate 6 1 is transferred from the substrate feed module 1 to the changer 14 . The changer rotates through +120° and the first semiconductor substrate 6 1 is transferred to the second workstation 10 . There, the alignment of the first semiconductor substrate 6 1 is determined and the identification 30 on the first semiconductor substrate 6 1 is then read. In the meantime, the changer 14 , lowered axially, rotates through −120°. The changer then makes a z stroke and removes the first semiconductor substrate 6 1 from the second workstation 10 . The changer rotates through +120° and transfers the first semiconductor substrate 6 1 to the third workstation 12 , where the micro inspection is carried out. After the micro inspection, the changer 14 makes another z stroke, removes the first semiconductor substrate 6 1 from the third workstation 12 and rotates through −120°. The first semiconductor substrate 6 1 in turn passes to the second workstation 10 and, there, the notch 32 is determined, so that the first semiconductor substrate 6 1 is aligned. In the meantime, the changer 14 , lowered axially, rotates through +120°. The changer 14 then makes an axial stroke, removes the first semiconductor substrate 6 1 from the second workstation 10 and rotates through −120°. The first semiconductor substrate 6 1 is then at the transfer position 8 a and is transferred to the substrate feed module 1 . A second semiconductor substrate 6 2 is removed from the substrate feed module 1 and, using the second semiconductor substrate 6 2 , the method already described above is carried out as for the first semiconductor substrate 6 1 .
[0038] It is self-evident that, depending on the number of semiconductor substrates 6 in the arrangement 3 , or changes in the flow of the semiconductor substrates 6 through the arrangement 3 , such as the removal of defective semiconductor substrates 6 , the residence time of the semiconductor substrates at the individual workstations 6 may change. Consequently, this also has an effect on the cycle time.
[0039] The invention has been described with reference to a special embodiment. However, it is self-evident that changes and modifications can be carried out without leaving the scope of protection of the following claims in so doing. | The invention relates to an arrangement for transporting and inspecting semiconductor substrates ( 6 ), having at least three workstations ( 8, 10, 12 ), a changer ( 14 ), which has at least three arms ( 14 a, 14 b, 14 c ) which are designed to load the individual workstations ( 8, 10, 12 ) with semiconductor substrates ( 6 ). A measuring device ( 15 ) is assigned to the second workstation ( 10 ), determines the deviation of the current position of the semiconductor substrate ( 6 ) and makes it available to the arrangement ( 3 ) for the further inspection of the semiconductor substrate ( 6 ). In addition, the changer ( 14 ) is not equipped with means for exact positioning of the semiconductor substrates ( 6 ) in the workstations ( 8, 10, 12 ). | 7 |
CROSS REFERENCE TO RELATED APPLICATION
This application is a 35 U.S.C. §371 national stage application of PCT International Application No. PCT/EP2010/069106, filed on 7 Dec. 2010, the disclosure and content of which is incorporated by reference herein in its entirety. The above-referenced PCT International Application was published in the English language as International Publication No. WO 2012/076042 A1 on 14 Jun. 2012.
TECHNICAL FIELD
The invention relates to the field of communications networks, and in particular to the selection of service domains for call/sessions in IP Multimedia Subsystem Centralized Services networks.
BACKGROUND
The IP Multimedia Subsystem (IMS) is the technology defined by the Third Generation Partnership Project (3GPP) to provide IP Multimedia services over mobile communication networks. IP Multimedia services provide a dynamic combination of voice, video, messaging, data, etc. within the same session. The IMS is defined in the 3GPP Specification 23.228.
The IMS makes use of the Session Initiation Protocol (SIP) to set up and control calls or sessions between user terminals (or user terminals and application servers). The Session Description Protocol (SDP), carried by SIP signalling, is used to describe and negotiate the media components of the session. Whilst SIP was created as a user-to-user protocol, IMS allows operators and service providers to control user access to services and to charge users accordingly.
FIG. 1 illustrates schematically how the IMS 3 fits into the mobile network architecture in the case of a GPRS/PS access network. As shown in FIG. 1 control of communications occurs at three layers (or planes). The lowest layer is the Connectivity Layer 1 , also referred to as the bearer, or traffic plane and through which signals are directed to/from user terminals accessing the network. The GPRS network includes various GPRS Support Nodes (GSNs) 2 a , 2 b . A gateway GPRS support node (GGSN) 2 a acts as an interface between the GPRS backbone network and other networks (radio network and the IMS network). A Serving GPRS Support Node (SGSN) 2 b keeps track of the location of an individual Mobile Terminal and performs security functions and access control. Access to the IMS 3 by IMS subscribers is performed through an IP-Connectivity Access Network (IP-CAN). In FIG. 1 the IP-CAN is a GPRS network including entities linking the user equipment to the IMS 3 via the connectivity layer 1 .
The IMS 3 includes a core network 3 a , which operates over the Control Layer 4 and the Connectivity Layer 1 , and a Service Network 3 b . The IMS core network 3 a includes nodes that send/receive signals to/from the GPRS network via the GGSN 2 a at the Connectivity Layer 1 and network nodes that include Call/Session Control Functions (CSCFs) 5 . The CSCFs 5 include Serving CSCFs (S-CSCF) and Proxy CSCFs (P-CSCF), which operate as SIP proxies within the IMS in the middle, Control Layer.
At the top is the Application Layer 6 , which includes the IMS service network 3 b . Application Servers (ASs) 7 are provided for implementing IMS service functionality. Application Servers 7 provide services to end-users on a session-by-session basis, and may be connected as an end-point to a single user, or “linked in” to a session between two or more users. Certain Application Servers 7 will perform actions dependent upon subscriber identities (either the called or calling subscriber, whichever is “owned” by the network controlling the Application Server 7 ).
IMS relies on Internet Protocol (IP) as a transport technology. Using IP for voice communications, however, presents some challenges, especially in the mobile community where Voice Over IP (VoIP) enabled packet switched (PS) bearers may not always be available. To allow operators to start offering IMS-based services while voice enabled PS-bearers are being built out, the industry has developed solutions that use existing Circuit Switched (CS) networks to access IMS services. These solutions are referred to as IMS Centralized Services (ICS). ICS is described in 3GPP TS 23.292 and is also the name of the Work Item in 3GPP Release 8 addressing these matters. ICS allows a User Equipment (UE) to connect to a CS access network and to have access to Multimedia Telephony services.
Referring to FIG. 2 , a UE 8 can access an MSC Server 9 via a CS Access network 10 . It also accesses a CSCF 5 via a Gm reference point, and a Service Centralization and Continuity Application Server (SCC AS) 11 via a Gm reference point. SIP is used to perform service control between the ICS UE 8 and the SCC AS 11 over the Gm interface. For a speech service, the ICS UE 8 can use its CS access to transfer voice media. The ICS specification defines how it is possible to use a CS bearer controlled via the Gm interface.
When a SCC AS 11 receives an incoming call, or other type of session request (or other type of media component, such as video), it will select an access domain. The procedures specified in TS 23.292 allow for CS access to be selected, but keep the provision of services entirely in the IMS. This can result in unnecessary routing of signalling and media.
For example, if a UE is accessing services via a CS access network (i.e. anchored on the CS domain), and receives a call from another UE, also anchored on CS, then the current ICS solution will force the call from the CS domain to the IMS to perform the Terminating-Access Domain Selection (T-ADS), and then route it back to the CS domain after detecting that the UE is anchored on CS. This is illustrated in FIG. 3 . An originating CS-anchored UE 301 initiates a call/session with a terminating UE 302 , which is registered in both the CS and IMS network domains. The signalling for T-ADS is via the Visited Mobile Switching Centre, VMSC 1 303 in the CS network to which the originating UE 301 is anchored, and then via a Gateway Mobile Switching Centre, GMSC 1 304 to MGCF 305 , I-CSCF 306 , S-CSCF 307 and eventually to Domain Selection AS 308 (e.g. an SCC AS) in the home IMS network of the terminating UE 302 . To enable the access selection the AS 308 accesses data relating to the terminating UE 302 from the Home Subscriber Server, HSS, 309 . To complete the Terminating procedure the signalling is then routed back through the IMS via S-CSCF 307 , I-CSCF 306 and MGCF 305 to GMSC 2 310 and VMSC 2 311 to which terminating UE 302 is anchored in the CS network.
Analysis of the B-number (of the terminating UE 302 ) will determine whether or not the terminating UE is in the CS domain. This will be the case if the B-number cannot be resolved by ENUM, or if the B-number is within a number range for another operator that is not classified as a IMS operator.
Possible solutions to reduce the amount of unnecessary signalling that have been proposed include upgrading the Home Location Register, HLR 312 to perform the terminating domain selection. However, the HLR and HSS databases are usually deployed independently of each other and the lack of a uniform interface means it is difficult to query between HLR and HSS. Therefore this solution is not practical, at least until such time as there is a unified storage and query between the HLR and IMS HSS.
SUMMARY
The present invention proposes an alternative solution, which ensures that the Service Domain Selection is always handled by the IMS, while allowing calls initiated in the CS domain to continue in CS to/from the served user. In addition, embodiments provide means to distribute service settings from the IMS to the CS domains without the need to synchronise the HLR and HSS data in the event that the CS service domain is selected. Certain assumptions have been made, including that terminating calls from the PSTN or via the GRX interface are routed to the entity that routes the incoming call—i.e. the GMSC. Also, in some CS access networks the routing entity, i.e. the MSC server, may already be enhanced, or have an enhanced capability for ICS where the user includes an ICS flag, but here it is assumed that the MSC server is either not enhanced for ICS or the ICS flag is not provided to the MSC. It is also noted that ICS users must always receive IMS services.
In one aspect there is provided a method of using IMS Centralised Services, ICS, in the selection of a service domain on the terminating side of a call originated by an originating side User Equipment, UE, to a terminating side UE being served by a CS access network. The method includes receiving, in the terminating UE's CS access network, a call set-up message from the originating UE. A request is sent to a Service Domain Selection, SDS, function for selection of a service domain for the call. A service domain selection indication is received from the SDS function and, based on the received selection indication, the call is routed either via the IMS service domain or directly to the terminating UE via the CS service domain.
The call set-up message may be received at a Gateway Mobile Switching Centre, GMSC. The GMSC sends the request to a Service Control Point, SCP, that includes the SDS function, which checks the SDS data of the terminating UE. The selection of the service domain is determined by the SDS function.
The method may also include receiving CS service data at the GMSC including instructions for the processing of certain call events in the CS domain. The CS service data may include data derived from IMS service data and/or predefined data stored in the IMS. The CS service data may include data for processing by an MSC or a Visitor Location Register, VLR, in which case the GMSC forwards that data to an appropriate MSC or VLR.
In another aspect there is provided a method of using IMS Centralised Services, ICS, in the selection of a service domain on the originating side of a call originated by a User Equipment, UE, being served by a Circuit Switched, CS, access network to a terminating side UE. The method includes receiving a call set-up message from the originating side UE. A request is sent to a Service Domain Selection, SDS, function in the originating UE's home IMS network. A service domain selection indication is received from the SDS function, and, based on the received selection indication, the call is routed either via the IMS service domain or via the CS domain.
The call set-up message may be received at a Mobile Switching Centre, MSC, the MSC sending a request to a Service Control Point, SCP, that includes a SDS function. The SDS function checks the SDS data of the originating UE. The selection of the service domain is determined by the SDS function.
The method may also include receiving CS service data at the MSC including instructions for the processing of certain call events in the CS domain. The CS service data may be derived from IMS service data and/or include predefined data stored in the IMS.
In another aspect there is provided a method of using IMS Centralised Services, ICS, in the selection of a service domain relating to a call involving a User Equipment, UE, being served by a CS access network. The method includes receiving a request from a routing node for a service domain selection at a Service Control Point, SCP, in the UE's IMS network. The SCP includes a Service Domain Selection, SDS, function that retrieves data relating to the UE from a Domain Selection function. Based on the retrieved data, either the IMS service domain or the CS service domain is selected as the service domain for routing the call. An indication of the selected service domain is sent to the routing node.
The method may also include providing CS service data to the routing node, including instructions for the processing of certain call events in the CS domain. The CS service data may be derived from IMS service data and/or include predefined data stored in the IMS.
In embodiments, the SCP may be collocated with a Service Continuity Centralisation Application Server, SCC-AS, having an Access Domain Selection function. Alternatively, the SCP may be collocated with a Telephony Application Server, TAS.
Selecting the service domain may be based, at least in part, on one or more of the following criteria:
where the originating or terminating UE requires IMS-specific services, selecting the IMS domain; where the originating UE is utilising an IMS Voice over PS access, selecting the IMS domain; where the call forwarding and call barring settings are synchronised between CS and IMS, selecting the CS domain; predetermined operator preferences.
In another aspect there is provided an Application Server, AS of an IMS network. The AS receives a request from a routing node, for a service domain selection relating to a call originated by, or destined for a User Equipment, UE, being served by a Circuit Switched, CS, access network. The AS retrieves SDS data relating to the UE and, on they retrieved data, selects either the IMS service domain or the CS service domain. The AS provides a response to the routing node from which the request was received. The response includes instructions for routing the call in accordance with the selected service domain.
When the selected service domain is the CS domain, the AS may also provide CS service data, including instructions for the processing of certain call events in the CS domain.
In another aspect there is provided a Mobile Switching Centre, MSC. On receiving a call set-up request originated by a User Equipment, UE, being served by a Circuit Switched, CS, access network, and destined for a terminating UE being served by a CS access network, the MSC sends a service domain selection information request to a home IMS network of the originating UE. On receiving the requested information from the IMS, the MSC routes the call via either the IMS service domain or the CS service domain in accordance with a selection instruction in the received information. If the call is routed via the CS domain, the MSC processes additional CS service data provided with the received information, including instructions for the processing of certain call events in the CS domain.
In another aspect there is provided a Gateway Mobile Switching Centre, GMSC. On receiving a call set-up request originated by a User Equipment, UE, being served by a Circuit Switched, CS, access network and destined for a terminating UE being served by a CS access network, the GMSC requests service domain selection information from a home IMS network of the terminating UE. On receiving the requested information from the IMS, the GMSC routes the call via either the IMS service domain or the CS service domain in accordance with a selection instruction in the received information. If the call is routed via the CS domain, the GMSC processes additional CS service data provided with the received information that includes instructions for the processing of certain call events in the CS domain.
The GMSC may also determine if the CS service data includes data for processing by an MSC or a Visitor Location Register, VLR, and forwards that data to an appropriate MSC or VLR.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates schematically in a block diagram an IP Multimedia Subsystem network;
FIG. 2 illustrates schematically in a block diagram an IMS Centralized Services network;
FIG. 3 illustrates schematically using a block diagram the signalling path for terminating a call in an IMS Centralized Services network in accordance with current standard procedure;
FIG. 4 illustrates schematically using a block diagram the signalling paths for terminating a call in a CS access network using IMS Centralized Services in accordance with the present disclosure;
FIG. 5 illustrates schematically using a block diagram the signalling paths on the originating side of a call anchored in a CS access network using IMS Centralized Services in accordance with the present disclosure;
FIG. 6 is a flow diagram illustrating method steps in a method of service domain selection for a terminating call using IMS Centralized Services in accordance with the present disclosure;
FIG. 7 is a flow diagram illustrating method steps in a method of service domain selection for an originating call using IMS Centralized Services in accordance with the present disclosure.
FIG. 8 is a flow diagram illustrating method steps in a method of service domain selection using IMS Centralized Services relating to a call involving a User Equipment, UE, being served by a CS access network in accordance with the present disclosure.
DETAILED DESCRIPTION
The methods described below make use of a Service Domain Selection (SDS) function, which is configured to access a Domain Selection function and to intelligently select what service domain, IMS or CS, to use for a call/session. To do this the SDS acquires knowledge of the UEs reachability over both PS and CS access. In the call set-up procedure the SDS is queried to determine whether to route the call to the IMS or whether to continue the call setup in the CS domain. On the terminating side of the call, the SDS is queried by the GMSC when it receives a call set-up request. On the originating side of the call, the SDS is queried by the MSC. Each of these is described in more detail below. The SDS function could be implemented as part of an existing function, such as the SCC AS or a Telephony Application Server, TAS. In the description below, the SCC AS is used as an example, but this could also be done, for example, in the TAS.
To make the decision, the SDS applies certain criteria. For example:
where the originating or terminating UE requires IMS-specific services, selecting the IMS domain; where the originating UE is utilising an IMS Voice over PS access, selecting the IMS domain; where the call forwarding and call barring settings are synchronised between CS and IMS, selecting the CS domain.
In the event that the terminating side UE is registered in both the IMS and CS networks, the SDS function decides whether to locally route the call in the CS domain or whether to route it via the IMS, depending on certain predetermined criteria, for example operator preferences.
Referring to FIG. 4 , the terminating side of a call/session includes a serving network, 400 to which the terminating UE (not shown) is attached, and the UE's home network 402 . The network entities, or nodes, shown include both CS and IMS entities (see FIG. 1 ). The serving/access network includes a routing entity, an example of which is an MSC Server, 404 , and a P-CSCF 406 . Other network entities, such as gateways are also shown but these are not important for the present discussion. The home network includes a gateway routing entity, which in this example is a GMSC 408 , as well as certain IMS entities, including a MGCF 410 , which links to the GMSC 408 , a S-CSCF 412 , an I-CSCF 414 , and HSS 416 , an ENUM telephone number mapping server 418 and a SCC AS 420 , which includes an entity that performs a domain selection, in this example a Terminating Access Domain Selection, T-ADS function. As shown in FIG. 4 , the SCC AS 420 also hosts a SCP in the form of the SDS function 422 , as described above.
FIG. 4 shows the signaling paths in the set-up of the terminating side of a call. In accordance with established procedure, the call set-up request signal is received at the GMSC 408 . As mentioned above, the B-number (of the terminating UE 302 ) used in the call will determine that the terminating UE is using the CS domain. This will be the case if the B-number cannot be resolved by ENUM, or if the B-number is within a number range for another operator that is not classified as an IMS operator. However, unlike in established ICS procedures as described in 3GPP TS 23.292, instead of routing the signaling immediately to the IMS, the GMSC is configured to initiate a check shown as path 42 , with the SDS 422 (shown in FIG. 4 as being collocated with the SCC AS 420 ) as to whether the call should be routed via the IMS or whether to continue to route the call directly to the terminating UE via the CS domain. The SDS 422 will use the Access Domain Selection function of the SCC AS 420 to discover the capabilities and service parameters of the terminating UE, and apply predetermined criteria to make a selection as to whether the call should be routed via the IMS or continue directly via the CS domain.
If the IMS is selected, the call is routed from the GMSC 408 to the IMS, in accordance with the established procedure of 3GPP TS 23.292 shown by path 43 a —i.e. via MGCF 410 , S-CSCF 412 , SCC AS 420 , and P-CSCF 406 . If the CS domain is selected, the call is routed directly from the GMSC 408 to the MSC-S 404 , as shown in path 43 b.
FIG. 5 shows the corresponding situation at the originating side including a serving network, 500 to which the originating UE (not shown) is attached, and the originating UE's home network 502 . The network entities shown include a MSC Server 504 , and a P-CSCF 506 , a GMSC 508 , a MGCF 510 , a S-CSCF 512 , an I-CSCF 514 , HSS 516 , ENUM 518 , and a SCC AS 520 , which includes an Originating Access Domain Selection, OAS function. The SCC AS 520 also hosts a SCP in the form of the O-SDS function 522 .
FIG. 5 shows the signaling paths in the set-up of the originating side of a call initiated by the originating UE in the CS domain. In accordance with established procedure, the call set-up request signal 51 is received at the MSC 504 . Instead of routing the signaling immediately to the IMS, the MSC 504 is configured to initiate a check, shown as path 52 , with the SDS 522 (shown in FIG. 5 as being collocated with the SCC AS 420 ) as to whether the call should be routed via the IMS or whether to continue to route the call directly to the terminating UE via the CS domain. The SDS 522 will use the Access Domain Selection function of the SCC AS 520 to discover the capabilities and service parameters of the originating UE, and apply predetermined criteria to make a selection as to whether the call should be routed via the IMS or continue directly via the CS domain.
If the IMS is selected, the call is routed from the MSC 504 to the IMS, in accordance with the established procedure of 3GPP TS 23.292 shown by path 53 a —i.e. via I-CSCF 514 , S-CSCF 512 , and SCC AS 520 . If the CS domain is selected, the call is routed directly from the MSC-S 504 , as shown in path 53 b.
FIG. 6 is a flow diagram illustrating the principal method steps for the method of using ICS in the selection of a service domain on the terminating side of a call, where the terminating side UE is being served by a CS access network. At step 601 , a call set-up message from the originating UE is received at the GMSC 408 (see FIG. 4 ). At step 602 , the GMSC 408 sends a Service Domain Selection, SDS, request to the SCP, which in the embodiment illustrated in FIG. 4 is collocated with SCC AS 420 , and includes an SDS function for selecting a service domain for the call. At step 603 , the GMSC receives a reply from the SCP that includes an indication of the service domain selection made by the SDS function. In addition, if the CS service domain was selected, the GMSC may also receive CS service data, including instructions for the processing of certain call events in the CS domain. These will be described further below. At step 604 , the GMSC 408 detects if the received selection indication indicates that the CS domain has been selected, and if so, at step 605 continues routing the call directly to the terminating UE via the CS domain. In addition, if additional CS service data has been provided at step 603 , then the GMSC will process this. The data may include instructions which are to be processed by the GMSC, or may include data that is relevant for the MSC or VLR serving the terminating UE, in which case the GMSC, at step 606 , forwards the CS data to the MSC/VLR.
Alternatively, if at step 604 the selection indication indicates that the IMS has been selected, then at step 607 , the GMSC 408 routes the call via the IMS service domain.
FIG. 7 is a flow diagram illustrating the principal method steps for the method of using ICS in the selection of a service domain on the originating side of a call, where the originating side UE is being served by a CS access network. At step 701 , a call set-up message from the originating UE is received at the MSC 504 (see FIG. 5 ). At step 702 , the MSC 504 sends a Service Domain Selection, SDS, request to the SCP, which in the embodiment illustrated in FIG. 5 is collocated with SCC AS 520 , and includes an SDS function 522 for selecting a service domain for the call. At step 703 , the MSC receives a reply from the SCP that includes an indication of the service domain selection made by the SDS function. In addition, if the CS service domain was selected, the MSC may also receive CS service data, including instructions for the processing of certain call events in the CS domain. These will be described further below. At step 704 , the MSC 504 detects if the received selection indication indicates that the CS domain has been selected, and if so, at step 705 continues routing the call directly to the terminating side via the CS domain. In addition, if additional CS service data has been provided at step 703 , then the MSC will process this.
Alternatively, if at step 704 the selection indication indicates that the IMS has been selected, then at step 707 , the MSC 504 routes the call via the IMS service domain.
FIG. 8 is a flow diagram illustrating the principal method steps for the method of using IMS Centralised Services, ICS, in the selection of a service domain relating to a call involving a User Equipment, UE, being served by a CS access network. At step 801 a request is received at a SCP from a MSC or a GMSC for a service domain selection. The SCP includes a SDS, function, and may, for example, be collocated with a SCC AS, as shown in FIG. 4 or FIG. 5 . At step 802 , the SDS retrieves data relating to the UE that it needs to make the service domain selection. This may include retrieving UE data from a Domain Selection function (e.g. an ADS function). At step 803 , the SDS applies selection criteria to make a selection, based on the accessed data, selecting either the IMS service domain or the CS service domain as the service domain for routing the call. At step 804 the SCP also determines if there is any CS service data that should be provided to the MSC/GMSC. At step 805 , the SCP sends a reply to the MSC or GMSC, including an indication of the selected service domain, together with any CS service data determined at step 804 .
The CS service data determined at step 804 , is accessed and provided in accordance with predefined rules programmed into the SCP/SDS. The CS data may be derived from IMS service data, in which case the SDS/SCP derives the information according to the predefined rules. Alternatively, the CS service data may be pre-defined and provisioned into the IMS, in which case the SCP/SDS simply accesses the data according to the predefined rules.
Thus, for a terminated call, where the SCP/SDS decides to terminate the call in the CS domain, the additional service data is provided to the GMSC which the GMSC has to execute. However, if service data actually to be executed by the MSC/VLR and not by the GMSC, the GMSC forwards the service data to the MSC/VLR. For an originated call, where the SDS decides to originate the call in the CS domain, the SCP/SDS provides the additional service data to the MSC which the MSC has to execute.
One example for implementing the methods described above is the use of the CAMEL (Customized Applications for Mobile network Enhanced Logic) Subscription Information (CSI). For terminating calls, CAMEL T-CSI can be used to interact between the GMSC and the SDS/SCC AS. For originated calls, CAMEL O-CSI can be used to interact between the MSC and the SDS/SCC AS. In both cases, when the SDS selects the IMS, the T/O-CSI provides a routing number in a response sent to the GMSC/MSC. If no routing number is provided, then the call continues to be routed in the CS domain. The CS service data can be carried as part of the T/O-CSI responses.
The methods and network solution described enable calls originated in the CS domain, or terminated to a GMSC, to only be sent to the IMS if they need to receive IMS services. In addition the solution enables the IMS to provide CS service data to GMSC and MSC/VLR for execution in the CS domain. This enables more calls to be handled in the CS domain, while still benefiting from services that would otherwise require the call to be routed via the IMS. | The invention includes methods of using IMS Centralized Services, ICS, in the selection of a service domain relating to a call involving a User Equipment, UE, being served by a CS access network. In one aspect a method includes receiving a request from a routing node, such as a Mobile Switching Center, MSC, or a Gateway Mobile Switching Center, GMSC, for a service domain selection at a Service Control Point, SCPin the UE's IMS network ( 801 ). The SCP has a Service Domain Selection, SDS, function, which retrieves data relating to the UE from a Domain Selection function ( 802 ). Based on the retrieved data, the SDS selects either the IMS service domain or the CS service domain as the service domain for routing the call ( 803 ), and sends an indication of the selected service domain to the routing node ( 805 ). Other aspects include methods for domain selection at the originating and terminating sides of the call, and network entities configured to carry out the methods. | 7 |
BACKGROUND OF THE INVENTION
This invention relates to optical image processing whereby a pattern of light intensity is electrically converted by a Fourier transformation from an amplitude spatial function to an amplitude frequency function. The advantages of processing a Fourier transform are well known. The sampling theorems allow one to minimize the collection of data. The space and frequency shifting theorems allow one to shift image position and size. Computer programs for fast Fourier transforms have been developed, allowing broadcasting of telemetry information in the form of transforms.
Fourier transformation is basically a mathematical process in which a non periodic amplitude-time function, that is, a complex wave form, is broken down into a series of sine wave components of all frequencies which make up the complex wave form. The amplitude-time is multiplied by a sinusoidal function and the product is integrated. The frequency and phase of the multiplying function determines the value of the integral, which is proportional to the amplitude of the spectrum component of that particular frequency and phase. To obtain the total frequency spectrum of the complex wave form, the frequency of the multiplying sinusoidal function must be varied over the respective band while the phase must be adjusted for maximum amplitude at each frequency. Since there are an infinite number of discrete frequency components in most complex waves, there would be an infinite number of terms; as a partical matter, the Fourier integral is evaluated at discrete frequencies so as to obtain a realistic picture of the amplitude frequency function.
The Fourier power spectrum is equal to the square of the individual terms in the Fourier series. The Fourier power spectrum contains essentially the same information as the Fourier series, except that the negative sign of a series frequency component is lost when the turn is squared.
Devices for the transformation of electrical pulses often use optical components to process the signal.
For instance interference fringes produced by two coherent light beams may be intensity modulated in accordance with an input signal and phase modulated with a systematic signal. The interference pattern is then measured with a photoelectric cell, to yield the transform of the input signal. Other devices use an input signal to vary the position of an arbitrary optical image on a film, which is then rapidly processed and read out as a transform. On the other hand, the present invention concerns a device which uses electrical components to obtain a power spectrum, which is related to a transform of an optical signal as explained below.
Recent developments in surface wave technology have produced a family of devices known as Direct Electronic Fourier Transform (DEFT) devices. They are described by Philipp Kornreich et al. in Proceedings Of The IEEE, Vol. 62, No. 8, pp 1072 (August 1974). Basically, light falling on a "photocathode film" causes electron emission by the photoelectric effect. A transducer driven by a variable frequency generator sets up sound (strain) waves in the film. The strain waves modulate the electron emission. The photoelectrons are collected on an electrode and the collection potential between the electrodes is measured as the output. The film may be metal, or a semiconductor material. If a semiconductor is used the device relies on Elastophotoconductance rather than photoelectric effects, and output is measured across the semiconductor. The output is proportional to the light intensity and the strain. By varying the strain frequency, a Fourier transform of the light intensity is obtained.
Certain mechanical problems are inherent in the use of strain wave modulation, however, such as a limited dynamic range, control of propagation time, etc. These problems are not associated with a new type of semiconductor device known as a charge coupled device (CCD). Such devices are described more fully below, and still more fully by Gilbert F. Amelio in Scientific American, volume 230, page 22 (February 1974), and is U.S. Pat. No. 3,930,255, which description are hereby incorporated in and made a part of the present specification. Such devices are essentially a grid of cells (frequently photosensitive) which can store and read out a charge at a rate proportional to a read out or "clock" voltage. They have heretofor been contemplated for use as memory devices or visual image sensors as for t.v. cameras.
SUMMARY OF THE INVENTION
An optical image is forcused through an electro-optical modulator onto a charge coupled device (CCD) having an array of photosensitive elements. By varying either the readout frequency of the CCD or the electro-optical modulation frequency, a modulated output is obtained whose amplitude is proportional to the spatial Fourier transform of the optical image.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic representation of the elements of the present invention.
FIG. 2 is a diagramatic illustration of the operation of the device.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The charge coupled device (CCD) is a relatively new concept in semiconductor electronics. Charge coupling refers to the transfer of a mobile electric charge within a semiconductor storage element to a similar, adjacent storage element by the external manipulation of voltages. Devices containing a 100 by 100 grid of storage elements have been manufactured on a silicon chip measuring only 0.12 by 0.15 inch. The device typically has a "p type" silicon substrate selectively altered to form an "n type" silicon layer with a silicon dioxide insulating layer on its surface. An array of electrodes is deposited on the surface of the insulating material and connected in two or more circuits so that they may be sequentially charged. When a periodic waveform called a "clock voltage " is applied to the electrodes, some of the electrons in the vicinity of each electrode will form a discrete packet of charge and move from one element to the next for each clock cycle. The electrons are said to move from one element to the next by displacement of the local "potential well".
A signal can be put into the silicon substrate at one point on the CCD and by turning over adjacent electrodes with the clock voltage, the signal can be transferred along a so-called "channel" to an output at another point on the CCD. The signal transfer from input to output is called the scan, which can be designed to operate in one, or several, directions and across the surface of the device.
The silicon in CCD's is very sensitive to light and generates mobile electrons through the Einstein photoelectric effect. This "electro-optic" creation of electrons is proportional to the intensity of the incident light and represents an input signal which by displacement of the potential well to an output which will carry a signal representative of the light pattern.
A simple image sensor can be envisioned in which an input signal is generated by photoelectrons in the vicinity of each electrode; a pattern of photoelectrons is then carried by the clock voltage to an output connection at the end of the channel. A variety of more complex practical image sensors, are available, but they all work on this basic principle. The operation is somewhat similar to an analog computer in that a series of discrete charge packages are stored then read out.
The input signal appears at the output after a delay caused by the time required to shift the charge packages through the channel. This delay is equal to the number of electrode regions to be read divided by the clock period.
CCD's are also capable of storing charges for a time before being read out. Such features may be employed herein, if desired.
Referring now to FIG. 1, a lens 1 serves to focus an image 2 onto a CCD array 3 through an electro-optical modulator 4.
The electro-optic modulator in various forms is well known in the field of optics, being frequently used to modulate lasers. A typical electro-optical modulator is a Pockels cell which employs a pair of parallel polarizers on either side of a suitable birefringent material to which an electrical field is applied. This changes the birefringence which in turn changes the polarization form of the light and its degree of passage through the second polarizer. Thus, a variable field applied to the birefringent material will modulate optical transmission through the device. Other electro-optical devices such as PLZT cells or an acousto-optical cell may be employed for purposes of the present invention within recognized engineering trade-off considerations.
The modulator 4 is driven with a constant frequency sine wave, thus turning the image at the CCD 3 at frequency fm. By way of example, optical image 2 is a bright field with four periodic dark bars in the center. If CCD 3 is scanned with clock driver 5 charge "buckets" will travel across the CCD surface, collecting charge in the form of photoelectrons as they go. If dark bar center to center separation of image 2 is L and scan velocity is V B , the modulation frequency, f m , equals V B /L. Two adjacent charge buckets being clocked across the CCD cells will collect electrons as shown in FIG. 2. Note that the second bucket sees either O modulator transmission or a dark bar and thus collects very little photoelectric charge.
It can be seen that, for this situation, some "buckets" will fill more rapidly with photocurrent charge than others. A modulated output will be observed as the CCD is scanned. By changing either the optical modulation or the clock frequency, the amplitude of the output modulation will decrease, since the necessary synchronization will be destroyed.
If we place an arbitrary optical image on the CCD and a vary either the electro-optical modulation frequency or the CCD clock frequency, a modulated output will be observed only at frequencies for which an optical spatial frequency (S.F.) obeys the relation
S.F. = V.sub.B /F.sub.m .
A plot of output modulation amplitude versus S.F. will be proportional to the square of the bandlimited spatial Fourier transform of the optical image, along the direction of the CCD scan.
A consideration of the operation of the CCD and the modulator transmission curve show in FIG. 2 makes it apparent that the present device cannot measure negative components of a signal. For this reason, the devices in its present embodiment, fields the Fourier power spectrum of the input signal. A two dimensional Fourier transform could be obtained by: (1) employing several CCD arrays oriented along different directions, (2) rotating either the image or the arrary, or (3) designing a special CCD array capable of scanning in several directions. | Direct spatial Fourier power spectra of optical images are obtained by maulating either the image focused onto a photosensitive charge coupled device (CCD) or the readout from the CCD. | 6 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to a tissue-specific gene promoter, and in particular, to a promoter useful for anther-specific expression in plant, and application thereof.
2. Description of the Prior Art
In the improvement of crop's characteristics, or in relative studies utilizing plant gene transfer technology, conventionally, a gene to be expressed or studied is constructed downstream of a specific promoter sequence and the gene to be studied is then expressed or modulated with the activation ability of said promoter. Among conventional techniques, over-expressing the target gene is mostly driven by the CaMV 35S promoter in plant. Unfortunately, CaMV 35S promoter is not a tissue-specific promoter in that it can not over-express a target gene at a specific plant tissue. Therefore, how to make over-expression of a target gene at a specific plant tissue or in a particular period is the key point to modulate a gene's expression.
Accordingly, for researches of bioscience or developments of the biotechnical industry, how to screen out promoters with different specificity to drive the expression of a transferred target gene at a target site and bring out a maximum benefit of gene transfer is the important topic for improving the development of biotechnical industry and increasing the economical benefit of crops.
At present, molecular biologists have found a number of promoters having spatial (i.e., specific cell or tissue) or temporal (i.e., at different growth and development stages) specificities, or promoters inducible by a specific substance such as UV-B or chemical substances, that can be used to activate the expression of a transferred target gene to achieve the purpose of modulating gene expression.
In genetic breeding, “heterosis” is a very important research trend for obtaining crop with better character. Heterosis is to be understood to mean that a first hybrid progeny (F1 progeny) generated from the hybridization of two parents has a character with average performance better than either parent. In the course of hybridization, if the crop of interest is a selfing crop, the parent should be subjected first to artificial castration and then pollination to increase in order to avoid selfing, which increases production cost. For example, in the breeding study of Cruciferae vegetables, selfing lineage of self incompatibility is currently used mostly to carry out F1 seed collection. Nevertheless, several bottlenecks such as instability of hybridization rate, difficulty in the propagation of selfing parent line, low seed collection due to selfing depression, as well as the unlikeliness for superior parent to have self incompatibility exist yet. To activate particular genes that may result in male sterility or ability to silence pollination-associated gene by means of an anther-specific promoter shall be an important contribution for improving character by applying biotechnology.
Though many studies have found promoters with anther- or pollen-specific activation activity, such as potato (Lang et al., 2008), tomato (Bate and Twell, 1998), maize (Hamilton et al., 1998), rice (Gupta et al., 2007), petunia (Garrido et al., 2006), antirrhinum (Lauri et al., 2006), lily (Okata et al. 2005), cabbage (Park et al., 2002) and the like, no study on gene promoter associated with an orchid has been reported so far.
Oncidium Gower Ramsey is an important export cut flower for Taiwan. Its flower has a bright yellow color. Since customers desire visual aesthetic feeling and prefer novel flower colors, flower color becomes one of the important factors determining values in the flower crop industry and articles. In view of the foregoing, the inventors attempted to isolate genes associated with the biosynthesis of yellow pigment from Oncidium, and screened out promoters with tissue-specificity through the analysis of a promoter of aureusidin synthase gene.
Also, in view of the importance of developing promoters with distinct specificity for the biotechnology industry, the inventors had been devoted to improve and innovate, and, after intensive studying for many years, has developed successfully a anther-specific expression promoter in plant, and application thereof according to the invention.
SUMMARY OF THE INVENTION
One object of the invention is to provide a tissue-specific promoter useful for the specific expression in plant anther.
Another object of the invention is to provide an application of the anther-specific expression promoter in plant, wherein, by using the particular tissue-specificity of said promoter, there is overexpression of the target gene on the anther of plant.
Still another object of the invention is to provide a gene expression vector containing an anther-specific expression promoter that, through transferring a target gene via said vector into plant cell, overexpression of said gene can be done specifically on the anther of said plant under the control of said promoter.
As promoter useful for plant anther-specific expression to achieve the above-described objects of the invention, the source for the sequence of said promoter is the genomic DNA of Oncidium Gower Ramsey. To this end, a gene fragment of aureusidin synthase gene AmAS1 (GenBank accession number AB044884, SEQ ID No: 1) from Antirrhinum majus was used as a probe, a plaque hybridization reaction was carried out with Oncidium genomic DNA library. The resulting products were purified several times to obtain Oncidium aureusidin synthase genomic clone, which was then subjected to restriction map analysis and nucleic acid sequencing. After matching with cDNA sequence of Oncidium aureusidin synthase gene OgAS1 (SEQ ID No: 2), it could be confirmed that a local sequence of 3,014 bp (SEQ ID No: 3) at upstream of the translation start site (gene code: ATG) of Oncidium aureusidin synthase gene OgAS1, which comprised a promoter local sequence of 2,985 bp, and a 29 bp 5′-end untranslated region (5′UTR) in the first exon (exon 1) of Oncidium aureusidin synthase gene OgAS1. This 3,014 bp DNA sequence (SEQ ID No: 3) was used as Oncidium aureusidin synthase gene OgAS1 promoter.
In order to analyze whether said Oncidium aureusidin synthase gene OgAS1 promoter (SEQ ID No: 3) was tissue-specific, said promoter sequence was ligated to the 5′-end of the gene sequence of a reporter gene β-glucuronidase (GUS) to be used as the promoter for said reporter gene. The ligation product was then constructed into an Agrobacterium tumefaciens cloning vector to form a plasmid OgAS1p-GUS; then, by using Agrobacterium tumefaciens transfection, said OgAS1p-GUS plasmid was transferred into model plants Arabidopsis thialana and Nicotiana tabacum L., and the activity of said gene promoter was assayed by GUS histochemical staining. The result indicated that said Oncidium aureusidin synthase gene OgAS1 promoter (SEQ ID No: 3) could drive target gene to be expressed at the plant anther. Accordingly, the activation ability of Oncidium aureusidin synthase gene OgAS1 promoter (SEQ ID No: 3) according to the invention was extremely tissue-specific.
In addition to providing a promoter useful for plant anther tissue-specific expression, the invention also provides a gene expression cassette, said gene expression cassette consists of: (1) a promoter sequence (SEQ ID No: 3) according to the invention, and (2) a stretch of polynucleotide encoding an open reading frame (ORF), that is a target gene, wherein said polynucleotide is connected to the 3′ end of the promoter according to the invention, and said promoter can activate the transcription of said polynucleotide in a organism containing said gene expression cassette. In a preferred embodiment, said target gene is a reporter gene β-glucuronidase (GUS).
Further, the Oncidium aureusidin synthase gene OgAS1 promoter (SEQ ID No: 3) according to the invention was constructed into a commercial gene cloning vector, including, but not limited to, pBI101, pBI121, pBIN19 (ClonTech), pCAMBIA1301, pCAMBIA1305, pGREEN (GenBank Accession No: AJ007829), pGREEN II (GenBank Accession No: EF590266), or pGreen0029 (John Innes Centre), to form a gene expression vector.
A target gene could be inserted in said gene expression vector such that said target gene was connected to the 3′ end of the promoter according to the invention to form the above-described gene expression cassette. Through gene transferring, the promoter of the invention together with the target gene linked to its 3′ end could be transferred into an objective plant, and further, the genomic constitution of the transgenic plant might be altered such that the promoter of the invention and said target gene could activate effectively the expression of said target gene in the objective transgenic plant and its progeny.
In another aspect, the invention provides a method for producing a transgenic plant or part of the organs of said transgenic plant.
In still another aspect, the invention provides a method for producing a tissue or cell containing the above-described gene expression cassette, said method comprising steps of:
step 1: providing cells or tissue of an objective plant;
step 2: transfecting a gene expression cassette containing promoter sequence (SEQ ID No: 3) of the invention into said cells or tissue of an objective plant obtained in step 2 to obtain a transfected cell or tissue of the plant; and
step 3: cultivating said transfected cell or tissue of the plant obtained in step 2 to generate a transgenic plant or part of organs of said transgenic plant containing gene expression cassette encoding promoter sequence (SEQ ID No: 3) of the invention.
In step 2 of the above method, said transfection includes, but not limited to: Agrobacterium tumefaciens -mediation, gene recombination viral infection, transposon vector transformation, gene gun transformation, electroporation, microinjection, pollen tube transformation, liposome-mediated transformation, ultrasonic-mediated transformation, silicon carbide fiber-mediated transformation, electrophoresis, laser microbeam, polyethylene glycol (PEG), calcium phosphate transformation, DEAE-dextran transformation and the like.
These features and advantages of the present invention will be fully understood and appreciated from the following detailed description of the accompanying Drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
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 Office upon request and payment of the necessary fee.
FIG. 1 is the result of Northern hybridization analysis for Oncidium; FIG. 1A shows the result of using Oncidium aureusidin synthase gene OgAS1 as the probe to analyze the expression of said gene in different sites of Oncidium plant; FIG. 1B shows the result of using actin as the internal control; wherein lane 1: root; lane 2: pseudo-bulb; lane 3: leaf; lane 4: flower.
FIG. 2A is a restriction map of the genome of Oncidium aureusidin synthase gene OgAS1 according to the invention; FIG. 2B shows the construction strategy for the plasmid OgAS1p-GUS containing the inventive Oncidium aureusidin synthase gene OgAS1 promoter.
FIG. 3 is a construction strategy for Agrobacterium tumefaciens cloning vector pGKU.
FIG. 4 shows analytical results of the expression of reporter gene β-glucuronidase (GUS) at various tissue sites of the progeny from Arabidopsis thialana transformants containing OgAS1p::GUS-NOS gene expression cassette; FIG. 4A : whole plant of 45-days old; FIG. 4B : siliques of Arabidopsis thialana ; FIG. 4C : floral organ of Arabidopsis thialana ; FIG. 4D : floral organ of Arabidopsis thialana ; all anther present blue color.
FIG. 5 shows analytical results of the expression for reporter gene β-glucuronidase (GUS) at various tissue sites in the progeny of Nicotiana tabacum L. transformant containing OgAS1p::GUS-NOS gene expression cassette: FIG. 5A : whole seedling at vegetative growth stage; FIG. 5B : floral organ of Nicotiana tabacum L., only anther presenting blue color; FIG. 5C : the pistil and stamen of Nicotiana tabacum L.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Example 1
Northern Hybridization Analysis of Oncidium Aureusidin Synthase Gene
In order to reveal the expression site of Oncidium aureusidin synthase gene at Oncidium, RNA was extracted from various organs of Oncidium plant, and Northern hybridization analysis was carried out by using Oncidium aureusidin synthase gene OgAS1 (SEQ ID No: 2) as the probe.
1. Extraction of Oncidium RNA
5 g of Oncidium material was ground with liquid nitrogen in a mortar. To each gram of ground tissue was added 2-3 ml of sarcosyl-free solution D [4 M guanidiun thiocyanate, 25 mM sodium citrate (pH 7.0), 0.1 M β-mercaptoethanol], and equal volume of PCI (phenol: chloroform: isoamyl alcohol=25:24:1), and the resulting mixture was mixed homogeneously in a homogenizer. Additional sarcosyl was added to a final concentration of 0.5%. After being mixed further in homogenizer, the mixture was centrifuged at 4° C. 10,800 rpm for 20 minutes (Beckman J2-MC, JS 13.1). The supernatant was drawn and extracted with equal volume of PCI, followed with equal volume of CI (chloroform: isoamyl alcohol=49:1). The supernatant was subjected to extracting by adding 1/10 volume of 3 M NaOAc (pH 5.2) and 2.5-fold volume of −20° C. 100% ethanol, shaking homogeneously and left to precipitate at −80° C. overnight. On the next day, the mixture was centrifuged at 4° C. 10,800 rpm for 15 minutes. The pellet was washed with each of 2 mL of 70% and 100% ethanol, and then centrifuged at 4° C. 10,800 rpm for 5 minutes. The supernatant was discarded, and RNA was dissolved completely in water treated with diethyl pyrocarbonate (DEPC). To the solution, LiCl was added to a final concentration of 2.5M. Then, 1% β-mercaptoethanol was added, and the solution was allowed to precipitate at −80° C. overnight. On the next day, it was centrifuged at 4° C. 10,800 rpm for 90 minutes. The pellet was washed with 70% and 100% ethanol. RNA thus obtained was air-dried, and dissolved again for quantitative analysis.
2. Northern Hybridization Analysis of Oncidium Aureusidin Synthase Gene
20 μg of total Oncidium RNA was glyoxylated at 50° C. for one hour, with a total reaction volume of 50 μL, comprising 10 mM sodium phosphate buffer (pH 7.0), 1 M deionized glyoxal, and 50% dimethyl sulfate. At the end of reaction, 10 μL 1×RNA loading buffer dye [containing 50% glycerol, 10 mM sodium phosphate (pH 7.0), 0.25% bromophenol blue] was added and electrophoresis was carried out on 1% agar gel. Then, the gel was treated with 50 mM sodium hydroxide for 30 minutes, and then with 200 mM sodium acetate for 30 minutes. The gel was then soaked in 1×TBE buffer [consisting of 90 mM Tris base, 2 mM EDTA (pH 8.0), and 89 mM boric acid] containing 1 μg/mL of ethidium bromide under shaking for 30 minutes. RNA loaded on the thus-treated gel was blotted on Hybond N membrane by capillary method. After 16-24 hours, its was treated with 5×SSPE at 65° C. for 5 minutes, and then dried in a vacuum oven at 80° C. for one hour. The membrane was transferred in a pre-hybridization solution (consisting of 5×SSPE, 5×BFP, 0.5% SDS, 50% formamide, 100 μg/mL salmon sperm DNA), and pre-hybridization reaction was carried out at 42° C. for more than 2 hours. Thereafter, the membrane was transferred in hybridization solution (consisting of 5×SSPE, 5×BFP, 0.5% SDS, 200 μg/mL salmon sperm DNA, 10% Dextran sulfate), where a hybridization reaction was performed at 65° C. for 16-18 hours. At the end of the reaction, it was washed twice with 2×SSPE and 0.1% SDS at room temperature for 15 minutes. The blotted membrane was then washed again with 1×SSPE and 0.1% SDS at 65° C. for 15 minutes. It was then subjected to exposure by pressing against an X-ray film. The result was shown in FIG. 1 , and was indicated that the gene was expressed mainly at floral organ.
Example 2
Cloning of Oncidium Aureusidin Synthase Gene Promoter
1. Source of Oncidium λEMBL3 Genomic Library (Genomic Library)
Oncidium genomic library was constructed by extracting genome DNA from leaves of Oncidium Gower Ramsey, which, by using bacteriophage λEMBL3 as vector, and replacing DNA through enzymatic cleavage, was used to construct said genomic library.
2. Preparation of Nucleic Acid Probe and Labeling
A gene fragment of aureusidin synthase gene AmAS1 (GenBank accession number AB044884, SEQ ID No: 1) from Antirrhinum majus was used as a template to prepare a nucleic acid probe by means of Prime-A-Gene kit (Promega, USA) under following conditions: total reaction volume: 50 μL; reaction mixture consisting of 1× labeling buffer, pH6.6 {50 mM Tris-HCL, pH8.3, 5 mM MgCl 2 , 2 mM DTT, 0.2 M HEPES [N-(2-hydroxyethyl)piperazine-N′-(2-ethanesulfonic acid)], 26A 260 unit/mL of random hexadeoxyribonicleotides}, 20 μM each of dATP, dGTP, dTTP, 500 ng/mL denatured DNA template, 400 μg/mL of Bovine serum albumin (BSA), 50 μCi [α- 32 P] dCTP (333 nM), and 5 unit Klenow DNA Polymerase. After reacting at 37° C. for 2 hours, 2 μL 0.5 M EDTA (pH8.0) was added to terminate the reaction, followed by adding 8 μL of tracing dye (50% glycerol, 0.25% bromophenol blue). The reaction solution was passed through a Sephadex-G50 chromatograph column, eluted with TE buffer (pH7.6), and fractions of each 160˜180 μL was collected in tubes. Each tube was counted in a liquid scintillation counter (Beckman 1801) to determine the radioactivity. Fractions with maximum radioactivity were used as the probe.
3. Selection of Oncidium Aureusidin Synthase Genomic Library
Plaque hybridization was used to select Oncidium genomic library. To this end, E. coli XL1-Blue MRA (P2) strain was used as the infection host for λEMBL3, and was cultivated in NZY medium (5 g/l of NaCl, 2 g/l of MgSO 4 -7H 2 O, 5 g/l of yeast extract). Selection was carried out under high stringency to obtain total of 150 million plaque forming units.
Next, bacteriophages were transferred on nitrocellulose membrane. The membrane was treated first with denaturing buffer (0.5 M NaOH, 1.5 M NaCl) for 2 minutes, and then treated with neutralization buffer [0.5 M Tris base, 1.5 M NaCl, 0.035% HCl (v/v)] for 5 minutes. Finally, it was soaked in 2×SSPE (1×SSPE, consisting of 0.18 M NaCl, 10 mM NaH 2 PO 4 , 1 mM EDTA pH7.4) for 30 seconds. It was placed in a vacuum oven at 80° C. for 2 hours to fix bacteriophage DNA. Thereafter, it was placed in a solution containing 2×SSPE and 0.1% SDS, and was shaken at room temperature for 1 hour. The nitrocellulose membrane thus treated was transferred in a pre-hybridization solution consisting of 5×SSPE, 5×BFP (1×BFP containing 0.02% BSA, 0.02% Ficoll-400000, 0.02% PVP-360000), 0.1% SDS, 50% formamide and 500 μg/mL of salmon sperm DNA, and a pre-hybridization reaction was carried out at 42° C. for 2 hours. A radio-labeled probe was used to carry out hybridization reaction with the membrane in 5×SSPE, 1×BFP, 0.1% SDS, 50% formamide and 100 μg/mL of salmon sperm DNA at 42° C. for 16˜18 hours. Then, the nitrocellulose membrane was treated twice with wash buffer I (5×SSPE, 0.1% SDS) at room temperature for 15 minutes. Subsequently, the nitrocellulose membrane was further treated twice each with wash buffer II (1×SSPE, 0.5% SDS) at 37° C. for 15 minutes to wash off non-specific probe. After developing by exposure against X-ray film at −80° C. (Kodak XAR film), bacteriophage bearing target gene DNA could be detected. Said bacteriophage was isolated from medium and was stored in SM buffer containing 0.03% chloroform and was subjected to purification several times to obtain Oncidium aureusidin synthase gene OgAS1 genome clone λOgAS9.
4. DNA Extraction from λOgAS9 Bacteriophage Clone
Bacteriophage liquor of the above-described objective clone λOgAS9 was applied over NZY solid medium by scribing bacteriophage liquor with toothpick. 3 mL Top agar containing host cell E. coli XL1-Blue MRA (P2) was added and cultivated on the NZY solid medium at 37° C. for 8 hours. On the next day, a single plaque agar gel was dug from one line with a capillary and was cultivated further by spreading over NZY solid medium at 37° C. for 7˜11 hours. Then, the culture medium was transferred to a refrigerator at 4° C., SM was added to release bacteriophages. The solution was collected in a centrifuge tube and chloroform was added thereto to 0.03%. The resulting mixture was centrifuged at 4° C. 7,000 rpm (Beckman J2-MC, JS-13.1) for 5 minutes, and then stored at 4° C. for use. Thereafter, large amount of the objective bacteriophage clone reproduced above was used to transfect host cells at a ratio of 5:1. To this, 1 mL SM buffer and 5 mL of 2.5 mM CaCl 2 was added and mixed, stored at room temperature for 15 minutes, and then at 37° C. for 45 minutes. It was then poured into 100 mL of 2×NZY liquid medium (0.4% MgSO 4 □7H 2 O, 2% NaCl, 1% bacto-yeast extract, 2% NZ amine, 0.2% casaimino acid, 5 mM MgSO 4 , 25 mM Tris-HCl pH7.5), and cultivated by shaking at 37° C. and 240 rpm for more than 8 hours. Thereafter, 4.5 mL chloroform was added thereto, and was treated by shaking at 37° C. and 240 rpm for 15 minutes, followed by centrifuged at 4° C. and 7,000 rpm for 20 minutes (Beckman J2-MC, JA 10 rotor). To its supernatant, 100 μL DNase I (1 mg/mL) and 100 μL RNaseA (10 mg/mL) were added, and the resulting mixture was treated at 37° C. and 80 rpm for 45 minutes. Next, 33 mL of 4 M NaCl was added, placed in an ice bath for 1 hour; followed by adding 33 mL of ice cold 50% polyethylene glycol, and settled at 4° C. overnight. The mixture was centrifuged at 4° C. and 5,000 rpm for 20 minutes (Beckman J2-MC, JA 10 rotor). The supernatant was discarded, and the pellet was air-dried. The solid precipitate was re-suspended in 500 μL PKB solution (10 mM NaCl, 10 mM Tris-HCl pH8.0, 10 mM EDTA, 0.1% SDS). To this suspension, proteinase K (final concentration 12.5 μg/mL) was added, and the resulting mixture was reacted at 37° C. for 20 minutes. The reaction mixture was then extracted successively with equal volume of phenol, PCI (phenol:chloroform:isoamyl alcohol=25:24:1), and CI (chloroform:isoamyl alcohol=24:1). The combined extract was centrifuged at room temperature and 14,000 rpm for 5 minutes. To the supernatant, 2-fold volume of −20° C. 100% ethanol was added, and the resulting mixture was centrifuged at 4° C. and 14,000 rpm for 10 minutes. The supernatant was decanted off, and the pellet was air-dried. The precipitated DNA was washed with 70% ethanol and 100% ethanol, respectively, dissolved in TE buffer (pH7.5), and stored at 4° C. for use.
5. Sequencing of DNA
An automatic nucleic acid sequencer ABI sequencer 377 was used to perform the sequencing of DNA, and thus determined the sequence of Oncidium aureusidin synthase genomic clone λOgAS9. It was analyzed with PC/Gene software available from IntelliGenetics Inc., and the result was shown in FIG. 2A . As shown, Oncidium aureusidin synthase genomic clone λOgAS9 had 2 exons, exon 1 and exon 2, with its translation start site (gene code: ATG) located at 30˜32 nucleotides in exon 1, while the 3,014 bp local sequence of the promoter ahead of the transcription start site of the exon 1 (i.e. the first nucleic acid sequence on the exon 1) was as shown in SEQ ID No: 3.
Example 3
Construction of a Vector Containing Oncidium Aureusidin Synthase Gene OgAS1 Promoter
As shown in FIG. 2B , the construction strategy of Oncidium aureusidin synthase gene OgAS1 promoter comprised of constructing the 3,014 bp promoter sequence (SEQ ID No: 3) ahead of the translation start site of Oncidium aureusidin synthase gene OgAS1 into an Agrobacterium tumefaciens cloning vector pGKU to replace the original CaMV 35S promoter (35Sp) in a manner that the 3′ end of the Oncidium aureusidin synthase gene OgAS1 promoter (SEQ ID No: 3) was linked to the 5′ end of reporter gene β-glucuronidase (GUS) gene sequence, and used as the promoter of said reporter gene.
Step 1: Construction of Agrobacterium tumefaciens Cloning Vector pGKU
The construction strategy of Agrobacterium tumefaciens cloning vector pGKU was shown in FIG. 3 . Briefly, a fragment of CaMV 35S promoter (35Sp)-reporter gene (GUS)-terminator (NOS-ter) (CaMV 35S::GUS-NOS) in a commercial vector pRT99GUS was constructed into a commercial Agrobacterium tumefaciens cloning vector pGreen0029 (John Innes Centre) to obtain Agrobacterium tumefaciens cloning vector pGKU. The construction strategy utilized polymerase chain reaction (PCR) to synthesize CaMV 35S promoter (35Sp) DNA fragment and reporter gene (GUS)-terminator (NOS-ter) DNA fragment, respectively, wherein, by means of the design of PCR primer, cleavage sites of NcoI restrictive enzyme were inserted at the 3′ end of CaMV 35S promoter (35Sp) DNA fragment and the 5′ end of reporter gene (GUS)-terminator (NOS-ter) DNA fragment, respectively. Finally, both PCR fragments were constructed into pGreen0029 to obtain Agrobacterium tumefaciens cloning vector pGKU.
Step 1.1: Obtaining CaMV 35S promoter (35Sp) fragment from commercial vector pRT99GUS
DNA of commercial vector pRT99GUS was used as the template, and the amplification of the DNA sequence of CaMV 35S promoter (35Sp) fragment was carried out through PCR, wherein sequences of primers used in said PCR were as followed:
forward primer S5 (containing HindIII restrictive enzyme cleavage site):
(SEQ ID No: 4) 5′-tgcatgcatgc aagctt g-3′ HindIII reverse primer S3 (containing NcoI restrictive enzyme cleavage site): (SEQ ID No: 5) 5′-ata ccatgg cccggggatcctctagagtcgaggtcct-3′ NcoI
The total reaction volume of PCR was 50 μl (consisted of: 1 μl genome DNA, 10 μl 5× Phusion HF buffer, 1 μl 10 mM dNTP, 1 μl 20 of μM forward primer, 1 μl of 20 μM reverse primer, 35.5 μl of sterile water, 0.5 μl Phusion DNA polymerase) and PCR conditions were: 98° C. for 30 seconds, followed with total 35 cycles of 98° C. 10 seconds, 60° C. 30 seconds, and 72° C. 60 seconds, and finally 72° C. for 10 minutes as elongation. PCR product of 544 bp in length was synthesized. PCR product was digested with HindIII and NcoI restrictive enzymes, and DNA fragment (fragment S) of 470 bp in length was recovered and stored at 4° C. till used.
Step 1.2: Obtaining Reporter Gene (GUS)-Terminator (NOS-Ter) Fragment from Commercial Vector pRT99GUS
Likewise, DNA of a commercial vector pRT99GUS was used as the template, and polymerase (PCR) was carried out to amplify DNA sequence of reporter gene (GUS)-terminator (NOS-ter) fragment, sequences of primers used in the PCR were as followed:
forward primer G5 (containing NcoI restrictive enzyme cleavage site):
(SEQ ID No: 6) 5′-ata ccatgg tacgtcctgtag-3′ NcoI reverse primer G3 (containing HindIII restrictive enzyme cleavage site): (SEQ ID No: 7) 5′-acggccagtgcc aagctt gcat-3′ HindIII
Total reaction volume of PCR was 50 μl (consisted of: 1 μl genome DNA, 10 μl 5× Phusion HF buffer, 1 μl of 10 mM dNTP, 1 μl of 20 μM forward primer, 1 μl of 20 μM reverse primer, 35.5 μl of sterile water, 0.5 μl Phusion DNA polymerase). PCR conditions were: 98° C. for 30 seconds, followed with total 35 cycles of 98° C. 10 seconds, 60° C. 30 seconds, 72° C. 60 seconds, and finally, 72° C. for 10 minutes as elongation. PCR product of 2,108 bp in length was synthesized. The PCR product was digested with HindIII and NcoI restrictive enzymes, DNA fragment (fragment G) of 2,093 bp in length was recovered and stored at 4° C. till used.
Step 1.3: Ligation of DNA
A commercial vector pGreen0029 was digested with HindIII restrictive enzyme. DNA fragment (fragment P) of 4,632 bp in length was recovered. DNA ligation was carried out on fragment P together with fragment S (step 1.1) and fragment G (step 1.2) to obtain Agrobacterium tumefaciens cloning vector pGKU. As shown in FIG. 3 , in Agrobacterium tumefaciens cloning vector pGKU, in addition to the character of pGreen, there were a CaMV 35S promoter (35Sp)-reporter gene (GUS)-terminator (NOS-ter) DNA fragment from commercial vector pRT99GUS, and an NcoI restrictive enzyme cleavage site at the 3′ end of CaMV 35S promoter (35Sp). Accordingly, by means of the SmaI restrictive enzyme cleavage site in pGreen0029 as the multiple cloning site and NcoI restrictive enzyme cleavage site, Agrobacterium tumefaciens cloning vector pGKU could replace CaMV 35S promoter (35Sp) with other promoter sequence so as to activate reporter gene GUS.
Step 2: Obtaining Oncidium Aureusidin Synthase Gene OgAS1 Promoter (OgAS1p) Sequence
Genomic DNA extracted from leaves of Oncidium Gower Ramsey plant in Example 2 was used as the template, polymerase chain reaction (PCR) was carried out to amplify the 3,014 bp sequence (SEQ ID No: 3) ahead the translation start site of Oncidium aureusidin synthase gene OgAS1, wherein, through the design of PCR primer, NcoI restrictive enzyme cleavage site was inserted at the 3′ end of the fragment for subsequent construction.
Sequences of primers used in PCR were as followed:
forward primer P1:
5′-gcattctagtgctctgaatgc-3′ (SEQ ID No: 8)
reverse primer P2 (containing externally added NcoI restrictive enzyme cleavage site):
(SEQ ID No: 9) 5′-aca ccatgg tgattgatgatc-3′ NcoI
Total reaction volume of PCR was 50 μl (consisted of: 1 μl genome DNA, 10 μl 5× Phusion HF buffer, 1 μl of 10 mM dNTP, 1 μl of 20 μM forward primer, 1 μl of 20 μM reverse primer, 35.5 μl of sterile water, 0.5 μl Phusion DNA polymerase). PCR conditions were: 98° C. for 30 seconds, followed with 35 cycles of 98° C. 10 seconds, 65° C. 30 seconds, and 72° C. 60 seconds, and finally, 72° C. 10 minutes as elongation. PCR product was digested with NcoI, whole length DNA fragment was recovered and stored at 4° C. till used.
Step 3: Ligation of DNA
Agrobacterium tumefaciens cloning vector pGKU obtained in step 1 was subjected to double SmaI+NcoI restrictive enzyme digestion. pGKU vector thus digested was recovered, and was ligated with DNA fragment prepared in step 2 to obtain plasmid OgAS1p-GUS bearing Oncidium aureusidin synthase gene OgAS1 promoter sequence (SEQ ID No: 3). In said OgAS1-GUS plasmid, DNA sequence of reporter gene β-glucuronidase (GUS) was linked to the 3′ end of Oncidium aureusidin synthase gene OgAS1 promoter (OgAS1p::GUS-NOS). Consequently, upon transformation of OgAS1-GUS plasmid in a plant body through Agrobacterium tumefaciens transformation, analysis on the mode for activating the gene expression of reporter gene β-glucuronidase (GUS) by Oncidium aureusidin synthase gene OgAS1 promoter could be studied.
Example 4
Transfection into Arabidopsis thialana Columbia Via Agrobacterium Tumefaciens -Mediated Process
Model plant Arabidopsis thialana Columbia was used as the material, and plasmid OgAS1-GUS prepared in example 3 was transfected into Arabidopsis thialana Columbia by means of Agrobacterium tumefaciens inflorescence infiltration process in a manner that the genomic constitution in the transgenic plant could be altered. As a result, the Oncidium aureusidin synthase gene OgAS1 promoter could activate the expression of reporter gene GUS in the objective transgenic plant and progeny thereof. In addition, expression site of reporter gene GUS on Arabidopsis thialana Columbia transformant could be analyzed by GUS histochemical staining, and hence detected whether Oncidium aureusidin synthase gene OgAS1 promoter exhibited tissue-specificity.
1. Cultivation of Arabidopsis thialana Columbia Plant Material
Seeds of Arabidopsis thialana were wet and cold stratified at 4° C. for 2-4 days and sowed in a medium consisting of peat: Perlite: vermiculite in a ratio of 10:1:1. Cultivation conditions were: 22-25° C., 16 hours light cycle, and 75% relative humidity. After about 4-6 weeks, the plant was pruned. As the rachis had grown to a length of about 3 inches on 4-8 days after pruning, the plant was subjected to transformation.
2. Preparation of Agrobacterium tumefaciens Liquor and Infiltration
Agrobacterium tumefaciens LBA4404 strain was inoculated in YEB solid medium (0.5% beef extract, 0.1% yeast extract, 0.5% peptone, 0.5% mannitol, 0.05% MgSO 4 , 1.25% agar, pH 7.5) containing suitable antibiotics (50 μg/ml of kanamycin, 50 μg/ml of ampicillin), and cultivated at 28° C. for 2 days. Then, single colony was picked and inoculated in 20 ml YEB liquid medium containing suitable antibiotics (50 μg/ml of kanamycin, 50 μg/ml of ampicillin) and cultivated by shaking at 28° C. and 240 rpm for 1 day. 5 ml bacteria liquor thus obtained was added in 200 ml YEB liquid medium and cultivated at 28° C. and 240 rpm for 9 hours. The culture suspension was centrifuged at 4° C. and 4,200 rpm for 20 minutes (Beckman J2-MC, JA-10 rotor). The supernatant was discarded, and the pellet was suspended in 20 ml pre-cooled YEB medium. The resulted suspension was centrifuged again at 4° C. and 4,200 rpm for 20 minutes. The pellet was re-suspended in 20 ml pre-cooled YEB medium and was stored at 4° C. till used. Agrobacterium tumefaciens transformation was performed employing frozen-thaw method. 500 μl suspension of Agrobacterium tumefaciens to be transformed was well mixed with 1 μg OgAS1p-GUS plasmid DNA prepared in Example 3, and the mixture was treated successively on ice, in liquid nitrogen and at 37° C., each for 5 minutes. The bacteria liquor was then mixed with 1 ml YEB medium and cultivated by shaking at 28° C. and 240 rpm for 3˜4 hours. The bacterial liquor was applied over medium containing suitable antibiotics (50 μg/ml of kanamycin, 50 μg/ml of ampicillin), and cultivated at 28° C. for 2 days. Agrobacterium tumefaciens that had been transformed to contain plasmid OgAS1p-GUS prepared in example 3 was used to inoculate single colony of the above-described Agrobacterium tumefaciens on 5 ml YEB medium (0.5% beef extract, 0.1% yeast extract, 0.5% peptone, 0.5% mannitol, 0.05% MgSO 4 , pH 7.5) containing suitable antibiotics (50 μg/ml of kanamycin, 50 μg/ml of ampicillin) and cultivated by shaking at 28° C. and 240 rpm for 2 days. Then, it was poured in 250 ml YEB medium containing suitable antibiotics (50 μg/ml of kanamycin, 50 μg/ml of ampicillin), and cultivated again by shaking at 28° C. and 240 rpm for more than 24 hours. It was then centrifuged at 4° C. and 6,000 rpm for 10 minutes. The supernatant was discarded, and the pellet was suspended in 200 ml infiltration medium (½ MS, 5% sucrose, 0.044 μM ABA, 200 μl/l or 0.01% Silwet L-77, pH 5.7). Arabidopsis thialana Columbia plants to be transformed were placed upside down in the Agrobacterium tumefaciens suspension, and soaked there for 20 seconds. Arabidopsis thialana Columbia plants were taken off and kept wet for 24 hours. Seeds could be harvested after about 3˜4 weeks.
3. Sowing and Selection of Transformant
The transformed Arabidopsis thialana Columbia seeds thus-collected was rinsed several times with sterile water, treated with 70% ethanol for 2 minutes, treated with sterile water containing 1% Clorox and 0.1% Tween-20 for 20 minutes, and then rinsed 4-5 times with sterile water for 5 minutes each time. Thereafter, these seeds thus-treated were sown in germinating medium (½ MS, 1% sucrose, 0.7% agar, 50 μg/ml of kanamycin, 50 μg/ml of ampicillin) to carry out segregation assay of anti-antibiotic progeny. Homozygous transformant progeny thus obtained could be used in assay of promoter activity.
4. GUS Histochemical Staining
Tissue to be stained of the transformant was soaked first in pre-treatment buffer [50 mM Na 3 PO 4 (pH6.8), 1% TritonX-100] at 37° C. for 2 hours, rinsed then 2˜3 times with Triton X-100-free buffer (50 mM Na 3 PO 4 , pH6.8), and added thereto buffer (1 mM X-Gluc dissolved in 50 mM Na 3 PO 4 , pH6.8) containing X-Gluc (5-Bromo-4-chloro-3-indoxyl-beta-D-glucuronic acid). The mixture was evacuated at 25 inches-Hg for 5 minutes, returned to atmospheric pressure for 5 minutes, and this procedure was repeated once. Then, it was placed at 37° C. to react for 2 days. The enzymatic reaction and tissue discoloration were terminated with 70% ethanol, and the coloration status was observed under a microscope.
FIG. 4 shows the result of GUS activity analysis. As shown in FIG. 4 , reporter gene GUS activated by Oncidium aureusidin synthase gene OgAS1 promoter could be expressed only at anther in Arabidopsis thialana Columbia transformant floral organ ( FIGS. 4C and D), while no GUS activity could be detected in root, stem, leaf and pod of Arabidopsis thialana Columbia transformant ( FIGS. 4A and B). Results from GUS activity analysis indicated that, Oncidium aureusidin synthase gene OgAS1 promoter exhibited characteristics to activate anther-specific expression, and significant activation ability.
Example 5
Transformation of Nicotiana tabacum L. Via Agrobacterium tumefaciens -Mediated Process
Separately, Nicotiana tabacum L. cv Wisc. 38 was used as the material, and similarly, Agrobacterium tumefaciens -mediated transformation was employed to transform plasmid OgAS1p-GUS prepared in example 3 into Nicotiana tabacum L. to alter genomic constitution in the transgenic plant such that Oncidium aureusidin synthase gene OgAS1 promoter could activate effectively the expression of reporter gene GUS at objective transgenic plant and progeny thereof. Furthermore, GUS histochemical staining was used to analyze expression site of reporter gene GUS in Nicotiana tabacum L. transformant to detect whether Oncidium aureusidin synthase gene OgAS1 promoter exhibits likewise a tissue-specificity in Nicotiana tabacum L. plant.
1. Preparation of Agrobacterium tumefaciens liquor
The same procedure described in example 4 was followed in this example.
2. Transformation of Agrobacterium tumefaciens
The same procedure described in example 4 was followed in this example.
3. Small amount preparation of thus-transfected Agrobacterium tumefaciens plasmid
The same procedure described in example 4 was followed in this example.
4. Transformation and selection of Nicotiana tabacum L.
Leaves of sterile seeding Nicotiana tabacum L. cv Wisc. 38 plants were cut into square of 1.5 cm×1.5 cm, placed on N01B1 solid medium (MS, adding 0.1 mg/L of 1-naphthyl acetic acid, 1 mg/L of BA, 3% sucrose, pH 5.7, 0.7% agar) and cultivated at 25° C., 16-hour lighting environment for 1 day. Then, the square leaves were dipped in bacterial liquor for 3-5 minutes. Next, they were placed on N01B1 solid medium, and cultivated at 25° C., 16-hour lighting environment for 3 days. Thereafter, those square leaves were soaked and washed in 20 mL N01B1 liquid medium containing 250 mg/L of cefotaxime for 1 minute. Subsequently, they were transferred on N01B1 solid medium containing 250 mg/L of cefotaxime and 100 mg/L of kanamycin, and were selected at 25° C., 16-hour lighting environment for about 3 weeks. Upon germination of adventitious buds from square leaves, those leaves were moved onto N01B1 solid medium containing 250 mg/l of cefotaxime and 200 mg/l of kanamycin. Selection was carried out at 25° C., 16-hour lighting environment. As shoots had grown to longer than 1 cm, shoots without etiolation could be cut and cottage cultivated in MS solid medium containing 250 mg/L of cefotaxime and 200 mg/L of kanamycin at 25° C. and 16-hour lighting environment till rooting. The plants were used in GUS activity assay.
5. Gus Histochemical Staining
The Nicotiana tabacum L. transformant survived in the above selection was subjected to GUS histochemical staining analysis followed the procedure described in example 4.
Results of GUS activity analysis shown in FIG. 5 indicated that reporter gene GUS activated by Oncidium aureusidin synthase gene OgAS1 promoter could be expressed only at anther of floral organ in Nicotiana tabacum L. transformant ( FIGS. 5B and C); while Nicotiana tabacum L. seedlings at vegetative growth stage could not take place GUS coloration ( FIG. 5A ). Therefore, GUS activity analytical results from both of Arabidopsis thialana Columbia and Nicotiana tabacum L. transformants indicated that, Oncidium aureusidin synthase gene OgAS1 promoter could exhibit significant anther-specific activation ability in different species.
In summary, anther-specific promoter and application thereof provided according to the invention gives following advantages over other conventional techniques:
1. The promoter of the invention can activate the expression of gene behind its 3′ end to express in anther, and by means of this particular tissue-specificity of said promoter, over-expressing target gene at anther of a plant.
2. The promoter of the invention can be transferred into a plant through a form of vector, and enables the over-expression of the target gene to take place in anther of the transgenic plant and progeny thereof. As the result, a vector containing the promoter of the invention can be used as a tool to modulate gene expression, which provides great value on industrial application.
While the detailed description provided above is directed to a possible embodiment of invention, it should be understood that said embodiment is not construed to limit the scope of the invention as defined in the appended claims, and those embodiments or alteration that can be made without departing from the spirit and scope of the invention are intended to fall within the scope of the appended claims.
Accordingly, the invention has indeed not only an innovation on the species gene, but also has particularly an expression uniqueness, and therefore, the application should meet sufficiently requirement of patentability on novelty and non-obviousness, and should deserve an invention patent right.
Many changes and modifications in the above described embodiment of the invention can, of course, be carried out without departing from the scope thereof. Accordingly, to promote the progress in science and the useful arts, the invention is disclosed and is intended to be limited only by the scope of the appended claims. | The invention provides an anther-specific expression promoter in plant, wherein said promoter is a promoter of Oncidium aureusidin synthase gene OgAS1, and has a sequence as SEQ ID No: 3. The invention provides further a gene expression cassette that comprised a promoter having a DNA sequence as SEQ ID No: 3, and a polynucleotide that encode an open reading frame and is linked to the 3′ end of said promoter, wherein said promoter can activate the transcription of said polynucleotide in an organism containing said gene expression cassette. The invention provides also a gene expression vector that contains a promoter having DNA sequence as SEQ ID No: 3. The invention provides further a process for producing a transgenic plant or part of organ, tissue or cell of said transgenic plant containing the above-described gene expression cassette. | 2 |
BACKGROUND OF THE INVENTION
This invention relates to radio communications equipment in general and to system failure monitors in communications equipment in particular.
The increase in complexity in advanced electronic communication equipment has brought with it the need for improved maintenance techniques and methods necessary to keep an item in proper condition or to restore it to proper condition once it has failed. This includes a variety of problems particularly related to the increasing use of extremely complex solid state elements and the use of digital techniques.
The use of these advanced communications devices has particular application to aviation in that significant advances in data transfer rates, weight and cost considertions, as well as reliability, can be made through these technical advances. However, the aircraft environment under normal operating conditions provides an extremely varied temperature, pressure and mechanical stress environment. Vibration caused by the engines of the aircraft as well as repeated mechanical forces caused by landings and other normal flight-encountered air turbulence, have particularly caused problems in maintaining antenna systems on the aircraft. Repeated temperature fluctuations additionally have caused problems in antenna mounting and electrical connections.
Diversity systems have been developed primarily to reduce fading characteristics inherent in essentially all forms of electromagnetic radiation communication. Fading is a drift in the level of received radio signals beyond intelligibility. It is often caused by changes in the upper atmosphere or by increases in distance from the transmitter to the receiver; or by obstruction in the signal path, an additional reason for development of a diversity system to provide a receiving antenna which will always be illuminated by the transmitted signal. A good example of this type of diversity system is the discrete address beacom system (DABS) developed for providing the aircraft surveillance and communications necessary to support aircraft traffic control automation in the dense air traffic environments expected in the future. An excellent background of the DABS concept is provided in the Federal Aviation Administration Report No. FAA-RD-8041 published April 1980. Chapters 4 and 5 of that publication have particular application to the implementation of the present invention and are hereby incorporated by reference thereto.
The DABS transponder mounted in the aircraft, as envisaged by the above reference FAA report, incorporates the use of a diversity receiver having two antennas, one mounted on the upper side of the aircraft, and a second mounted on the underside of the aircraft. This will enable either or both of the receiving antennas to be constantly illuminated within the operating range of the ground based transmitter, irrespective of aircraft attitude relative to the horizon, speed of the aircraft, or relative position to the ground-based transmitter, notwithstanding the fading effects previously discussed.
If, however, one of the antennas fails leaving the other antenna receiver system in operation, it is desirable, for maximum serviceability of the system, to detect this problem as soon as possible. For example, if an aircraft makes a flight wherein the uppermost antenna receiver apparatus is never utilized, primarily because the lower mounted antenna apparatus remains constantly illuminated, the inoperability of the upper mounted antenna will go essentially undetected unless the aircraft on a subsequent flight assumes an attitude which will block the lower antenna from reception and, as can be clearly seen, this is the precise attitude and time of a loss of reception (such as a climb-out on take-off) when the loss in communications could be catastrophic.
A significant contributing element to the maintenance problem is the intermittent nature of certain types of failures. For example, a broken antenna connector cable may provide a low impedance contact at ground level; however, upon attaining altitude and after a period of flight wherein the aircraft is exposed to much lower ambient temperature than experienced at ground level, the broken connector becomes separated and essentially appears as a high impedance or open contact. Upon returning to ground, the warmer temperatures cause the broken connector to once again come into contact and thereby make the receiver apparatus functional once again. The first problem, that is of detection, become difficult utilizing a ground test procedure because in fact the failure only exists under circumstances attained during flight. A second problem exists in attempting to locate and determine the cause of the failure once the fact of a failure has been established. This intermittent type failure poses a significant safety hazard in a crowded air traffic environment, primarily because of the difficulty of detection of such failure.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide a maintenance monitor capable of detecting a discrepancy in the integrity of antenna systems used in a diversity communication system.
A yet further object of the invention is to provide a continuously monitoring apparatus capable of providing the history of functional capability of a diversity communication system.
Briefly, in accordance with the present invention, an antenna system monitor in a diversity communication apparatus is disclosed having means for receiving a plurality of signals containing substantially similar information, means for comparing at least two of the signals to detect dissimilarities in the information in the received signals, and means for relating detected dissimilarities to a failure in the means for receiving. Essentially, this requires the recording of the occurrence of properly received signals from both diversity antenna systems simultaneously, and storing that information for subsequent examination.
An antenna function monitor apparatus in a discrete address beacon system transponder comprises at least two antennas; at least two receivers, each coupled to a different one of the antennas; at least two decoders, each coupled to a different one of the receivers; at least two data latches, each coupled to a different one of the decoders wherein a properly decoded signal in one of the decoders triggers the respective latch; and means for transferring the data stored in all of the latches into a non-volatile memory and for resetting the data latches. The data stored in the latches is transferred on a periodic basis wherein the period is long enough to provide relatively large numbers of signals to be received by the respective antennas. A failure to receive any of the large number of transmitted signals by one or both of the antenna-receiver combinations is thereafter stored as a failure indication in non-volatile memory on-board the aircraft.
BRIEF DESCRIPTION OF THE DRAWING
A functional block diagram of a portion of a DABS transponder having incorporated the present invention is shown wherein the added elements required to practice the present invention are related to the already-existing transponder elements.
DETAILED DESCRIPTION OF THE INVENTION
Referring now to the drawing, antenna 110 is mounted on the upper side of an aircraft and antenna 111 is mounted on the under side of the same aircraft. The principle elements of the DABS transponder are interconnected in a similar manner to that depicted in FIG. 4-2 on page 77 of the incorporated FAA publication. Receiver 112 has an input connection from antenna 110 and amplifies received signals for input into the differential phase shift keying demodulator 116 and thereafter into the decoder 118. This structure is essentialy similar to the typical DABS transponder depicted in FIGS. 4-2 and 4-3 of the above-referenced FAA publication. FIG. 4-3 however utilizes a single DPSK demodulator. As will be shown, alternative embodiments as shown in FIGS. 4-2 and 4-3 are easily adapted to incorporate the present invention. For purposes of complete explanation of the present invention and to avoid confusion, a transponder system as shown in the present application utilizing two demodulators, two decoders, and two encoders, will be utilized to demonstrate the interconnection of the present invention to a DABS transponder.
Receiver 113 similarly receives a signal from antenna 111 and amplifies it for input into the DPSK demodulator 117. That signal is therafter input into the decoder 119. Under normal properly operating circumstances, the signals received by antennas 110 and 111 will be substantially the same and will occur simultaneously. Should antenna 111 or alternatively antenna 110 not receive a signal, the transponder system as described in the incorporated FAA document is designed to receive the required information and respond on the antenna having the strongest signal. In the worst case circumstance where one antenna fails completely, the transmitter is designed to continuously respond on the operating antenna. Transmitter 130 is coupled to encoder 120 and encoder 121 and together with selection logic and other control circuitry of the transponder (not shown) the proper antenna for transmission is connected utilizing switch 114 and 115 whch are controlled by the selection logic and thereafter transmitter 130 is able to respond to the interrogation signal.
The present invention, however, is concerned with properly decoded signals only. A properly decoded signal from decoder 118 establishes a "functional" signal to be input into data latch 122. Similarly, decoder 119 also registers a properly received decode into data latch 123. Both data latch 122 and 123, in the simplest embodiment, are simple flip-flop storage elements consisting of two cross-coupled logic gates that store a pulse applied to one logic input until a "reset" pulse is applied to the other input. The latched data is controlled with respect to periodic readouts into the CPU interface 129 by software in the CPU 128. The timer 125 controls the CPU operation and the software control of the data latches is shown in Table 1.
TABLE 1______________________________________Antenna System Monitor Software Description______________________________________INITIALIZERESET ANTENNA DATA LATCH ARESET ANTENNA DATA LATCH BSTART INTERVAL TIMERTEST TIMERSubroutine: If timer not timed out, go to TEST TIMERTEST WHEELS DOWNSubroutine: If wheels down, go to RESETANTENNA DATA LATCH AREAD DATA LATCH ANTENNA AREAD DATA LATCH ANTENNA BINCREMENT NON-VOLATILE MEMORY A WITHDATA ANTENNA AINCREMENT NON-VOLATILE MEMORY B WITHDATA ANTENNA BGo to RESET ANTENNA DATA LATCH A______________________________________
The CPU interface 129, the CPU 128, and the non-volatile memory 131 in one embodiment are all incorporated into a typical DABS transponder utilizing microprocessor control. Alternatively, these units may be added to provide the antenna monitor function in a unit either not already having a microprocessor or having a system not readily adapted to attaching and controlling the latches 122 and 123 as herein described. The RS-232 interface 124 is shown connected to the CPU interface and is provided for outputting data on line 126 to a plug-in test monitor when the aircraft is undergoing maintenance on the ground. Similarly, timer 125 is provided for clocking the CPU in a typical application and both timer 125 and interface 124 while utilized in conjunction with the present invention have additional uses in the control and operation of the transponder itself in this exemplary embodiment and are utlized in a typical manner. The wheels down signal 127 is provided by a sensor capable of detecting when the aircraft is on the ground. This sensor has been referred to as a "squat switch" and detects whether or not the aircraft is on the ground or, if in fact, there is no weight on the wheels and the aircraft is airborne. As can be seen in Table 1, the use of the wheels down or "squat switch" in the software control program for the antenna monitor allows the CPU to conserve memory by only storing operational information during the actual airborne period of the aircraft.
Data between the CPU and CPU interface is carried on bus 132, and between the CPU and memory on bus 134. Likewise the address bus 133 couples the CPU to the CPU interface, while address bus 135 couples the CPU to the memory 131.
In actual operation, the period set for reading latches 123 and 122 is set at approximately 10 to 15 minutes to allow for hundreds or thousands of DABS interrogations from the ground-based unit to be received by the antennas. This enables the decoders to provide a "functional" input into the data latch during the 10 minute period of flight and if both antenna receiver systems are operational (a single properly decoded signal during the 10 minute period) both data latches will have "functional" data stored therein until the conclusion of that 10 minute period. Thereafter, the CPU interface 129 reads the condition of the latch and upon software command by the CPU, the interface can then transfer the data to the non-volatile memory 131. The 10 and 15 minute interval is somewhat arbitrary, however it must be long enough to provide for a period of flight such as climb-out on take-off or a maneuver wherein one of the antennas is temporarily masked during the maneuver, and yet allow both antennas to once again become illuminated prior to completion of the 10 to 15 minute interval. If, however, during the entire period one of the antenna receiver systems does not decode a signal, then that is a "non-functional" input to the data latch and that then is subsequently stored into the non-volatile memory in a similar fashion. The non-volatile memory utilized has the advantages of being programmable while in the air and additionally maintaining memory should a power failure occur. Electrically erasable programmable read only memories (EEPROMs) or electrically alterable programmable read only memories (EAROMs) are currently available on the market and are suitable for this purpose.
Once the aircraft has landed, the maintenance technician installs a test unit by plugging into the RS-232 interface 124 or alternative digital interface and by directing the CPU 128 to read out the contents of memory 131. The data obtained by the data latches during each of the periods of flight is compared to determine if during one or more of those periods one of the antennas was operating while the other was not. In this manner, the technician is immediately apprised of the fact that there is an intermittent failure presumably at the low temperature portions at high altitude if in fact a temperature fluctuation has caused the failures.
An alternative method of connecting the data latches to a single DPSK demodulator and decoder unit is provided by connecting data latch 122 and 123 to the video processor stage of the diversity transponder and providing for a readout and reset of the latches at a timed interval. The decoder then functions to enable the latches to input data from the video processors.
Additional applications include, but are not limited to, multimode communication systems such as a transmitter-receiver combination utilizing two distinct frequencies to establish positive communications without regard to potential fading effects, and communication systems having different modes of primary communication, for example, a system utilizing groundwave propagation in conjunction with skywave propagation to maintain positive communications.
An alternative embodiment in a time diversity apparatus wherein a signal is repeated over and over again to insure positive communication where the present invention is utilized to detect when, if ever, the signal is not properly received. The technician, by utilizing the information gained from the present invention, can then locate and eliminate the source of the failure of communication if it is in fact a structural failure or, at least identify the fading characteristic as that caused by atmospheric disturbance or for other reasons. In this embodiment, only one data latch is required and it is operated at a more frequent time interval relative to the frequency of the repeated transmissions so as to provide a continuous monitoring capability.
Likewise, polarity diversity systems utilize separate antenna receiving structures, although they may be combined in some embodiments and the present invention essentially as described herein can be utilized to detect structural failures in the described manner.
While this invention has been described with reference to an illustrative embodiment, it is not intended that this description be construed in a limiting sense. Various modifications of the illustrative embodiment, as well as other embodiments of the invention, will be apparent to persons skilled in the art upon reference to this description. It is therefore contemplated that the appended claims will cover any such modifications of embodiments as fall within the true scope of the invention. | Disclosed is an antenna monitor for a diversity communication system having the capability of detecting differences in reception characteristics between a plurality of reception paths or modes and storing that failure information in a non-volatile memory store. Subsequently, the memory is read to determine if the antenna systems are functioning improperly. | 7 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. application Ser. No. 10/735,309, filed Dec. 12, 2003, now issued as U.S. patent Ser. No. ______ (Attorney Docket 02280), and incorporated herein by reference in its entirety.
TECHNICAL FIELD
[0002] The present invention is related to the capture of clickstreams generated by television viewers when making television programming selections. More particularly, the present invention is related to the collaborative capture of clickstreams both locally and remotely.
BACKGROUND
[0003] When a television viewer watches television, the viewer periodically makes selections to control what is being viewed. The viewer may change to a different channel and program, may choose to channel surf during commercials, may choose to shut down the television equipment and not watch any programming during certain time periods, etc. The sequence of these user commands are known as a clickstream which provides an indication of what the viewer is or is not watching on television when the clickstream is captured in relation to time, current channel before a change, current channel after a change, etc.
[0004] Initially, this clickstream was not captured in any way. The behavior of the television viewer was not tracked, and there was no way to identify trends in the behavior of the television viewer without requiring the television viewer to become involved, such as manually recording what the viewer watches or installing special equipment in the home of the viewer specifically for the purpose of tracking what programs the viewer watched.
[0005] The introduction of set top boxes that tune in broadcasted channels for the viewer gave rise to a way to track the television watching behavior of the viewer without requiring the viewer to become involved. The set top box receives multiple streams of television programming and executes the commands from the viewer such as channel changes to control which stream is being viewed by the viewer. The set top box may also be provided with clickstream capture functionality so that when the set top box receives a user command, the command is captured and stored within the set top box in addition to being executed within the set top box. In this way, the set top box effectively captures the viewing behaviors of the viewer.
[0006] The clickstream that has been captured may then be periodically forwarded from the set top box to a service provider system where it can be put to use. The service provider system may process the clickstream relative to profile information of the viewers producing the clickstreams to produce statistics about television viewing habits, such as statistics based on demographics. The service provider and/or television content providers may then utilize these statistics for various purposes. For instance, this information may be used to determine what television programming to provide to consumers.
[0007] While this set top box approach does provide the clickstream capture, it has drawbacks because for advanced television networks, some controls such as the switching between streams of programming may be performed within the television network for a viewer rather than at the set top box such that the set top box only receives a single stream at a time. Thus, the set top box may not include the intelligence to recognize the significance of one user command from another but instead simply transfers the user command to the television network for execution such that the set top box is ineffective at capturing the clickstream for these events.
SUMMARY
[0008] Embodiments of the present invention address these issues and others by providing a collaborative clickstream capture. At least some of the user commands are transferred from the premises of the viewer, such as by a set top box, to a remotely located component such as a video control system within a television network. These user commands are captured at the remotely located component and are stored remotely from the premises of the viewer. Additionally, the set top box continues to capture and store user commands as well, such as user commands that are implemented at the set top box rather than those transferred to the network.
[0009] One embodiment is a method of capturing user commands related to viewing television programming. The method involves receiving a first user command at a viewer appliance at a premises of the viewer and subsequently receiving a second user command at the first component. Information related to the first user command is stored at the viewer appliance concurrently relative to receiving the first user command. Relative to receiving the second user command, the second user command is concurrently forwarded from the viewer appliance to a component located remotely from the premises of the viewer. Information related to the second user command is stored remotely from the premises of the viewer upon receiving the second user command at the component.
[0010] Another embodiment is a method of capturing user commands related to viewing television programming. The method involves receiving a first user command at a viewer appliance at a premises of the viewer and subsequently receiving a second user command at the viewer appliance. Information related to the first user command is stored at the viewer appliance concurrently relative to receiving the first user command. The first user command is executed at the viewer appliance to alter a first aspect of the television programming being viewed by the viewer while the information related to the first user command continues to be stored at the viewer appliance. The second user command is forwarded concurrently relative to receiving the second user command from the viewer appliance to a component located remotely from the premises of the viewer. The second user command is executed at the component to alter a second aspect of the television programming being viewed by the viewer. Information related to the second user command continues to be stored upon receiving the second user command at the component after the second user command has been executed by the second component.
[0011] Another embodiment is a system for capturing user commands related to viewing television programming. The system includes a reception mechanism located at a premises of a viewer for receiving a first and a second user command. A transfer mechanism is located at the premises of the viewer for transferring the second user command concurrently relative to the reception mechanism receiving the second user command. A control mechanism executes the first and second user commands received by the reception mechanism to control aspects of the television programming being provided to the viewer. A capture mechanism is located remotely from the premises of the viewer and receives the second user command being transferred concurrently by the transfer mechanism. A first storage mechanism is located at the premises of the viewer and continues to store information related to the first user command after the first user command has been executed by the control mechanism. A second storage mechanism is located remotely from the premises of the viewer and continues to store information related to the second user command after the second user command has been executed by the control mechanism and received by the capture mechanism.
[0012] Another embodiment is a method of capturing user commands from a viewer that are related to viewing television programming. The method involves receiving the user command at a viewer appliance at the premises of the user. Upon receiving the user command, it is determined whether to store information related to the user command at the viewer appliance and the information related to the user command is stored at the viewer appliance when it is determined that the information related to the user command is to be stored at the viewer appliance. When it is determined not to store the information related to the user command at the viewer appliance, then the user command is forwarded from the viewer appliance.
[0013] Another embodiment is a method of capturing user commands from a viewer that are related to viewing television programming. The method involves receiving the user command at a viewer appliance at the premises of the viewer. Upon receiving the user command, it is determined whether to store information related to the user command at the viewer appliance and the information related to the user command is stored at the viewer appliance when it is determined that the user command is to be stored at the viewer appliance. Upon receiving the user command, it is determined whether to execute the user command at the viewer appliance and the user command is executed at the viewer appliance when it is determined that the user command is to be executed at the viewer appliance. When it is determined not to execute the user command at the viewer appliance, then the user command is forwarded from the viewer appliance.
[0014] Another embodiment is a method of capturing user commands from a viewer that are related to viewing television programming. The method involves receiving the user command at a component remotely from the premises of the viewer. Upon receiving the user command, it is determined whether to store information related to the user command remotely from the premises of the viewer and the information related to user command is stored remotely from the premises of the viewer when it is determined that the user command is to be stored remotely from the premises of the viewer. The user command is executed at the component.
[0015] Another embodiment is a method of capturing user commands from a viewer that are related to viewing television programming. The method involves receiving the user command at a component remotely from the premises of the viewer. Upon receiving the user command, the information related to the user command is stored remotely from the premises of the viewer. Upon receiving the user command, it is determined whether to execute the user command at the component and the user command is executed at the component when it is determined that the user command is to be executed at the component.
DESCRIPTION OF THE DRAWINGS
[0016] FIG. 1 shows an illustrative clickstream capture system architecture for implementing embodiments of the present invention where the television programming is broadcast to a viewer appliance that executes the user commands while some clickstream capture is performed locally and other clickstream capture is performed remotely from the viewer premises.
[0017] FIG. 2 shows an illustrative set of logical operations within the system of FIG. 1 for implementing embodiments of the present invention where clickstream capture occurs locally and remotely and user commands are executed locally.
[0018] FIG. 3 shows an illustrative clickstream capture system architecture for implementing embodiments of the present invention where at least a portion of the television programming is switched within the television network such that the television network executes user commands while some clickstream capture is performed locally and other clickstream capture is performed remotely from the viewer premises.
[0019] FIG. 4 shows an illustrative set of logical operations within the system of FIG. 3 for implementing embodiments of the present invention where some clickstream capture occurs locally and some occurs remotely and user commands are executed remotely.
[0020] FIG. 5 shows an illustrative set of logical operations within the system of FIG. 3 for implementing embodiments of the present invention where clickstream capture is performed locally and remotely and some user commands are executed locally and some are executed remotely.
[0021] FIG. 6 shows an illustrative set of logical operations within the system of FIGS. 1 and 3 for implementing embodiments of the present invention where all clickstream capture occurs both locally and remotely and execution of user commands occurs locally.
[0022] FIG. 7 shows an illustrative set of logical operations within the system of FIG. 3 for implementing embodiments of the present invention where all clickstream capture occurs both locally and remotely and execution of user commands occurs remotely.
[0023] FIG. 8 shows an illustrative set of logical operations within the system of FIG. 3 for implementing embodiments of the present invention where all clickstream capture occurs both locally and remotely and execution of some user commands occurs locally and execution of some user commands occurs remotely.
DETAILED DESCRIPTION
[0024] Embodiments of the present invention provide for the collaborative capture of clickstreams that are generated by TV viewers. With clickstream capture occurring at a remote location such as within the television network while clickstream capture is also occurring at the premises of the viewer, those user commands executed either locally or at the remote location may be captured. Furthermore, redundant clickstream capture may also be provided, such as for delivery of the captured clickstream from the local viewer appliance or other device to remote external locations.
[0025] FIG. 1 shows one example of a system for capturing the clickstreams where the television programming that is being provided to the viewer is a broadcast system. Multiple channels of television programming are being broadcast simultaneously to the viewer appliance, which then tunes to the particular channel of programming that the viewer desires to watch. The broadcast television programming is provided to viewers from a central location 102 , such as a community access television (“CATV”) headend or a telephone company (“telco”) central office (“CO”) which may provide Internet connectivity for streaming programming to the viewer.
[0026] The central location 102 includes various components for receiving the television programming to be broadcast to the television viewers. Much of the television programming originates from a satellite reception via a satellite receiver dish 106 . Additional direct local feeds 108 receive direct transmission via a wireline link to local television stations. Also, additional local off-air reception via antennas 110 may also receive local programming that is not otherwise received through the direct local feeds 108 .
[0027] These programming sources provide received programming to a content reception and processing system 104 . This system 104 takes the various channels of television programming being received and creates a channel line-up. The channel line-up is the distribution of the channels being provided by the service provider over the particular channels designated by the service provider. The content reception and processing system 104 receives a particular stream of programming and assigns it to a particular channel within the channel line-up.
[0028] The content reception and processing system 104 provides the individual streams of programming to a video broadcast system 112 . The video broadcast system 112 then broadcasts each of the streams of programming within its assigned channel of the channel line-up. The video broadcast system 112 broadcasts these channels, as well as data such as guide data, over a distribution network 116 that feeds each of a plurality of individual television viewer premises 118 . Typically, the distribution network 116 includes a network of coaxial or other lines that extend over a region being served, where each of the lines terminates at viewer premises 118 .
[0029] The broadcasts may be either in an analog or a digital format. The network 116 may carry either format or both formats, such as where one set of channels of the channel line-up are broadcast as analog while another set of channels of the channel line-up are digital. Additionally, the network 116 may carry two-way communications such that communications may be provided back to the central location 102 from viewer premises 118 . Alternatively, the network 116 may carry only one-way communications from the central location 102 to viewer premises 118 .
[0030] In addition, there may be alternative sources of television programming to a viewer appliance 120 at viewer premises 118 . An alternative source of content 128 may be provided to the viewer through an alternative network 130 such as a digital satellite connection, a digital off-air reception, etc. Thus, the viewer may select from various sources of content when providing user commands, and these user commands are captured for later processing.
[0031] At viewer premises 118 , the incoming stream of channels is provided to the viewer appliance 120 . The viewer appliance 120 such as a set top box or broadband gateway allows a viewer to provide commands to control aspects of the television programming being viewed, such as channel changes and/or additional aspects such as audio format and volume control. The viewer appliance typically outputs the selected channel to a television 122 . The viewer appliance 120 may be a gateway in place of a set top box so as to receive user commands from different areas of the premises 118 and distribute the selected channel to televisions located in different areas as opposed to having a viewer appliance 120 at each location where a television 122 is present. It should be appreciated that the viewer appliance 120 may be incorporated into the television 122 rather than being a separate component.
[0032] When a viewer is watching television, the viewer provides user commands to control the aspects of television programming as desired. The viewer may provide a user command by pressing buttons on a remote control 127 that provides a corresponding signal to the viewer appliance 120 that is received by a reception module 123 . Alternatively, the viewer may provide a user command by pressing buttons located on the viewer appliance 120 itself. The viewer appliance 120 executes the command through a control module 125 to control the television programming as desired by the viewer. In addition to executing the command, as the command is received the viewer appliance 120 , the user command (i.e., a control message) may be captured and stored at the viewer appliance in storage 129 and/or the user command may be forwarded to an external location by a transfer module 121 .
[0033] For example, user commands relative to the television programming may be forwarded back to the central location 102 for capture and storage. The viewer appliance 120 may also capture and store these commands for redundancy. Furthermore, user commands relative to the television programming coming from the alternative network 130 may be captured and stored in the viewer appliance 120 if the alternative network 130 is a one-way network and/or the alternative content source 128 lacks the ability to capture and store user commands.
[0034] For user commands that are captured and stored within the viewer appliance 120 , the commands may be stored with a time stamp as to when they are received and may also be stored with additional information such as the end result of execution of the command, e.g., “on channel 3.” These clickstream captures are held until a pre-determined time, and at that time, the set of clickstream data that has been captured and stored over the preceding period is then transferred as a data set back to a marketing information system (“MKIS”) 114 . The MKIS 114 is interfaced to the two-way network 116 such that user commands are directed to the MKIS 114 where they are stored in storage 115 of the MKIS 114 and are matched with the viewer profile information for the viewer who sent the user command. As discussed below, matching the user command data at the MKIS 114 allows for additional downstream processing to occur that enables statistics such as those based on demographics to be determined about television viewing behaviors.
[0035] Rather than forwarding the captured set of clickstream data back to the central location 102 through the distribution network 116 , the viewer appliance 120 may be provided an alternative route to forward the captured set of clickstream data. For example, the distribution network 116 may only be a one-way network or the destination for the user commands may be other than the central location 102 . Thus, the viewer appliance 120 may be provided with a connection to an alternative data network 124 which interconnects an MKIS 114 ′ to the viewer appliance 120 . For example, the viewer appliance 120 may be connected to a digital subscriber line (“DSL”) or other broadband connection, a public switched telephone network (“PSTN”), wireless, etc., that leads to the network 124 . Thus, when the time comes for the viewer appliance 120 to forward the stored set of clickstream data, it is forwarded through the alternative network 124 to the MKIS 114 ′ where it is stored in storage 115 ′ and matched with viewer profile information.
[0036] For user commands that are captured remotely, the viewer appliance 120 may forward the user commands as they are received to an external location in various ways. For example, where the distribution network 116 is a two-way network, the user command may be transferred over the network 116 back to the central location 102 . The destination for the user command in this example is the MKIS 114 .
[0037] Typically, the MKIS 114 stores the user commands coming from a particular viewer premises 118 in association with an identifier of the viewer such that the MKIS 114 matches the user command to a profile for the viewer, such as the demographical categories of the viewer. Also, the MKIS knows the context in which the user command is received due to the MKIS 114 storing a time stamp for when the user command is received and also having stored the preceding user commands. Accordingly, downstream processing can determine behaviors of TV viewers relative to the content being provided based on knowing when a user command or stream of user commands (i.e., a clickstream) is received relative to what content is being shown on a particular channel at that particular time. Thus, one can determine that a television viewer switches from one program to another, switches the channel during commercials, mutes the television when certain content is present, etc. Furthermore, an analyst may match these behaviors statistically with the various demographic categories known for the viewers. This same process is also applicable to the set of clickstream data that has been captured and stored by the viewer appliance 120 that is periodically transferred as a set to the MKIS 114 as discussed above.
[0038] Rather than forwarding the user commands as they are received back to the central location 102 through the distribution network 116 , the viewer appliance 120 may be provided an alternative route to forward the user commands. For example, the distribution network 116 may only be a one-way network or the destination for the user commands may be other than the central location 102 . Thus, the viewer appliance 120 may be provided a connection to an alternative data network 124 which interconnects an MKIS 114 ′ to the viewer appliance 120 . For example, the viewer appliance 120 may be connected to a digital subscriber line (“DSL”) or other broadband connection, through to network 124 . Thus, when the viewer appliance 120 receives the user command, it is forwarded through the alternative network 124 to the MKIS 114 ′ where it is captured from the stream of communication and is stored in storage 115 ′ as described above.
[0039] FIG. 2 shows the logical operations performed within the system of FIG. 1 to capture the user commands at a location remote from viewer premises 118 , such as at the MKIS 114 . Initially, the user command is received at the viewer appliance 120 at reception operation 202 . As described above, this may be from the viewer entering a command through a remote control or by entering the command directly on the viewer appliance 120 . Then at query operation 204 , the viewer appliance 120 detects whether this is a user command that is to be stored at the viewer appliance 120 , such as by performing a look-up or as an automatic function of the user command. For example, this may be a user command that is to be stored at both the viewer appliance 120 and in the television network of the central location 102 . As another example, this may be a user command relative to an alternative content source 128 , where the alternative content source 128 lacks the ability to capture and store the user commands such that the viewer appliance 120 must capture and store them to preserve them for future uses.
[0040] Upon detecting that the user command is not to be stored at the viewer appliance 120 , the viewer appliance 120 proceeds by forwarding the user command to the MKIS 114 at forward operation 206 . It should be noted that additional discussion of FIG. 2 , in particular forward operation 206 , will also be provided below with reference to the system of FIG. 3 , which introduces a switch 316 and a video control system 318 that may also be relevant to the forward operation 206 . Upon the MKIS 114 receiving the forwarded user command information, the user command is captured and stored as appropriate for future processing at capture operation 208 . Also upon receiving the user command, the viewer appliance 120 executes the user command to alter the aspects of the television programming at execution operation 212 . While forward operation 206 and execution operation 212 are shown to occur in series, it will be appreciated that the viewer appliance 120 may perform these two operations in parallel such that there is no perceived delay by the viewer in entering the command and seeing the result of its execution.
[0041] Upon detecting that the user command is to be stored at the viewer appliance 120 at query operation 204 , the viewer appliance 120 captures and stores the user command at capture operation 210 . The viewer appliance 120 also executes the user command to control the aspect of the television programming as desired by the viewer, such as changing a channel or controlling the volume at execution operation 212 . While capture operation 206 and execution operation 212 are also shown to occur in series, it will be appreciated that the viewer appliance 120 may also perform these two operations in parallel such that there is no perceived delay by the viewer in entering the command and seeing the result of its execution.
[0042] FIG. 3 shows another example of a system for capturing the clickstreams, but in this example the television programming that is being provided to the viewer includes at least video-on-demand. In the video-on-demand system, the streams of programming to be sent to the viewer are switched within the television network of central location 302 such that only one of the streams is being sent through a network 324 to a viewer appliance 328 . The system of FIG. 3 may also but not necessarily include broadcasted programming where multiple streams are being provided to and selected by the viewer appliance 328 as discussed above in relation to FIG. 1 . The video-on-demand and broadcast television programming is provided to viewers from a central location 302 .
[0043] The central location 302 of this example includes various components for receiving the television programming to be provided to the television viewers. Again, much of the television programming originates from a satellite reception via a satellite receiver dish 306 . Additional direct local feeds 308 receive direct transmission via a wireline link to local television stations. Also, additional local off-air reception via antennas 310 may also receive local programming that is not otherwise received through the direct local feeds 308 .
[0044] These programming sources provide received programming to a content reception and processing system 304 . This system 304 takes the various channels of television programming being received and creates a channel line-up. The content reception and processing system 304 receives a particular stream of programming and assigns it to a particular channel within the channel line-up.
[0045] The content reception and processing system 304 provides the individual streams of programming to a video broadcast system 312 . The video broadcast system 312 then broadcasts each of the streams of programming within its assigned channel of the channel line-up. The video broadcast system 312 broadcasts these channels, as well as data such as guide data, to a switch 316 at the central location 302 . This switch 316 then switches between the various sources of programming to provide a particular stream of programming through the distribution network 324 to viewer premises 326 according to a selection by a viewer.
[0046] In addition to receiving the broadcasted channel line-up from the video broadcast system 312 , the switch 316 may receive television programming content from various other sources as well. For example, the switch 316 may receive content from a content storage and origination system 314 . The content storage and origination system 314 may provide video-on-demand programming such as movies and other programming that viewers may want to watch at any given time such that content is stored and can be selected for playback to the viewer at any time the viewer requests. Such video-on-demand services are often provided on a fee per use basis or monthly fee basis. The switch 316 may also receive content through the Internet 322 from a source of television programming content and may provide television programming as well as data services to the end viewer through the distribution network 324 .
[0047] A video control system 318 is included at the central location 302 to provide additional intelligence for operation of the switch 316 . The switch 316 receives user commands for the changing from one stream to send to the viewer appliance 328 to another. The switch 316 may select one stream or another, such as those streams from the video broadcast system 312 , without further assistance. However, certain channels of the video broadcast system 312 or content from the content and storage origination system 314 may be controlled on an account basis. The video control system 318 verifies that a particular viewer requesting a given channel or content has authorization to receive that channel or content and controls the switch 316 to either provide the channel/content or not provide the channel/content.
[0048] The streams being provided to viewer premises 326 may be either in an analog or a digital format. The network 324 may carry either format or both formats, such as where one set of channels of the channel line-up being received by the switch 316 are broadcast as analog while another set of channels of the channel line-up are digital. Additionally, the network 116 carries two-way communications such that communications are provided back to the switch 316 of the central location 302 from viewer premises 326 such that the switch 316 can select the particular stream to provide back through the network 324 to viewer premises 326 .
[0049] In addition, there may be alternative sources of television programming to the viewer appliance 328 at viewer premises 326 . An alternative source of content 332 may be provided to the viewer through an alternative network 334 such as a digital satellite connection, a digital off-air reception, etc. as discussed above in relation to FIG. 1 . Thus, the viewer may select from various sources of content when providing user commands, and these user commands are captured for later processing in the system of FIG. 3 .
[0050] At viewer premises 326 , the incoming stream of channels is provided to a viewer appliance 328 . The viewer appliance 328 allows a viewer to provide commands to control aspects of the television programming being viewed on the television 330 , such as channel changes and/or additional aspects such as audio format and volume control.
[0051] When a viewer is watching television, the viewer continues to provide user commands to control the aspects of television programming as desired. Again, the viewer may provide a user command by pressing buttons on a remote control 335 that provides a corresponding signal to the viewer appliance 328 that is received by a reception module 331 . Alternatively, the viewer may provide a user command by pressing buttons located on the viewer appliance 328 itself. As the command that is relevant to the content being provided from the central location 302 is received, the viewer appliance 328 forwards the user command (i.e., a control message) back to the switch 316 at the central location 302 through a transfer module 329 rather than merely storing a record of it in storage 337 for future transfer. Where the command is a change to a new stream of programming, then the switch 316 and video control system 318 executes the command to begin providing a different stream, rather than the viewer appliance 328 executing the change. Where the user command is other than a channel change, such as a selection of audio format or volume, then the viewer appliance 328 also executes the command through a control module 333 .
[0052] For the situation where the user command is not executed within the central location 302 , such as for a volume change or for a user command relevant to an alternative source of content 332 , then the user command may not be forwarded to the central location 302 since the central location 302 will not execute it. However, to prevent this user command from being lost, the viewer appliance 328 may capture and store this user command along with contextual information such as time received and then at a pre-determined time in storage 337 , and subsequently forward the collection of stored user commands to an MKIS 320 such as over the two-way network 324 or over an alternative network interconnected to the same or different MKIS 320 .
[0053] Once a user command that has been forwarded from the viewer appliance 328 is received at the switch 316 , it may be captured by the video control system 318 or the switch 316 from the stream of information being received from the network 324 . The MKIS 320 is interfaced to the switch 316 and video control system 318 such that the user command is then passed to the MKIS 320 where it is stored in storage 321 in association with the contextual information that has been matched with the user command at the video control system 318 , such as the identifier of the viewer who generated the command, the time at which the viewer appliance 328 , switch 316 , or video control system 318 received the user command, etc. Additionally, the video control system 318 may also match the user command being forwarded to the MKIS 310 with a result of the user command or may only forward the result. For example, the user command may be a channel up button, whose result is a change from channel 2 to channel 3 such that the video control system 318 forwards an “on channel 3” result to the MKIS 320 for storage.
[0054] The viewer appliance 328 may also forward the user command as it received to an external location in other ways. For example, in systems where the MKIS 320 is not interfaced to the switch 316 and/or video control system 318 , the MKIS 320 may be accessed through alternative network as described above in relation to FIG. 1 . The viewer appliance 328 may be provided a connection to such an alternative data network which interconnects an MKIS 320 to the viewer appliance 328 . Like in the example of FIG. 1 , the viewer appliance 328 may be connected to a digital subscriber line (“DSL”) or other broadband connection. When the viewer appliance 328 receives the user command, it is forwarded back through the network 324 for execution while it is simultaneously forwarded through the alternative network to the MKIS 320 where it is captured from the stream of communication and is stored as described above.
[0055] Returning to FIG. 2 , these logical operations may be performed within the system of FIG. 3 for situations where the viewer appliance 328 will execute the user commands and the viewer appliance 328 and/or the central location will capture and store the user commands. For example, the switch 316 of FIG. 3 may pass multiple broadcasted channels to the viewer appliance 328 at a time to allow the viewer appliance 328 to select the particular stream that the viewer is interested in watching. The system may be configured so that the network records such channel changes by the viewer appliance 328 , but the viewer appliance 328 records other user commands it executes such as volume changes. In this situation, once the user command is passed to the switch 16 or video control system 318 at forward operation 206 , the user command is then passed on to the MKIS 320 for capture and storage at capture operation 208 without the switch 316 or video control system 318 executing the user command which has already been executed in the viewer appliance 328 .
[0056] FIG. 4 shows the logical operations that may be performed within the system of FIG. 3 where all user commands being received at the viewer appliance 328 are executed within the television network of the central location 302 . The logical operations begin with the viewer appliance 328 receiving the user command at reception operation 402 . Then, the viewer appliance 328 detects at query operation 404 whether the viewer appliance 328 is to capture and store this command, such as by a look-up or by an automatic function of the user command. For example, although the central location 302 is going to execute the user command, it may be a less significant user command such that the central location 302 does not capture and store it so that the viewer appliance 328 must capture and store it to preserve it. Alternatively, the central location 302 may also capture and store it but it is desired to capture and store it within the viewer appliance 328 for redundancy.
[0057] Upon detecting that the user command is not to be stored at the viewer appliance 328 , then the viewer appliance 328 forwards the user command to the switch 316 and video control system 318 at forward operation 406 . The switch 316 and video control system 318 then detects at query operation 408 whether the user command is to be captured and stored within the central location 302 , again by a look-up or as an automatic function of the user command. Query operation 408 may be complementary to query operation 404 such that those commands captured and stored by the viewer appliance 328 are not stored by the central location 302 but those commands not captured and stored by the viewer appliance 328 are captured and stored by the central location 302 . However, the system may be configured otherwise where some of those captured and stored at the viewer appliance 328 are also captured and stored in the central location 302 .
[0058] Upon detecting that the user command is to be stored on the central location 302 , then the user command is captured at the switch 316 or video control system 318 and forwarded for storage to MKIS 320 at capture operation 410 . Also, the switch 316 or video control system 318 executes the user command at execution operation 412 , either in series or in parallel with capture operation 410 . When the viewer appliance 328 detects at query operation 408 that the user command is not to be stored within the central location 302 , then operational flow proceeds directly to execution operation 412 where the user command is executed.
[0059] Upon the viewer appliance 328 detecting at query operation 404 that the user command is to be stored within the viewer appliance 328 , then operational flow proceeds to capture operation 414 . Here, the viewer appliance 328 captures and stores the user command, along with the related contextual information such as time of reception. Also, operational flow returns to forward operation 406 where the user command is forwarded to the switch 316 or video control system 318 .
[0060] FIG. 5 shows illustrative logical operations for utilizing the capture and store functions of the viewer appliance 328 for user commands that the viewer appliance 328 executes while utilizing the capture and store functions of the central location 302 for user commands that the central location 302 executes within the system of FIG. 3 . The logical operations begin at reception operation 502 where the viewer appliance 328 receives the user command. Then, at query operation 504 , the viewer appliance 328 detects whether the received command is a command that the viewer appliance 328 executes, such as by a look-up or by an automatic function of the user command. For example, certain channel changes may be executed in the central location 302 while other channel changes or volume changes are executed at the viewer appliance 328 .
[0061] Upon detecting that the user command is not for execution at the viewer appliance 328 , the viewer appliance 328 forwards the user command to the switch 316 or video control system 318 at forward operation 506 . The switch 316 or video control system 318 captures the user command and forwards it to the MKIS 320 along with contextual information and/or results of execution at forward operation 508 . Also, at execution operation 510 , the switch 316 or video control system 318 executes the user command to control an aspect of the television programming such as changing the channel being provided to viewer premises 326 . As previously noted with regard to FIG. 4 , forward operation 508 and execution operation 510 may be performed in series as shown or may be performed in parallel to eliminate any delay in providing the result of the command to the viewer.
[0062] Upon detecting that the user command is for execution at the viewer appliance 328 , the viewer appliance 328 captures and stores the user command at capture operation 512 . The viewer appliance 328 also executes the user command at execution operation 514 , which may be performed in series or in parallel with capture operation 512 .
[0063] FIG. 6 shows an illustrative set of logical operations that may be performed within the systems of FIG. 1 or FIG. 3 . Here, the user commands are all captured and stored at both the viewer appliance 328 and the central location 302 , such as for redundancy, and are executed at the viewer appliance 328 . The logical operations begin at reception operation 602 where the viewer appliance 328 receives the user command. The viewer appliance 328 then captures and stores the user command at capture operation 604 and forwards the user command to the MKIS 320 for capture and storage at forward operation 606 . The viewer appliance 328 also executes the command at execution operation 608 which may be performed in series or in parallel with forward operation 606 .
[0064] FIG. 7 shows an illustrative set of logical operations that may be performed within the system of FIG. 3 . Here, the user commands are all captured and stored at both the viewer appliance 328 and the central location 302 , such as for redundancy, and are executed within the central location 302 . The logical operations begin at reception operation 702 where the viewer appliance 328 receives the user command. The viewer appliance 328 then captures and stores the user command at capture operation 704 and forwards the user command to the switch 316 or video control system 318 for capture and storage at forward operation 706 . The switch 316 or video control system 318 captures the user command and forwards it to the MKIS 320 for storage at capture operation 708 . The switch 316 or video control system 318 also executes the command at execution operation 710 which may be performed in series or in parallel with capture operation 708 .
[0065] FIG. 8 shows an illustrative set of logical operations that may be performed within the system of FIG. 3 . Here, the user commands are all captured and stored at both the viewer appliance 328 and the central location 302 , and some of the user commands are executed at the viewer appliance 328 while others are executed within the central location 302 . The logical operations begin at reception operation 802 where the viewer appliance 328 receives the user command. The viewer appliance 328 then captures and stores the user command at capture operation 804 and determines at query operation 806 whether the command is for execution at the viewer appliance 328 .
[0066] Upon detecting that the command is not for execution at the viewer appliance 328 , the viewer appliance 328 forwards the user command to the switch 316 or video control system 318 at forward operation 808 . The switch 316 or video control system 318 captures the user command and forwards it to the MKIS 320 for storage at capture operation 810 . The switch 316 or video control system 318 also detects at query operation 812 whether the user command is for execution by the switch 316 or video control system 318 .
[0067] Query operation 812 may be complementary to query operation 804 such that those commands not to be executed by the viewer appliance 328 are to be executed by the central location 302 while those commands that are to be executed by the viewer appliance 328 are not to be executed by the central location 302 . However, the system may also be configured such that there are user commands that may be executed within the viewer appliance 328 and within the central location 302 . For instance, one scenario may be that the central location 302 executes the command by providing a new stream of programming to the viewer appliance 328 , and the viewer appliance 328 executes the same user command by changing to a new input or channel to receive the new stream of programming.
[0068] Upon the switch 316 or video control system 318 detecting at query operation 812 that the user command is to be executed by the central location 302 , then the switch 316 or video control system 318 executes the command at execution operation 814 . Upon detecting that the user command is not to be executed by the central location 302 , then the process ends with respect to the current user command and waits for the next user command at reception operation 802 . While capture operation 810 is shown in series with query operation 812 and execution operation 814 , these operations may also be performed in parallel to eliminate any delay in providing the result of execution to the viewer.
[0069] When the viewer appliance 328 detects at query operation 806 that the user command is for execution at the viewer appliance 328 , then operational flow proceeds to execution operation 816 where the viewer appliance 328 executes the user command. Then, operational flow proceeds to forward operation 808 and continues as described above.
[0070] Thus, the embodiments of clickstream capture provide for the collaborative capture and storage of the user command between the viewer appliance and an external location. This eliminates that requirement that the viewer appliance or central location capture and store all user commands, but all user commands may be captured and stored at both locations for redundancy. As an advantage of performing clickstream capture collaboratively between the viewer appliance and an external location, those user commands being executed at one location may be captured and stored there while those commands being executed at another location may be captured and stored there, or some combination. As the external location typically has much greater capacity than an individual viewer appliance, the external location may store all user commands while the user commands to be captured and stored at the viewer appliance are filtered so that only those of significance are stored. For any clickstream capture that occurs at the viewer appliance, the clickstream data set may then be periodically forwarded to a downstream location for processing in conjunction with the clickstream data that has been captured and stored in the central location of the television network or other external location.
[0071] The data that has been stored in the MKIS of the embodiments discussed above may then be used for various purposes. It may be used to target advertising for particular times and television programs. It may also be used to determine the proper characteristics for advertisements such as length and content. Furthermore, the data may be used to determine the proper television programming to provide at any given time. Accordingly, the data that is obtained has significant value in relation to making determinations about what content is provided for television viewers. Usage of this data for such purposes is discussed in more detail in U.S. application Ser. No. 09/467,889, filed on Dec. 21, 1999, and entitled METHOD AND SYSTEM FOR PROVIDING TARGETED ADVERTISEMENTS.
[0072] Although the present invention has been described in connection with various illustrative embodiments, those of ordinary skill in the art will understand that many modifications can be made thereto within the scope of the claims that follow. Accordingly, it is not intended that the scope of the invention in any way be limited by the above description, but instead be determined entirely by reference to the claims that follow. | Methods and systems capture user commands. A user command is received at a viewer's appliance. A determination is made whether the user command is automatically locally stored in memory of the viewer appliance. A look-up is performed when the user command is not automatically locally stored in the viewer appliance to determine if local storage is require. When the look-up determines that local storage is required, then the user command is captured and locally stored for execution at the viewer appliance. When the look-up determines that local storage is not required, then the user command is forwarded to a remote location for remote storage in a network. | 7 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part application of U.S. patent application Ser. No. 09/566,165, entitled “Rapidly Deployable Cuff Device”, filed on May 5, 2000, now abandoned, which claims the benefit of the filing of U.S. Provisional Patent Application Serial No. 60/132,555, entitled “Personnel Immobilization Devices”, filed on May 5, 1999, and the specifications thereof are incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention (Technical Field)
The present invention relates to cuff devices for immobilizing personnel.
2. Background Art
The current, commonly deployed handcuff design has gone essentially unchanged for more than 150 years. They are difficult to apply to a combative suspect because of their small cuff size. If a suspect is able to keep his hands in motion, it often takes several officers to secure the handcuffs. Furthermore, many suspects and prisoners know how to defeat traditional handcuffs, through the use of keys or by simply breaking the handcuffs in two at its weakest link. Additionally, injuries are not uncommon with traditional handcuffs.
Examples of non-traditional cuff devices include U.S. Pat. No. 4,964,419, to Karriker, and U.S. Pat. No. 5,680,781, to Bonds et al. In neither case are the cuff loops fully encased within an elongated body, as with the present invention.
The present invention provides a cuff device that is easily deployed but not easy to defeat. It also doubles as a baton weapon so that officers can carry one item rather than both handcuffs and a baton.
SUMMARY OF THE INVENTION (DISCLOSURE OF THE INVENTION)
The present invention is of a cuff device comprising: an elongated body; a flexible cable fully encased within the body; a loop extraction system for extracting a loop of the cable from an end of the elongated body large enough to fit over an extremity of a suspect; and a loop retraction system for retracting the loop to fit snugly over the extremity. In the preferred embodiment, the device additionally comprises a second flexible cable fully encased within the body and a loop extraction system for extracting the second cable as with the first cable. The elongated body is preferably a baton, most preferably a PR-24 form factor baton. A handle is attached perpendicularly to the elongated body, having a threaded rod and nut system or a piston with a locking device for preventing movement of the loop when retracted over the extremity. The cable is preferably braided steel securely attached to a nut or piston, which travels on a threaded rod or within the baton body. A lock is employed to prevent, when engaged, extraction of the cable. The extraction and retraction system preferably includes a power system, such as DC motors powered by one or more batteries (e.g., a single nine-volt battery). In a device having two loops, a 24-inch long body will keep the suspect's wrists apart by approximately 24 inches when the loops are retracted over the wrists, and a 12-inch long body will keep a suspect's ankles apart by approximately 12 inches when the loops are retracted over the ankles.
A primary object of the present invention is to provide a cuff device that is easily deployed but not easy to defeat.
Primary advantages of the present invention are that it is also useful as a baton and to permit a single officer to readily control a cuffed suspect.
Other objects, advantages and novel features, and further scope of applicability of the present invention will be set forth in part in the detailed description to follow, taken in conjunction with the accompanying drawings, and in part will become apparent to those skilled in the art upon examination of the following, or may be learned by practice of the invention. The objects and advantages of the invention may be realized and attained by means of the instrumentalities and combinations particularly pointed out in the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings, which are incorporated into and form a part of the specification, illustrate several embodiments of the present invention and, together with the description, serve to explain the principles of the invention. The drawings are only for the purpose of illustrating a preferred embodiment of the invention and are not to be construed as limiting the invention. In the drawings:
FIGS. 1-18 are a series of drawings illustrating use of the invention to control a suspect;
FIG. 19 is a sectional view of the invention with both straps retracted.
FIG. 20 is a side view of the motor/shaft assembly of the invention;
FIG. 21 is side view of the handle of the invention;
FIG. 22 is an end view of the handle of the invention; and
FIG. 23 is a view of the piston/cable assembly of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Best Modes for Carrying out the Invention
The present invention is a flexible cuff device combined with a baton-configuration dispenser. Preferably two cables in a loop configuration are dispensed, one from each end, that fit individually over the two wrists of a suspect. Once the cables have been placed over the wrists, they can be retracted to create a very snug fit. The device can then be locked to prevent unauthorized removal. Alternatively, a single strap can be dispensed to simultaneously fit over both wrists of a suspect.
With two switches 20 , 20 ′ located on the baton/dispenser (one for each cuff cable), the cuff cables extract out of each end of the baton. The cables fit over each wrist. Once one cable has been placed over a suspect's wrist, the cuff can be immediately retracted with the push of the button on the baton/dispenser to snugly isolate the suspect's wrist on the end of the baton. This gives the operator excellent leverage over a combative suspect. The suspect can now be quickly pulled to the ground or, by twisting the baton/dispenser, the suspect's arm can be bent into an uncomfortable position, thus taking the fight out of the suspect. Then the suspect's second wrist can be easily secured. The baton/dispenser has the added advantage of being used as a defensive device by the officer.
The present invention renders it much more difficult to physically overwhelm the restraints because the design forces the suspect's arms far apart, thus reducing leverage, and the cuff material preferably has a breaking strength of approximately 1200 pounds. Additionally, the design makes it physically impossible for a restrained suspect to unlock the device with a key.
The tactical baton/handcuff system of the invention is preferably deployed in a PR-24 form factor model, which is the form factor for the baton most commonly in use in the United States of America today (e.g., the Monadnock PR-24 Control Baton). The cables are preferably two 24″ long, 0.125″ diameter 7×19 braided galvanized steel cable. The main body tubing is preferably made from extruded aluminum tubing preferably having a diameter of 1.25″ and a wall thickness of 0.125″. The perpendicular handle is preferably made from extruded aluminum tubing preferably having a diameter of 1.25″ and a wall thickness of 0.062″. The main body tubing and the handle tubing are preferably welded together. The handle end cap and main body end caps are preferably made from injection-molded nylon. A high security key-lock is preferably included, most preferably a round multi-tumbler key-lock installed into the handle end cap.
Electrical cable drives are preferred in conjunction with DC motors and a battery. The motors preferably drive a threaded rod and a nut to which the cables are attached. The motors are preferably set such that retraction ceases when resistance to retraction occurs, such as when a suspect's wrist or ankle is tightly held by the cable loop. As will be readily understood by those of skill in the art, a variety of pneumatic, electrical, and mechanical power means can be employed, and the baton/dispenser can be made retractable. Furthermore, the cuff device of the invention can be deployed within a unit that is shorter than a standard police baton and used as a leg hobbler, or within a unit that is collapsible or foldable to make the unit more compact.
Referring to FIGS. 1-18, these figures illustrate the use of the preferred embodiment of the invention to restrain a suspect. In FIG. 1, the officer (left) is approached by a confrontational man (right). The officer swings the invention at the suspect's right knee to knock him off balance. In FIG. 2, as the suspect loses balance, the officer grabs his left arm. In FIGS. 3 and 3 ( a ), the officer uses the invention as leverage to spin the suspect around. In FIGS. 4-5, the officer continues to turn the suspect away from him and uses the invention to help twist the suspect's left arm behind him. In FIGS. 6-7, the officer now places the invention in the small of the suspect's back to further immobilize him. In FIGS. 8-9, the officer extracts the straps from the two ends of the baton/dispenser by pressing a button on the baton's handle. In FIG. 10, the officer places the suspect's left hand in the cuff strap while still using the baton's location in the suspect's small of the back to immobilize him. In FIG. 11, the officer now presses a button on the baton handle in order to retract the left cuff. Notice that the baton is still pressed in the suspect's small of the back and that the suspect is completely immobilized and that his left hand and arm are now under control. In FIG. 12, while still pressing the baton in the suspect's small of the back, the officer now switches his grip on the baton handle in order to put the suspect's right hand in the second cuff. In FIGS. 13-14, the officer now presses a second button on the baton handle and grabs the suspects right wrist to begin bringing it back to be placed in the right cuff strap. The suspect is still immobilized. Note that the officer would be able to achieve the same position even without the presence of a wall or vehicle by pulling the suspect to the ground. In FIG. 15, the officer presses the second button on the baton handle to immediately retract the cuff strap on the suspect's right wrist. In FIGS. 16-17, the suspect is now completely secured. The entire operation can take less than four seconds. If the suspect continues to resist, the officer can easily control the suspect by a simple twist of the baton to pull him off balance. The officer can also rotate the handle of the baton by about 10 degrees in order to torque the suspect's back and keep him off balance. The suspect is now ready to be placed in a law enforcement vehicle.
Referring to FIGS. 19-23, the cuff device 10 comprises an elongated body 12 (preferably a PR-24 form baton), preferably made of aluminum. The short handle portion 14 of the body preferably comprises a handle cap 16 , a keyed locking switch 18 , momentary switches 20 , 20 ′ for controlling extrusion and retraction of the cable loops, and one or more batteries 22 (preferably a single nine-volt battery). The elongated body preferably comprises two motors 26 , 26 ′ (one for each cable loop), preferably nine-volt electric motors, pistons 28 , 28 ′, cables 30 , 30 ′, motor screw shafts 32 , 32 ′, springs 33 , 33 ′, handle end caps 34 , 34 ′, wiring harness 36 (preferably of 24 gauge spring steel wire), and battery terminal adapter 38 (preferably a 4 pine male threaded terminal adapter).
Again, the present invention provides a cuff system that is easier to deploy than standard cuffs, can be better used to control a suspect, and is less likely to injure a struggling suspect. The multi-purpose baton of the invention can incorporate other features, including in embodiments without the flexible cables or with only a single flexible cable. For example, an end of the baton can incorporate one of the following: (1) a tear gas, pepper spray, or other form of chemical irritant dispenser that is inserted into one end of the baton and can be activated by pressing a button on the handle of the baton; (2) an electric stun gun attachment that can fit over one end of the baton and can be activated by pressing a button on the handle of the baton; (3) a catch-net launcher that can fit externally over one end of the baton and can launch a nylon catch net to entangle a suspect by pressing a button on the handle of the baton; and (4) a ring airfoil projectile launcher that can fit externally over one end of the baton and can launch a ring airfoil projectile at a target by pressing a button on the handle of the baton.
Although the invention has been described in detail with particular reference to these preferred embodiments, other embodiments can achieve the same results. Variations and modifications of the present invention will be obvious to those skilled in the art and it is intended to cover in the appended claims all such modifications and equivalents. The entire disclosures of all references, applications, patents, and publications cited above are hereby incorporated by reference. | A cuff device comprising an elongated body, a flexible cable within the body, a loop extraction system for extracting a loop of the cable from an end of the elongated body large enough to fit over an extremity of a suspect, and a loop retraction system for retracting the loop to fit snugly over the extremity. A second cable is preferred, with one cable deployed from each end of the elongated body, preferably a PR-24 form factor baton. | 4 |
TECHNICAL FIELD
[0001] The present invention relates to an overlay network node and to an overlay network including such a node. Such a node may provide robust reply routing for such overlay networks.
BACKGROUND
Operating Environment and Related Technologies
[0002] In the past years, there has been a lot of research interest towards overlay networks which, in this context, mean networks where overlay routing is done above the internet protocol layer (IP) layer, and especially toward Distributed Hash Table (DHT) algorithms, such as EpiChord (B. Leong, B. Liskov, and E. Demaine, “EpiChord: Parallelizing the Chord Lookup Algorithm with Reactive Routing State Management”, in Proceedings of the IEEE International Conference on Networks (ICON 2004), volume 1, 2004, http://erikdemaine.org/papers/EpiChord_ICON2004/paper.pdf), Kademlia (P. Maymounkov and D. Mazieres, “Kademlia: A Peer-to-peer Information System Based on the XOR Metric”, In 1 st International Workshop on Peer-to-peer Systems 2009, http://pdos.csail.mit.edu/˜petar/papers/maymounkov/kademlia-lncs.pdf), CAN (S. Ratnasamy, P. Francis, M. Handley, R. Karp, and S. Shenker, “A Scalable Content-Addressable Network”, In proceedings of ACM SIGCOMM 2001, http://berkeley.intel-research.net/sylvia/cans.pdf) and Chord (R. Stoica, D. Morris, M. Karger, F. Kaashoek, and H. Balakrishnan, “Chord: A Scalable Peer-to-peer Lookup Service for Internet Applications,” in Proceedings of the ACM SIGCOMM '01 Conference, San Diego, Calif., August 2001, pp. 149, http://pdos.csail.mit.edu/papers/chord:sigcomm01/chord_sigcomm.pdf). Typical peer-to-peer (P2P) networks make use of an overlay routing network on top of the IP routing network. Such overlay networks allow the storage locations of files to be reached based upon an overlay network key.
[0003] In the case of Distributed Hash Tables (DHT), the key is a hash of a filename. DHTs have the property that the keys are evenly spread across the address space and the allocation of key ranges to specific nodes in the overlay network (“supernodes”) therefore results in the file storage load also being evenly spread. Most part of the research efforts have been focused on developing and enhancing the DHT algorithm itself and not so much effort has been focused on deploying DHTs to existing communication networks. However, there are a number of applications that utilize DHTs in the Internet, such as file sharing (e.g. eMule and BitTorrent) and interpersonal communication applications (e.g. Skype).
[0004] Interpersonal communication is currently done with non-standardized applications, like Skype™, but in the near future it will be possible to use standardized technology, namely P2PSIP (Peer-to-Peer Session Initiation Protocol), for communication in overlay networks.
[0005] Even though the procedure described herein, namely Robust Reply Routing for Overlay Networks (R 3 ), can be used with various overlay networks, perhaps the most prominent case is its use with P2PSIP technology. The idea in P2PSIP is to combine SIP (Session Initiation Protocol) (J. Rosenberg, H. Schulzrinne, G. Camarillo, A. Johnston, J. Peterson, R. Sparks, M. Handley, and E. Schooler, “SIP: Session Initiation Protocol,” RFC 3261 (Proposed Standard), Internet Engineering Task Force, June 2002, http://www.rfc-editor.org/rfc/rfc3261.txt) and P2P (Peer-to-peer) technologies in a novel manner. Although it will be possible to build isolated P2PSIP networks, it is expected that a number of such networks will be connected via gateways to existing SIP-based networks, such as the IP Multimedia Subsystem (IMS). This way, IMS users and P2PSIP users will be able to communicate with each other seamlessly.
[0006] P2PSIP technology is currently being standardized in the IETF (Internet Engineering Task Force). The P2PSIP working group (Homepage of the P2PSIP working group at the Internet Engineering Task Force, http://www.ietf.org/html.charters/p2psip-charter.html (Referenced Jan. 17, 2008)) was chartered in March 2007. Despite the fact that the P2PSIP working group has not existed for very long, there are already several drafts, for example S. Baset, H. Schulzrinne, and M. Matuszewski, Peer-to-Peer Protocol (P2PSIP), November 2007, draft-baset-p2psip-p2pp-01, http://www.ietf.org/internet-drafts/draft-baset-p2psip-p2pp-01.txt (Referenced Jan. 17, 2008); D. Bryan, S. Baset, M. Matuszewski, and H. Sinnreich, P2PSIP Protocol Framework and Requirements, July 2007, draft-bryan-p2psip-requirements-00, http://tools.ietf.org/id/draft-bryan-p2psip-requirements-00.txt (Referenced Jan. 17, 2008); D. Bryan, E. Shim, and B. Lowekamp, Use Cases for Peer-to-Peer Session Initiation Protocol (P2P SIP), July 2007, draft-bryan-p2psip-usecases-00, http://www.watersprings.org/pub/id/draft-bryan-p2psip-usecases-00.txt (Referenced Jan. 17, 2008); J. Hautakorpi, G. Camarillo, and J. Koskela, Utilizing HIP (Host Identity Protocol) for P2PSIP (Peer-to-peer Session Initiation Protocol), November 2007, draft-hautakorpi-p2psip-with-hip-01.txt, http://www.ietf.org/internet-drafts/draft-hautakorpi-p2psip-with-hip-01.txt (Referenced Jan. 17, 2008); C. Jennings, B. Lowekamp, E. Rescorla, and J. Rosenberg, REsource LOcation And Discovery (RELOAD), November 2007, draft-bryan-p2psip-reload-02, http://www.ietf.org/internet-drafts/draft-bryan-p2psip-reload-02.txt (Referenced Jan. 17, 2008); and M. Matuszewski, J-E. Ekberg, and P. Laitinen, Security requirements in P2PSIP, November 2007, draft-matuszewski-p2psip-security-requirements-02, http://www.ietf.org/internet-drafts/draft-matuszewski-p2psip-security-requirements-02.txt (Referenced Jan. 17, 2008), targeted for P2PSIP.
[0000] Problems with Existing Solutions
[0007] Reply routing in overlay networks is typically done by utilizing intermediary nodes. Today there exist two different reply routing mechanisms:
1) Reply routing mechanism used in existing request/reply protocols, such as in SIP and in Simple Object Access Protocol (SOAP) (Martin Gudgin, Marc Hadley, Noah Mendelsohn, Jean-Jacques Moreau, Henrik Frystyk Nielsen, Anish Karmarkar, and Yves Lafon, SOAP Version 1.2 Part 1: Messaging Framework (Second Edition), W3C Recommendation, April 2007, http://www.w3.org/TR/2007/REC-soap12-part1-20070427/.) 2) Simple reply routing mechanism used in existing DHT-algorithm implementations.
[0010] Either of these reply routing mechanisms can utilize a soft-state in intermediary nodes (e.g. written by the corresponding request) or state in reply messages (cf. Via headers in SIP). The placement of state information does not make a considerable difference in this context.
[0011] The problem with mechanism 1) is that those reply mechanisms are not developed for networks with non-robust intermediary nodes. It is noteworthy that DHT algorithms, and applications based on them, are typically executed in non-robust endpoints, such as laptops or mobile phones. Hence, it may be assumed that failures in reply routing are quite common. In a typical DHT-based overlay network, the amount of intermediate nodes between the sender and the final recipient of a message can be up to log(N), where N is the total number of nodes in the overlay network. Thus, in a large P2P network (such as a world-wide P2PSIP telephony network), the amount of intermediate hops can become rather large so that the probability of intermediate node failure is higher and its impacts are more pronounced than e.g. in a traditional SIP network.
[0012] The problem with mechanism 2) is that it is vulnerable to intermediate node failures. If an intermediate node fails while the reply is in transit, the only way to remedy the failed request/reply transaction is for the original sender to resend the request after a timeout. This kind of model for failure tolerance is very inefficient and especially ill-fitted for interpersonal communication. Furthermore, existing reply routing mechanisms in overlay networks (e.g. the ones used in P2P networks such as eMule and in BitTorrent) are not well-suited to environments with Network Address Translators (NATs), such as the Internet.
[0013] Another somewhat related technology is Internet Indirection Infrastructure (i3). However, the reply routing is not so significant an issue in i3 as it is in P2PSIP because, in i3, only the initial connection setup goes via multiple hops in an overlay whereas, in P2PSIP, most of the signaling goes via multiple hops in an overlay. Furthermore, the implementation from i3 uses iterative routing and therefore the reply routing is quite straightforward and not well suited to environments with NAT devices.
Description of the Existing Reply Routing Mechanism
[0014] The existing reply routing mechanism used by recursive DHTs is illustrated in FIG. 1 of the accompanying drawings. In this mechanism, replies follow the same path 5 - 8 through the overlay network as the request did ( 1 - 4 ). The state information required for reply routing can be stored either in each intermediary node as a soft-state or as a path definition in the reply message itself (cf. Via headers in SIP). In FIG. 1 , nodes are presented as boxes (S=source, Ix=Intermediary x, D=destination), requests as arrows, replies as dashed arrows, and existing connections as tubes. The overlay network is presented as a large circle. Although the overlay network is presented in Chord-like fashion (that is, using a ring-like topology), the R 3 is suited to almost all overlay network technologies and DHT-algorithms.
[0015] The problem with the recursive model illustrated in FIG. 1 is that the reply cannot be routed back to the node S if any one of the intermediate nodes (e.g. I 1 , I 2 ) becomes unreachable. As an example, assume that the node I 1 becomes unreachable after it has forwarded the request to the node I 2 . There can be various reasons for unreachability of a node. For example, batteries may have run out, an operating system may have crashed, or connectivity may have been lost (e.g. due to node mobility). Also, instead of becoming unreachable, the node I 1 may simply decide to leave the overlay gracefully soon after having forwarded the request, meaning that is no longer available when the reply should be forwarded back towards the node S.
[0016] In any of these scenarios, the reply from the node D cannot be routed back to the node S because the path ( 1 - 4 ) that the request followed through the overlay network no longer exists. Further, it may take a long time before the node S realizes that the request/reply transaction has failed. Because the reply cannot find its way back to the node S, the node S has to wait for a transaction timeout to occur before it can reattempt to transmit the request. If the purpose of the P2P request/reply transaction is e.g. to find out the contact information of a callee during call establishment, then this kind of waiting directly increases the call setup delay.
[0017] In addition to the recursive routing model illustrated in FIG. 1 , it is also possible to consider using semi-recursive (D sends a reply directly to S) or iterative (S contacts all intermediary nodes one by one) overlay routing models in FIG. 1 . However, the recursive overlay routing is the only sufficient model for environments where Network Address Translators (NATs) exist, such as the Internet. The semi-recursive routing model fails in the presence of NATs, because if the node D (i.e. the destination node) is behind a NAT, the NAT will typically drop the incoming reply if it is sent directly from S to D without involving the intermediate nodes. On the other hand, the iterative routing model is inefficient in NATed environments, because a NAT hole-punching technique would need to be used separately for each node along the path between D and S when routing the request.
SUMMARY
[0018] According to a first aspect of the invention, there is provided an overlay network node comprising: first means for forwarding, from a preceding node of the overlay network, a request originating in a source node of the overlay network and destined for a destination node of the overlay network; and second means, responsive to the preceding node being unavailable, for forwarding a reply, originating in the destination node and destined for the source node, to the request via another node of the overlay network, different from the preceding node, towards the source node.
[0019] The second means may be arranged to convert the reply into a further request destined for the second node. The second means may be arranged to covert the reply into a payload of the further request.
[0020] The node may comprise an overlay routing table, the second means being arranged to select the other node from the overlay routing table. The second means may be arranged to select the other node as nearest the source node according to a proximity metric of the overlay routing table.
[0021] The source node may be arranged to provide a transaction identifier in the request and each of the first and second means may be arranged not to change at least part of the transaction identifier representing the end-to-end path of the request and the reply. Each of the first and second means may be arranged to update a non-fixed part of the transaction identifier in accordance with a local part of a node path of the request and reply through the overlay network. The second means may be arranged to identify the preceding node from the non-fixed part of the transaction identifier.
[0022] As an alternative the first means may be arranged to store a representation of the identity of the preceding node and the second means may be arranged to identify the preceding node from the stored representation.
[0023] The node may comprise a router of the overlay network.
[0024] The node may comprise a network server.
[0025] According to a second aspect of the invention, there is provided an overlay network comprising at least one node according to the first aspect of the invention.
[0026] The network may comprise a peer-to-peer network. The network may comprise a peer-to-peer session initiation protocol network.
[0027] According to a third aspect of the invention, there is provided a method of routing a reply in an overlay network comprising, in a node of the overlay network: forwarding, from a preceding node of the overlay network, a request originating in a source node of the overlay network and destined for a destination node of the overlay network; and, in response to the preceding node being unavailable, forwarding a reply, originating in the destination node and destined for the source node, to the request via another node of the overlay network, different from the preceding node, towards the source node.
[0028] The second means may convert the reply into a further request destined for the source node. The second means may convert the reply into a payload of the further request.
[0029] The second means may select the other node from an overlay routing table. The second means may select the other node as nearest the source node according to a proximity metric of the overlay routing table.
[0030] The source node may provide a transaction identifier in the request and each of the first and second means may not change at least part of the transaction identifier representing the end-to-end path of the request and the reply. The first and second means may update a non-fixed part of the transaction identifier in accordance with a local part of a node path of the request and reply through the overlay network. The second means may identify the preceding node from the non-fixed part of the transaction identifier.
[0031] The first means may store a representation of the identifier of the preceding node and the second means may identify the preceding node from the stored representation.
[0032] According to a fourth aspect of the invention, there is provided a program for programming a computer to perform a method according to the third aspect of the invention.
[0033] According to a fifth aspect of the invention, there is provided a computer-readable medium containing a program according to the fourth aspect of the invention.
[0034] It is thus possible to provide a “Robust Reply Routing for Overlay Networks (R 3 )” in the form of a mechanism which allows an overlay network to recover rapidly from intermediate node failures. This kind of failure tolerance is very important when overlay networks are deployed in real-life communication networks, such as the Internet or third generation (3G) networks. The need for failure tolerance is emphasized by the fact that intermediary nodes in overlay networks are typically non-robust endpoints.
[0035] It is further possible to introduce into routers of an overlay routing network a functionality that introduces a fallback reply routing mechanism in the event that a recursive routing mechanism fails. This fallback mechanism involves routing replies according to the rules for forwarding requests.
[0036] For the avoidance of doubt, a “recursive” routing mechanism is considered to be a mechanism that involves forwarding a reply message from a destination node to a source node back along the path that was taken by the request that initiated the reply. Each node in the path may maintain a state for the request, identifying the node from which the request was received.
[0037] The routers of a typical overlay network may be considered “super-routers”, each super-router maintaining a routing table mapping a set of overlay network addresses to IP addresses and port numbers. In the event that a super-router in the recursive reply forwarding path, or a link to that router, fails, the preceding super-router in the path applies the fallback mechanism by identifying the next hop super-router from its overlay routing table.
[0038] Failure of a super-router or link may be detected by the lack of an acknowledgement in respect of a forwarded reply message or as a result of some ongoing monitoring function.
[0039] This technique is applicable in particular to peer-to-peer networks and in particular, though not necessarily, to peer-to-peer SIP networks such as might be used to set up a voice call.
[0040] It may be advantageous to include within the request and reply messages a transaction identifier that includes a fixed part, e.g. generated by the source, and a variable part that is updated at each super-node upon receipt. In the event that the reply is routed using the recursive mechanism, the variable or hop-by-hop part allows each receiving router to identify the next hop router. However, in the event of a failure as considered above, whereby the reply is routed via an alternative path, the fixed part allows the source to link the reply to the request.
[0041] In order to avoid a super-router receiving a reply, following failure detection, from dropping the reply, the super-router detecting the failure preferably tunnels the reply to the next-hop super-router by including the reply as a payload within a new request addressed to the source super-router. Upon receipt of the packet at the source, the payload is extracted and matched to the correct transaction.
[0042] A router embodying the functionality may be implemented as an appropriately programmed computer. For example, the computer may be a mobile phone, smart phone, PDA, laptop computer, or a desktop computer. The computer may alternatively be a network server.
BRIEF DESCRIPTION OF THE DRAWINGS
[0043] FIG. 1 is a diagram illustrating a recursive routing model of a known overlay network;
[0044] FIG. 2 is a diagram illustrating an overlay network constituting an embodiment of the invention;
[0045] FIG. 3 is a diagram illustrating part of an overlay network node of the network of FIG. 2 constituting an embodiment of the invention;
[0046] FIG. 4 is a diagram illustrating the structure and/or function of the node of FIG. 3 ; and
[0047] FIG. 5 is a diagram illustrating the structure of a request or reply data packet.
DETAILED DESCRIPTION
[0048] R 3 minimizes the effects of intermediate node failure on the performance of the overlay network by delegating the responsibility for failure recovery to nodes along the routing path. This can considerably speed up the process of recovering from an intermediate node failure.
[0049] The R 3 mechanism is illustrated in FIG. 2 , where the originator of a request message is a source S and the destination is the destination D. In the figure, one intermediate node, I 1 , becomes unreachable after it has forwarded the request to another intermediate node, I 2 . As already mentioned, there can be various reasons for unreachability of a node, for example batteries have run out, operating system has crashed, or connectivity has been lost (e.g. due to node mobility). Also, instead of becoming unreachable, node I 1 may simply decide to leave the overlay gracefully soon after having forwarded the request, meaning that it is no longer available when the reply should be forwarded. In any of these scenarios, node I 2 would benefit from an alternative way to forward the reply (instead of just trying to forward it via the failed node I 1 ). This is the core idea of R 3 ; R 3 enables the node I 2 to find a different path through the overlay for forwarding the reply if it has noticed that the next hop along the path towards the node S has failed. Any suitable mechanism for detecting connection breakages may be used and examples of suitable known mechanisms include polling, timeouts, and end of stream indications. In FIG. 2 , the node I 2 uses traditional overlay routing for forwarding the reply. That is, I 2 uses the same kind of overlay routing that is used for routing requests: I 2 performs a node lookup operation in its local routing table to find the best next hop node on the path towards node S. I 2 already has an existing connection to I 3 (in other words I 3 is on I 2 's overlay routing table) and it can easily forward the reply to I 3 . I 3 in its turn also applies traditional overlay routing for the reply and before long the reply will reach the source node.
[0050] The steps in FIG. 2 are as follows:
1. The source node S wishes to send a request to the destination node D. To route the request, the node S searches its local routing table to find the best next hop node (that is, a node whose identifier is closest to the identifier of the destination node D according to a proximity metric used by the DHT). The node S sets the transaction identifier of the request using the mechanism described herein. 2. Each intermediate node along the path towards the destination node D in turn performs a search similar to the one in the step (1) in its local routing table to find the best next-hop node (that is, a node whose identifier is closest to the identifier of the destination node D according to the proximity metric used by the DHT). 3. The node I 1 , which is the second-last intermediate node to forward the request, also performs the procedure described in the step (2). 4. The node I 2 , which is the last intermediate node to forward the request, also performs the procedure described in the step (2). 5. Finally, the request reaches the destination node D. The destination node D generates a reply to the request and sends it to the node I 2 . The details of this procedure are described below. 6. The intermediate node I 2 receives the reply. Because the intermediate node I 1 is no longer reachable, the node I 2 uses the procedure described below to find a new route for the reply. The next hop on this route is a node I 3 . Instead of sending the reply as it is, the node I 2 needs to tunnel the reply through the overlay by placing it in the payload of a new request. 7. The Node I 3 uses overlay native (DHT-specific) routing to route the reply to the next intermediate node. 8. Each intermediate node along the path towards the node S uses the DHT-specific routing procedure to find the next hop node. 9. Finally, the reply reaches the node S. The node S can map the reply to the original request by using the procedure described below.
[0060] As can be seen from FIG. 2 , R 3 can speed up recovery from intermediate node failure considerably. Without R 3 , the node S would wait for its transaction timer to fire before resending the request. In the case of P2PSIP, this has the effect of directly increasing the session setup delay. Further, even the retransmitted request might fail if the overlay routing has not yet managed to recover from the failure of the node I 1 , which would increase the session setup delay even more. However, when using R 3 , there would be no need to retransmit the request since the reply would with a high probability be able to reach the node S through the alternative path before the transaction timer at the node S fires.
Identifying Replies Forwarded Using R 3
[0061] The common mechanism to map replies to requests is to use transaction identifiers. Transaction identifiers are carried in requests and replies. When receiving a reply, a node uses the transaction identifier carried in the reply to map the reply to a previously sent request. Existing overlay networks typically use transaction identifiers in two different ways:
1. Each intermediate node forwards the transaction identifier unmodified. That is, the same transaction identifier is used end-to-end. 2. Each intermediate node generates a new transaction identifier for the request it forwards. That is, the scope of the transaction identifier is a single hop in the overlay.
[0064] The problem with the first approach is that it is not possible to tell the difference between retransmitted requests and requests that are looping in the network. This is because both types of requests carry the same transaction identifier. However, the benefit of this approach is that it works directly with R 3 since, even if the reply follows a different path through the network from the request, replies can still be mapped to the correct request at the node that initiated the request/reply transaction.
[0065] In the case of the second approach, a request and its associated reply will have different transaction identifiers if the reply follows a different path through the network from the request. This poses a problem for R 3 ; when receiving the reply routed using R 3 , the node S (i.e. the original sender of the request) would not be able to associate the reply with the request, provided that nodes store soft state. If the first approach is used, then this problem does not exist.
[0066] R 3 solves the problem with the second approach by using two types of transaction identifiers: an end-to-end transaction identifier and a hop-by-hop transaction identifier. The end-to-end transaction identifier is generated by the original sender of the request (the node S in FIG. 2 ). Each intermediate node forwards the end-to-end transaction identifier unmodified, but generates a new hop-by-hop transaction identifier in the usual manner. The destination node (the node D in FIG. 2 ) copies the end-to-end transaction identifier to the reply it generates, and each intermediate node forwards the end-to-end transaction identifier in the reply unmodified. If the reply follows a different path through the network from that which the request followed (due to R 3 procedures), then the end-to-end transaction identifier allows the node S to associate the reply with the correct request.
[0067] Introducing another transaction identifier means that a new field would be needed in peer-to-peer protocol messages. However, this can be avoided, since R 3 allows one to split the existing transaction identifier field carried in peer-to-peer protocol messages into two parts: a prefix and a suffix. The prefix is generated by the original sender (node S) of the request and it identifies the transaction in an end-to-end manner; each intermediate hop forwards the prefix unmodified and the node D, when generating the reply, copies the prefix into the transaction identifier of the reply. The suffix is used as the hop-by-hop transaction identifier and each intermediate hop can freely modify it before forwarding the message.
Tunneling of Replies Forwarded Using R 3
[0068] As already explained, R 3 routes replies as if they were requests. In FIG. 2 , the node I 2 uses R 3 to forward a reply to the node I 3 , which has never seen the request to which the reply is being sent. Because the node I 3 has never seen the request, it cannot associate the reply with any existing transaction (the hop-by-hop transaction identifier or the end-to-end transaction identifier, or both, are different), and may thus simply choose to drop the reply. To avoid this problem, R 3 allows the intermediate node making the decision to initiate R 3 procedures (the node I 2 in FIG. 2 ) to tunnel the reply through the overlay. This means that the reply is carried in the payload of a new request targeted to the node that initiated the transaction to which the reply is related (i.e. the node S in FIG. 2 ). When the node S receives the request carrying the tunneled reply, it extracts the reply from the payload of the request and uses the end-to-end transaction identifier carried in the reply to map the reply to the correct transaction. This mechanism does not require additional processing at intermediate nodes, since only the target node (the node S) of the request carrying the tunneled reply needs to check the payload. Intermediate nodes only need to forward the request and can ignore the payload.
[0000] R 3 Processing within an Overlay Network Node
[0069] R 3 specific processing taking place within an overlay network node is illustrated in FIG. 3 . The processing is described from the viewpoint of the node I 2 of FIG. 2
[0070] The large dark gray coloured box 20 of FIG. 3 represents the node I 2 . In the bottom right corner, the node I 2 has received a reply from the node D (this step corresponds to the step 5 of FIG. 2 ).
1. As described hereinbefore, traditional reply routing in overlay networks is based either on a soft state stored at each intermediate node or on routing information included in the reply. If routing of replies is based on soft states, then the reply is sent to the IP address and port from which the request was received. If routing is based on routing information carried in the reply, the intermediate node forwarding the reply picks up the next hop entry in the list of intermediate hops included in the reply and sends the reply to the specified IP address and port. In FIG. 3 , after having received the reply in the step ( 1 ), the node I 2 first checks ( 11 ) whether it has enough information available to route the reply. Thus, the node I 2 either attempts to fetch the soft state stored when the request was received or uses the routing information carried in the reply. If the reply does not contain routing information or if the node I 2 fails to find any soft state associated with the reply, it drops the reply ( 15 ). 2. Next, the node I 2 checks ( 12 ) whether the connection it has with the next upstream intermediate node, I 1 , is still alive. Depending on whether the connection is alive or not, node I 2 proceeds to one of the two steps below:
a. If the node I 2 believes that the connection to the node I 1 is still alive, it tries ( 16 ) to forward the message on that connection. If the node I 1 is still reachable, it returns an acknowledgement to the reply. In this way, the node I 2 learns ( 17 ) that the reply was received and thus no further processing is needed ( 18 ). If, however, no acknowledgement is received, the node I 2 assumes that the node I 1 has left the overlay network and continues to a step ( 13 ). b. If the node I 2 has already learned before receiving the reply that the intermediate node I 1 has left the network, it continues to the step ( 13 ). The node I 2 may have learned this through several ways, for example: from a failed keep-alive or other failed periodic maintenance message it attempted to send; from a closed TCP connection (note that this only works for TCP); or the node I 1 may simply have informed the node I 2 of its departure if it has left the network gracefully.
3. Because the node I 2 now knows that the node I 1 has become unreachable, it has to find an alternative path for the reply. Therefore, the node I 2 uses the identifier of node S (the intended recipient of the reply) to perform ( 13 ) a lookup operation in its local routing table. This identifier is carried in the reply, and is a hash value (e.g. a 160-bit Secure Hash Algorithm One (SHA-1) hash). The lookup determines the remote node, in routing table of the node I 2 , whose identifier is closest to that of the node S. “Closeness” is determined by the DHT-specific proximity metric. In FIG. 3 , the remote node closest to node D is the node I 3 . 4. The node I 2 forwards ( 14 ) the reply to the node I 3 . The reply is tunnelled, that is, sent within the payload of a new request as has already been described.
[0077] The R 3 mechanism has a number of advantages over the existing solutions. The main advantages are the following:
It has been developed from the beginning for environments where intermediary nodes may be non-robust. Thus, it is well-suited to environments where all or part of the nodes in the overlay are mobile terminals (such as 3G terminals). In such environments, endpoints may wander out of coverage from time to time causing connectivity breakages in the overlay. It is suitable for environments with NAT devices, such as the Internet. The failure recovery is very efficient. R 3 minimizes the effects of intermediate node failure on the performance of the overlay network by delegating the responsibility for failure recovery to nodes along the routing path. This can considerably speed up the process of recovering from an intermediate node failure. Since it allows a fast recovery from intermediate node failures, R 3 can considerably reduce session establishment delay in P2PSIP networks which such errors occur. R 3 can also be used to optimize routing performance even if all the intermediary nodes would be reachable. R 3 can be used with most overlay routing technologies and DHT algorithms. Furthermore, the utilization of the R 3 mechanism can be easily detected by examining the communication patterns between nodes.
[0084] FIG. 4 is a structural/functional diagram illustrating any one of the nodes shown in FIG. 2 . The node is embodied as a programmed computer comprising a processor 30 , a memory 31 and an input/output interface 32 connected at 33 to the rest of the network. The memory 31 comprises a read-only memory containing a program for controlling the operation of the processor 30 , together with volatile and non-volatile memory as necessary for the functioning of the processor 30 . The interface 32 provides all of the interfacing functions necessary for the processor 30 to communicate with the remainder of the network.
[0085] The processor 30 is illustrated as comprising a plurality of functional units or “functions” 34 to 37 together with a local routing table 38 including part of the distributed hash table. These units represent functional units within the software controlling the processor 30 and illustrate the functions and data flows within the processor 30 .
[0086] The node shown in FIG. 4 is capable of generating requests, forwarding requests, performing the R 3 function and generating replies to requests. When generating a request, the request generating function 34 is used. The function 34 generates the request typically as a data packet, for example having the general structure illustrated in FIG. 5 . Each packet comprises header/addressing data illustrated at 40 to allow the packet to be transported by lower-level network functions. The packet also comprises a transaction identifier generated by the function 34 and comprising a fixed portion 41 and a non-fixed portion 42 . The packet further comprises a payload 43 in accordance with the nature or function of the request.
[0087] The fixed portion 41 of the transaction identifier represents end-to-end data specifying, for example, the addresses of the source node which created the request and of the destination node for which the request is destined. The non-fixed portion 42 comprises hop-by-hop address data, for example specifying the node which forwarded the request to the current node.
[0088] When the request generating function 34 has generated the request, it accesses the local routing table 38 in order to direct the request to an intermediate node whose address is within its local routing table 38 and which is nearest the destination node. As described hereinbefore, the table 38 is associated with or contains a proximity metric to allow the nearest available node to be selected as the intermediate destination for the request.
[0089] When the node shown in FIG. 4 receives a request for forwarding, the request/reply forwarding function 35 receives the request and forwards it as described hereinbefore. In particular, the fixed part 41 of the transaction identifier and the payload 43 are not changed and need not be processed by the function 35 , which forwards these portions of the request. The non-fixed portion 42 of the identifier is updated to represent the latest hop of the request. The function 35 interrogates the local routing table 38 to determine the node nearest the destination node and forwards the request as described hereinbefore.
[0090] When the node shown in FIG. 4 is the destination node, it determines that it is the destination for the request, for example by examining the fixed portion 41 of the transaction identifier. The reply generating function 37 is then performed and generates a reply destined for the source node. The reply has the same structure as the request as illustrated in FIG. 5 and contains the appropriate fixed and non-fixed portions of the transaction identifier and a payload 43 as appropriate. The function 37 determines the node which last forwarded the request to the destination node and sends the reply back to the “previous node”.
[0091] When the node shown in FIG. 4 is acting as an intermediate node returning the reply recursively towards the source node, the function 35 receives the reply and checks whether the preceding node in the recursive chain is still available in the sense that it is still accessible. If the preceding node is accessible, then the function 35 forwards the reply to the preceding node after updating the non-fixed part 42 of the transaction identifier as appropriate.
[0092] When the preceding node is no longer available, the R 3 function 36 is performed. As described hereinbefore, the function 36 determines an alternative node towards the source node which is accessible. The non-fixed portion 42 of the transaction identifier is updated appropriately. However, instead of returning the reply as a reply, the function 36 reformulates it as a request by placing the reply data in the payload 43 so that the nodes which subsequently receive the reply forward it and do not drop it. | An overlay network node ( 12, 20, 30 to 32 ) is arranged to provide robust reply routing for requests and replies travelling over the network. Each node comprises first means ( 35 ) which forwards each request originating in a source node (S) and destined for destination node (D). The node comprises second means ( 20, 36 ) which redirect replies if the node from which the corresponding requests were received is no long accessible. The reply is, for example, turned into a request containing the reply as its payload and is returned towards the source node according to the rules used for forwarding the requests. | 7 |
This application is the national stage of PCT/DE2004/00427 filed on Nov. 3, 2004 and claims Paris Convention priority of DE 103 51 255.1 filed Nov. 3, 2003.
The invention concerns a lowering device for a support structure for safely lowering all building industry loads.
Support structures for the building industry, such as ceiling formwork elements or floor tables are conventionally held by construction supports with adjustable length, which are adjusted to a predetermined length for a concrete pouring process. For example, a large number of construction supports, e.g. floor tables, are used for concrete pouring of large ceiling sections. When the ceiling to be poured with concrete has hardened to a sufficient degree, the formwork must be removed from the ceiling by shortening e.g. all telescopic construction supports which support the ceiling formwork until the formwork elements or floor tables can be removed and re-used at another location.
The removal of the formwork may be complicated when a plurality of construction supports are used to support heavy loads. Each construction support must be individually shortened, e.g. via a spindle procedure.
It is the object of the invention to provide a lowering device which can be moved in a safe, simple and rapid manner into a first working position and a second lowered position.
SUMMARY OF THE INVENTION
This object is achieved in accordance with the invention by a lowering device of a support structure, consisting of at least one plate, wherein a locking mechanism is formed on a first side of the plate, which can be moved into two positions, and wherein a support structure can be disposed at a second side of the plate, lifted relative to the stationary plate in a first position of the locking mechanism, and lowered relative to the stationary plate in a second position of the locking mechanism in response to the force of gravity, wherein the support structure engages the locking mechanism via at least one bolt, the bolt being displaceable relative to the plate from the first position into the second position and vice versa.
The inventive lowering device offers the essential advantage that a support structure can be adjusted to a required height by opening a locking mechanism which is stable under load and which automatically repositions itself, such that a support structure connected to the lowering device is immediately lowered by the desired amount. The lever ratios of the locking mechanism may thereby be selected such that even heavy loads of between e.g. 5 and 10 t can be lowered in a fast and safe manner by one worker using only little force. In its first position, the locking mechanism is self-locking under load, such that inadvertent opening of the inventive locking mechanism is not possible.
The inventive locking mechanism is preferably formed by one first and one second latch part which each surround at least part of a bolt at a first free end region thereof, wherein the bolts extend through elongated holes in the plate to permit displacement thereof relative to the plate, and the bolts can be fixed to the support structure in the region of their second free ends.
Safe lowering can thereby be advantageously ensured with a very simple structure.
In a further embodiment of the inventive locking mechanism, the second latch part is disposed for rotation around the bolt which it surrounds, and comprises a first and a second support surface via which the second latch part is supported on a projection of the plate in correspondence with its respective position, wherein the respective support surfaces have different separations from the axis of rotation formed by the bolt.
When the plate is stationary, this structure permits safe lowering of the support structure connected to the lowering device in dependence on the design of the two support surfaces of the second latch part and their separation from the axis of rotation of the second latch part. Lowering is possible only to the extent allowed by the matching support surfaces on the second latch part.
The first latch part advantageously comprises a first free end which partially covers an opening of the plate and surrounds the bolt in such a manner that, upon pivoting of the first latch part away from the opening, the second latch part automatically pivots into the second position under the action of the force exerted by the support structure onto the locking mechanism.
This is advantageous in that the locking mechanism can be triggered, i.e. be opened with only little force using an aid, e.g. a rod that can be inserted into the opening. The latch parts formed in the locking mechanism are pivoted and turned into a second end position, which limits the lowering motion of a support structure connected to the lowering device.
The inventive lowering device is further improved by mounting the plate to one end of a longitudinal housing having a bracket at the other end that has an elongated hole for receiving a bolt which can be connected to the support structure in a stationary manner, the bracket being overlapped by a frame which is rigidly connected to both the bracket and the plate.
This embodiment of the inventive lowering device permits connection of a conventional construction support to the lowering device in a torsion-proof and bending-resistant fashion. If the lowering device is mounted to a construction support in this fashion, the support structure connected to the lowering device can be lowered rapidly and safely by an amount predetermined by the locking mechanism.
The frame advantageously forms a housing which receives both the bracket and the plate, and comprises receptacles for a support for immovably connecting the lowering device to the support. A construction support can be quickly and safely mounted to the lowering device via such receptacles.
Lowering devices of this type are preferably mounted to the sides of truss girders of a floor table. If a floor table is held by numerous construction supports, each having an inventive lowering device, the floor table can be quickly and safely lowered and be re-used when the concrete pouring process is completed.
Further advantages can be extracted from the description of the attached drawings. The features of the invention mentioned above and below can be used individually or in arbitrary combination. The above-mentioned embodiments are not to be understood as exhaustive enumeration but have exemplary character.
The invention is described in more detail below with reference to an embodiment. The lowering devices or parts thereof shown in the figures are not necessarily true to scale.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 shows an inventive lowering device which can be mounted e.g. to a support structure and to a construction support;
FIGS. 2 a through 2 c show different views of the inventive lowering device of FIG. 1 ;
FIG. 3 shows a detail of an inventive lowering device comprising a locking mechanism formed in the lower part of the lowering device and located in a first position;
FIG. 4 shows a view of the locking mechanism of FIG. 3 in a second position;
FIG. 5 shows inventive lowering devices which can be mounted to a truss girder; and
FIG. 6 shows inventive lowering devices with construction supports which are held in the lowering devices to secure a support structure, e.g. a truss girder, via the lowering devices.
DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 shows a lowering device 10 which can be mounted to a construction support (not shown) and to a support structure (also not shown in the figure). The lowering device 10 is connected to a support structure via bolts 11 , 12 , 13 . The sections of the bolts 11 , 12 , 13 facing away from the support structure penetrate through a first elongated hole 14 and a second elongated hole 15 of the lowering device 10 . The bolts 11 , 12 , 13 and the support structure connected thereto can be displaced along the elongated holes 14 , 15 when a locking mechanism 16 of the lowering device 10 is opened.
The locking mechanism 16 comprises a plate 17 with a projection or stop 18 , a first latch part 19 , a second latch part 20 and the bolts 12 , 13 . The first and second latch parts 19 , 20 can be pivoted or turned about the bolts 12 , 13 . The second latch part 20 is supported on the projection 18 both in a first and in a second location of the locking mechanism 16 . FIG. 1 shows the locking mechanism 16 in its closed position, i.e. a support structure connected to the bolts 11 , 12 , 13 is in the lifted position.
The bolt 11 is displaceably held in a bracket 21 which also contains the elongated hole 14 . The bracket 21 , which is bent in an L-shape, abuts the support structure to be retained, via a first leg piece 22 . A frame portion 24 is preferably connected to a second leg piece 23 of the bracket 21 with material fit. The frame 24 with bracket 21 and plate 17 and the individual parts mounted thereto, form a housing extending in a longitudinal direction, which also has a first and a second receptacle 25 , 26 for guiding and fixing a construction support and which can preferably be adjusted in height.
The first receptacle 25 engages with a construction support held in this receptacle 25 in a positive fashion, and the second receptacle 26 is designed as finger that engages in the free end of a construction support. A construction support retained in the lowering device 10 can be securely connected to the lowering device 10 , e.g. via a bolt, through the opening formed on the finger.
The lowering device 10 of the figure is preferably a metal construction which can accept the load or a partial load of a support structure connected to the lowering device 10 .
FIGS. 2 a , 2 b and 2 c show different views of the lowering device 10 . FIG. 2 a shows a side view of the lowering device 10 and the positions of the bolts 11 , 12 , and 13 . The bolt 11 is disposed in the bracket 21 such that it can be displaced, and the bracket 21 also holds the receptacle 26 for fixing a construction support in the lowering device 10 . The bracket 21 is connected to the plate 17 holding the bolts 12 , 13 via the frame 24 . The lower end of the frame 24 comprises the first receptacle 25 .
FIG. 2 b shows the lowering device 10 in a positioned turned relative to FIG. 2 a such that the position and design of the bolts 11 , 12 , 13 and the design of the receptacles 25 , 26 on the bracket 21 and on the lower end of the frame 24 are clearly shown. The locking mechanism formed in the lowering device 10 is covered by a cover plate 27 which protects the moved parts of the locking mechanism from being soiled and damaged.
FIG. 2 c shows the lowering device 10 from a point of view which clearly shows the bearing of the bolt 11 in the bracket 21 and the bearing of the bolts 12 , 13 in the plate 17 . The receptacle 25 and the bracket 21 project beyond the frame 24 . The bolts 11 , 12 , 13 are displaceably disposed in the elongated holes 14 , 15 . The plate 17 has an opening 28 via which the locking mechanism formed on the other side of the plate 17 can be actuated. In a state of the lowering device 10 mounted to a support structure, the opening 28 must be accessible for the staff operating the lowering device 10 . The bolt 11 can be displaced in the elongated hole 14 in the direction of arrows 29 and the bolts 12 , 13 can be displaced in the elongated hole 15 in the direction of arrows 30 . When a support structure is mounted to the bolts 11 , 12 , 13 , the bolts 11 , 12 , 13 can be displaced in the direction of arrows 29 , 30 with the lowering device being stationary.
FIG. 3 shows a detail of the frame 24 with plate 17 mounted thereto, which receives the locking mechanism 16 . The first receptacle 25 projects beyond the plate 17 and the projection 18 which supports the second latch part 20 via a first support surface 31 lies in front of the plane formed by the plate 17 . The support surface 31 is supported on a stop surface 32 of the projection 18 . The first and second latch parts 19 , 20 are designed and matched to each other such that the locking mechanism 16 is safely and immovably held in its self-locking position shown in the figure even when the lowering device 10 is subjected to heavy loads by a support structure. When the bolts 12 , 13 are each rigidly connected to a support structure, and the locking mechanism 16 is stationarily mounted to a construction support, the locking mechanism 16 retains the support structure, fastened via the bolts 12 , 13 , in a lifted first position. A vertical load acting directly on the bolts 12 , 13 cannot change the position of the locking mechanism 16 . In the first location of the locking mechanism 16 , a free end 33 of the first latch part 19 partially covers the opening 28 formed on the plate 17 . If the closed locking mechanism 16 shown in FIG. 3 is opened by a force acting on the free end 33 of the first latch part 19 , by introducing a force in an anticlockwise direction onto the free end 33 , the first and the second latch part 19 , 20 move. The first latch part 19 can be turned about an axis of rotation 34 and the second latch part 20 is disposed to be rotatable about an axis 35 of the bolt 13 . If the first latch part 19 is loaded about the axis of rotation 34 in an anticlockwise direction via the first free end 33 , the first latch part 19 pivots away from the bolt 12 and the second latch part 20 simultaneously turns about the axis 35 of the bolt 13 in a clockwise direction. As the second latch part 20 turns in a clockwise direction, the bolts 12 , 13 move from a raised position ( FIG. 3 ) into a lower position within the elongated hole 15 .
FIG. 4 shows the locking mechanism 16 of the inventive lowering device in an open second position. In the second position of FIG. 4 , the bolts 12 , 13 are moved downwards in the longitudinal hole 15 and the plate 17 is stationary. The first latch part 19 is pivoted in a counter clockwise direction about the axis of rotation 34 via the free end 33 e.g. by pushing a rod from behind through the plate 17 into the opening 28 , thereby triggering a turning motion of the second latch part 20 in a clockwise direction such that a second support surface 36 of the second latch part 20 abuts the support surface 32 . During this rotation about the axis 35 , the bolt 13 , which is rotatably disposed in the second latch part 20 , as well as the bolt 12 are lowered. The axis of rotation 34 is lifted during this motion sequence. In the second position, the free end 33 of the first latch part 19 frees the opening 28 . When the bolts 12 , 13 move into the position shown in FIG. 4 , a support structure connected to the bolts 12 , 13 is also lowered with the plate 17 remaining stationary.
FIG. 4 also shows how the receptacle 25 may be formed on the plate 17 . The projection 18 is mounted or formed in the angled region of the plate 17 facing the receptacle 25 . The size of the latch parts 19 , 20 and the height of the projection 18 are adjusted such that the locking mechanism 16 can assume the second position on the plate 17 shown in this figure as well as the first position shown in FIG. 3 .
FIG. 5 shows three lowering devices 10 which can be mounted e.g. on a support structure such as a truss girder. Three lowering devices 10 are mounted to vertical struts 37 of a truss girder 38 by securely mounting the brackets 21 , at one end of the respective lowering device 10 , and the plates 17 , at the other end of the respective lowering device 10 , to the truss girders 38 using bolts. The bolts connecting the support structure to the lowering device 10 are guided in elongated holes of the lowering devices 10 in such a manner that they can be moved to different positions depending on the position of the locking mechanism formed in the lowering devices 10 . Construction supports of any outer shape can be inserted into the receptacles 25 , 26 . The receptacles 25 , 26 are designed in dependence on the outer shape and the properties of the respective construction supports.
FIG. 6 shows three lowering devices 10 including construction supports 39 introduced into the lowering devices 10 , as they are mounted to the truss girder 38 . The construction supports 39 retain the support structure mounted to the lowering device 10 at a predetermined height relative to the ground on which the ends of the construction supports 39 seat. The other ends of the construction supports 39 engage the lowering device 10 and are supported on the inner side of the brackets 21 . The frames 24 of the lowering devices 10 which connect the brackets 21 to the lower mounting points of the lowering device 10 are designed to hold a support structure, such as the truss girder shown in the figure, in a torsion-proof and bending-resistant fashion. If the construction supports 39 are aligned at a certain level and fixed to the lowering devices 10 , the locking mechanisms formed in the lowering devices 10 can lower the support structure mounted to the lowering devices 10 by moving the locking mechanisms 16 from the first position into the second position. If the support structure is e.g. lifted via aids such as a crane, the locking mechanisms 16 of the individual lowering devices 10 automatically move back into the first position. The latch parts of the locking mechanisms 16 are designed such that they always automatically pivot or turn into the first location when the load is removed.
A lowering device 10 of a support structure for the construction industry comprises at least one plate 17 which holds a locking mechanism 16 and either blocks the motion of the bolts 12 , 13 or releases that blockage. The bolts 12 , 13 are rigidly connected to a support structure and are also held in the locking mechanism 16 in a controlled manner, such that the support structure connected to the lowering device 10 is lifted in a first position and the support structure connected to the locking mechanism is lowered in the second position thereof to the extent permitted by the locking mechanism. | The invention relates to a lowering device ( 10 ) for the construction industry, which comprises a support structure. The lowering device comprises a plate ( 17 ) holding a locking mechanism ( 16 ) and blocking or releasing the mobility of bolts ( 12, 13 ). The bolts ( 12, 13 ) are firmly linked with a support structure and are fastened on the locking mechanism ( 16 ) in a controlled manner to such an extent that, in a first position, the support structure linked with the lowering device ( 10 ) is lifted and, in a second position of the locking mechanism, the support structure linked therewith is lowered as much as the locking mechanism permits. | 4 |
BACKGROUND OF THE INVENTION
Substituted 2,3-pyridinedicarboxylic acids are important intermediates in the manufacture of highly effective 2-(2-imidazolin-2-yl)nicotinate herbicides. Among the methods to prepare substituted 2,3-pyridinedicarboxylic acids is the nitric acid oxidation of the appropriately substituted quinoline precursor. However, certain substituted pyridinedicarboxylic acids are difficult to isolate from the spent nitric acid solution. Such compounds do not readily precipitate from the product solution.
The compound, 2,3-dicarboxypyridinium nitrate is described by P. Sutter and C. Weis in the Journal of Heterocyclic Chemistry, 23 p. 29-32 (1986), however no substituted 2,3-dicarboxypyridinium nitrates are found therein.
Therefore, it is an object of this invention to provide crystalline substituted 2,3-dicarboxypyridinium nitrate compounds which are useful in the isolation and purification of important 2,3-pyridine-dicarboxylic acid herbicide intermediates. It is another object of this invention to provide a means for producing the desired substituted pyridinedicarboxylic acid herbicide intermediates in improved yield and purity.
It is a feature of this invention that the desired dicarboxylic acid product may be obtained without necessitating a quenching step, thereby allowing the spent nitric acid to be recycled and eliminating the costly and potentially hazardous presence of solvent wastes.
SUMMARY OF THE INVENTION
The present invention provides a substituted 2,3-dicarboxypyridinium nitrate compound of formula I ##STR1## wherein Y and Z are each independently hydrogen, C 1 -C 6 alkyl optionally substituted with one or more C 1 -C 4 alkoxy, halogen or sulfonyl groups, nitro, formyl, C 1 -C 4 alkylcarbonyl, C 1 -C 4 alkylsulfonyl or phenyl optionally substituted with C 1 -C 4 alkyl, C 1 -C 4 alkylsulfonyl, halogen, or haloalkyl groups with the proviso that one of Y or Z must be other than or when taken together Y and Z may form a ring wherein YZ is represented by the structure ##STR2## L, M, Q and R are each independently hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylsulfonyl, C 1 -C 4 haloalkyl, nitro, phenyl optionally substituted with one C 1 -C 4 alkyl or halogen group or phenoxy optionally substituted with one halogen, C 1 -C 4 alkyl, nitro or CF 3 group with the proviso that only one of L, M, Q or R may represent a substituent other than hydrogen, halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy.
The invention further provides a method for the preparation of a formula I pyridinium nitrate compound which comprises reacting a substituted quinoline compound of formula II ##STR3## wherein Y and Z are as described for formula I above and R 1 , R 2 , R 3 and R 4 are each independently hydrogen, hydroxy, nitro, amino, SO 3 H or SO 3 Cl with the proviso that one of R 1 , R 2 , R 3 or R 4 is other than hydrogen; with nitric acid optionally in the presence of a catalytic amount of Manganese and a nitroaromatic solvent, at an elevated temperature to form a reaction mixture and concentrating the reaction mixture to give the crystalline formula I compound.
The formula I dicarboxypyridinium nitrate is readily converted to the corresponding pyridinedicarboxylic acid upon treatment with a solvent or solvent mixture. The thus-obtained, high purity pyridinedicarboxylic acid is an important intermediate in the production of 2-(2-imidazolin-2-yl)nicotinate herbicidal agents. Descriptions of these highly effective herbicidal agents and the use of substituted 2,3 -pyridinedicarboxylic acid in their preparation can be found in U.S. Pat. No. 4,798,619 among others.
DETAILED DESCRIPTION OF THE INVENTION
The Skraup reaction is a well-known and convenient source of the formula II substituted quinoline starting material used in the manufacture of substituted 2,3-pyridinedicarboxylic acid herbicide intermediates. The Skraup reaction is carried out in an aqueous acidic solution. Advantageously, it has now been found that crude Skraup reaction mixtures, without undue and tedious isolation procedures, may be used as a source of starting material in the nitric acid oxidation of formula II quinoline compounds to produce high purity substituted 2,3-pyridinedicarboxylic acid products. Surprisingly, it has been found that concentration of the spent nitric acid solution in the presence of a nitroaromatic solvent such as nitrobenzene or nitroxylenes yields a crystalline nitrate salt of formula I in high yield. The formula I dicarboxypyridinium nitrate is easily converted to the desired 2,3-pyridinedicarboxylic acid upon treatment with a second solvent or solvent mixture. The desired oxidation product is thus obtained without the need to quench the reaction solution and thereby allowing for the recyclization of the spent nitric acid. The procedure is illustrated in Flow Diagram I. ##STR4##
The formula I dicarboxypyridinium nitrate compounds of the invention allow the isolation and purification of important herbicide intermediate compounds. Many of the desired 2,3-pyridinedicarboxylic acid compounds are difficult to isolate from the spent nitric acid solution resulting from the oxidation procedure. Even after quenching the nitric acid with reagents such as formic acid or isopropanol and/or adjusting the pH of the reaction mixture, certain substituted pyridinedicarboxylic acids (e.g. 5-ethyl pyridinedicarboxylic acid) do not readily precipitate from solution. High concentration of the quenched nitric acid product solution results in exotherms, product decomposition, NO x gas emission and potentially explosive mixtures. Surprisingly, the substituted pyridinedicarboxylic acid compound crystallizes from solution as the pure nitric acid addition salt in high yield when the spent nitric acid oxidation reaction solution is concentrated in the presence of a nitroaromatic solvent such as nitrobenzene or nitroxylenes such as 3-nitro-o-xylene. Therefore, the presence of costly and potentially hazardous solvent wastes are eliminated.
In actual practice, a formula II quinoline compound, either isolated or present as a crude reaction product solution, optionally in the presence of a solvent, is added to a mixture of 70% nitric acid and a catalytic amount of Manganese at a temperature range of about 50°-150° C. to form a reaction mixture, the reaction mixture is heated at 50°-150° C. until the oxidation is complete. The unquenched reaction mixture is treated directly with a nitroaromatic solvent such as nitrobenzene, 3-nitro-o-xylene and the like and concentrated in vacuo to give the formula I dicarboxypyridinium nitrate compound as a crystalline precipitate. The pyridinium nitrate precipitate is isolated by filtration and converted to the corresponding free 20 2,3-pyridinedicarboxylic acid by treatment with a second solvent or solvent system.
Suitable solvents for the conversion of the formula I dicarboxypyridinium nitrate to the corresponding 2,3-pyridinedicarboxylic acid are ketones such as methyl isobutyl ketone, acetone and the like, mixtures of a ketone and a halogenated hydrocarbon such as methylene chloride, chloroform, ethylene dichloride and the like and water and mixtures of water and a co-solvent such as a ketone or halogenated hydrocarbon. Treatment of the formula I pyridinium nitrate compound of the invention with a suitable solvent or solvent mixture yields the desired substituted 2,3-pyridine-dicarboxylic acid in good yield and high purity.
The invention herein described is further illustrated by the following Examples and is not to be deemed limited thereby except as defined in the claims. Unless otherwise, noted all parts are parts by weight. The term HPLC designates high performace liquid chromatography.
EXAMPLE 1
Preparation of 2.3-dicarboxy-5-ethylpyridinium nitrate ##STR5##
A mixture of 70% nitric acid (480 g, 5.33 mole) and manganese dioxide (0.1 g, 1.75 mmole) is heated to 95° C., treated with a solution of 3-ethyl-8-hydroxyquinoline (51.5 g, 67.5% pure, 0.20 mole) in 100 g nitrobenzene over a 2 hour period, held at 90°-100° C. for 10 hours, cooled to room temperature, treated with an additional 200 g of nitrobenzene, concentrated in vacuo to a total weight of about 240 g and filtered. The filter cake is washed with nitrobenzene and methylene chloride and dried in vacuo to give the title product as a white solid, 49.2 g (95.3% yield), mp 109°-111° C. The product is used as is in Example 2.
EXAMPLE 2
Preparation of 5-ethyl-2.3 pyridinedicarboxylic acid ##STR6##
The nitrate salt obtained in Example 1 is dispersed in a mixture of lo0 mL of methylene chloride and 100 mL of methyl isobutyl ketone, heated at reflux temperature for 1 hour, cooled to room temperature and filtered. The filter cake is washed with a 1:1 mixture of methylene chloride:methyl isobutyl ketone and dried in vacuo to give 5-ethyl-2,3-pyridinedicarboxylic acid, 34.6 g, (89% isolated yield from 3-ethyl-8-hydroxyquinoline), 94.5% pure by HPLC.
EXAMPLE 3
Preparation of substituted 2.3-dicarboxypyridinium nitrate
Using essentially the same procedure described in Example 1 and employing the appropropriate substituted quinoline precursor, the following dicarboxypyridinium nitrate compounds are obtained:
______________________________________ ##STR7##Y Z mp °C.______________________________________CH.sub.3 H 167-168H H 155-158CH.sub.2 OCH.sub.3 H 92-94______________________________________
EXAMPLE 4
Preparation of 5-ethyl-2,3-pyridinedicarboxylic acid in high purity from crude 3-ethyl-8-hydroxyquinoline starting material via the isolation of 2.3-dicarboxy-5-ethylpyridinium nitrate ##STR8##
A mixture of 70% nitric acid and a catalytic amount of maganaese dioxide is treated with a solution of crude (67.5% pure) 3-ethyl-8-hydroxyquinoline (EHQ) in nitrobenzene (NBz) or 3-nitro-o-xylene (3-NOX) at 95° C., heated at 90°-100° C. until oxidation is complete, cooled to room temperature, concentrated in vacuo in the presence of the nitroaromatic solvent and filtered to give 2,3-dicarboxy-5-ethylpyridinium nitrate. The thus-isolated nitrate salt is dispersed in a 1:1 mixture of methylene chloride (CH 2 Cl 2 ) and methyl isobutyl ketone (MIBK) or acetone and CH 2 Cl 2 and filtered to give the desired 5-ethyl-2,3-pyridinedicarboxylic acid in high purity.
Varying the above reaction parameters and the solvent systems used to liberate the free pyridinedicarboxylic acid compound from the isolated dicarboxypyridinium nitrate, the following results are obtained and shown in Table I.
TABLE 1______________________________________Preparation of 5-Ethyl-2,3-pyridinedicarboxylic Acid HNO.sub.3Molar Ratio Oxid'n Nitrate Salt % Yield %HNO.sub.3 :EHQ Solvent Dispersant from EHQ Purity______________________________________16 3-NOX 3-NOX/HCOOH 83.3 78.116 3-NOX 3-NOX/HCOOH 84.2 78.216 NBz MIBK 74.9 98.016 3-NOX MIBK 75.7 93.516 NBz MIBK/HCOOH 73.0 96.316 3-NOX MIBK/HCOOH 78.5 94.416 3-NOX MIBK/HCOOH* 83.8 95.416 3-NOX MIBK/CH.sub.2 Cl.sub.2 86.2 91.916 3-NOX MIBK/CH.sub.2 Cl.sub.2 90.5 91.416 3-NOX MIBK/CH.sub.2 Cl.sub.2 80.4 93.118 3-NOX MIBK/CH.sub.2 Cl.sub.2 80.6 90.918 NBz MIBK/CH.sub.2 Cl.sub.2 83.8 94.5 18** NBz MIBK/CH.sub.2 Cl.sub.2 55.4 91.216 3-NOX Acetone 72.1 97.716 3-NOX Acetone/CH.sub.2 Cl.sub.2 67.8 96.518 3-NOX Acetone/CH.sub.2 Cl.sub.2 64.4 97.3______________________________________ *Water extraction **Starting material was not isolated from Skraup reaction mixture | There are provided crystalline substituted-2,3-dicarboxypyridinium nitrate salts, the preparation thereof and the use thereof in the isolation and purification of important substituted pyridinedicarboxylic acid herbicide intermediates. | 2 |
BACKGROUND
[0001] In situations where pipe needs to be connected together in a semi-permanent fashion, each pipe end is fitted with a flange, and the flanges are bolted together. There are several types of flanges, defined in part by the type of sealing surface provided on each flange face. For example, a raised face flange has a sealing surface that is raised in relation to the portion of the flange through which bolts extend, and the raised face is either smooth or has shallow circular grooves. When mating raised face flanges, a gasket material is positioned between the raised faces and held in place by compressive forces supplied by the bolts. A ring-type joint (RTJ) flange is yet another example of a type of flange. RTJ flanges have a circular ring groove on the flange face. A metallic ring, or ring gasket, is placed between two RTJ flanges in the ring groove, and the ring gasket is deformed or “coined” between the flanges to provide a seal. The compressive forces to deform the ring supplied by the bolts.
[0002] In addition to different types of flanges, there are also different ratings for flanges, even of the same type. For example, a raised face flange for 30 inch pipe may come in a variety of ANSI ratings directly related to the internal pressure expected in the pipe. Size of the sealing surface for raised face flanges may vary slightly from flange-to-flange for a given flange size, in spite of each flange having a central passage of the same internal diameter. Likewise, the depth, width and/or location of a ring groove for RTJ flanges may change for different pressure ratings or may vary slightly from flange-to-flange in spite of each flange having a central passage of the same internal diameter.
[0003] Ultrasonic flow meters are used to measure fluid flow (e.g., natural gas, oil, water) in a pipe. In some situations, ultrasonic meters are used to measure fluid flow for custody exchange purposes, and thus particular accuracy is needed. In order to verify the accuracy of an ultrasonic meter, new meters (and possibly rebuilt meters) require a flow calibration at a testing laboratory. However, selection of a flange type and pressure rating for a meter is customer dependent. Situations thus occur where a testing laboratory has a set of piping having an internal diameter matching that of an ultrasonic meter (e.g., 30 inches), as required by testing standards, but the testing laboratory may have flanges with different seal types and/or different pressure ratings. For example, the testing laboratory may use RTJ flanges having first pressure rating, and the meter to be tested may use raised face flanges having different pressure ratings than the RTJ flanges. Testing laboratories have addressed the issue in the past by having a plurality of pipe “spools” with each spool having different flange type on the meter end. However, construction and storing such spools is expensive, in some cases costing more than the meter to be tested.
BRIEF DESCRIPTION OF THE DRAWINGS
[0004] For a detailed description of exemplary embodiments, reference will now be made to the accompanying drawings in which:
[0005] FIG. 1 illustrates a raised face flange;
[0006] FIG. 2 illustrates a ring-type joint flange;
[0007] FIG. 3 illustrates a flange seal ring in accordance with at least some embodiments;
[0008] FIG. 4 illustrates a perspective view of a block assembly in accordance with at least some embodiments;
[0009] FIG. 5 illustrates a cross-sectional, elevation view of the block assembly of FIG. 5 taken along line 5 - 5 of FIG. 4 ;
[0010] FIG. 6 illustrates a cross-sectional, elevation view of the block assembly interacting with a raised face flange;
[0011] FIG. 7 illustrates a cross-sectional, elevation view of the block assembly interacting with a raised face flange having a raised face offset smaller than illustrated by FIG. 6 ; and
[0012] FIG. 8 illustrates a method in accordance with at least some embodiments.
NOTATION AND NOMENCLATURE
[0013] Certain terms are used throughout the following description and claims to refer to particular system components. As one skilled in the art will appreciate, flow meter designers and manufacturers may refer to a component by different names. This document does not intend to distinguish between components that differ in name but not function.
[0014] 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 connection. Thus, if a first device couples to a second device, that connection may be through a direct connection, or through an indirect connection via other devices and connections.
DETAILED DESCRIPTION
[0015] The following discussion is directed to various embodiments of the invention. Although one or more of these embodiments may be preferred, the embodiments disclosed should not be interpreted, or otherwise used, as limiting the scope of the disclosure. In addition, one skilled in the art will understand that the following description has broad application, and the discussion of any embodiment is meant only to be exemplary of that embodiment, and not intended to intimate that the scope of the disclosure is limited to that embodiment.
[0016] The various embodiments are directed to a flange seal ring that enables coupling of flanges of varying types (e.g., raised face, ring-type joint (RTJ)) and in some cases varying pressure ratings, without the need for adapters or pipe “spools”. For example, the flange seal ring of the various embodiments enables coupling a meter (e.g., ultrasonic meter) having a 150 ANSI raised face flange to piping of a testing laboratory having a 900 ANSI RTJ flange. Before turning to illustrative physical embodiments of the flange seal ring, the specification digresses briefly to a discussion of two specific types of flanges.
[0017] FIG. 1 illustrates a raised face flange 10 usable with the flange seal ring of the various embodiments (not shown in FIG. 2 ). In particular, FIG. 1 illustrates both a cross-sectional view 12 and an elevation view 14 of a raised face flange 10 . The sealing feature of a raised face flange is the raised face 16 . The raised face 16 is defined by an inside diameter 18 of the central bore or central passage 20 , and an outside diameter 22 of the raised face 16 . As the name implies, the raised face is offset from the bolt face 24 by a distance “D”, which distance varies depending on the pressure rating of the flange. For example, in some pressure ratings the offset D is 0.06 inches (1.524 millimeters (mm)), and yet for other, higher pressure ratings the offset D is 0.25 inches (6.35 mm). When coupling two raised face flanges, a gasket material occupies the space between the two sealing surfaces, and the seal is achieved by compressive force supply by bolts in bolt holes 26 .
[0018] FIG. 2 illustrates a RTJ flange 30 usable with the flange seal ring of the various embodiments (not shown in FIG. 2 ). In particular, FIG. 2 illustrates both a cross-sectional view 32 and an elevation view 34 of the RTJ flange 30 . The sealing feature of a RTJ flange is ring groove 36 . The ring groove 36 lies between the central passage 38 and the bolt holes 40 . On some RTJ flanges, the surface 42 within which the ring groove 36 is cut is also offset from the bolt face 44 by a distance “D”, but such an offset is not necessarily present. The width, depth and/or diameter of the ring groove 36 may vary for different pressure ratings, with larger ring grooves 36 (and correspondingly larger metallic ring gaskets) for higher pressure ratings. When coupling two RTJ flanges, the metallic ring gasket is placed between the flanges, and the metallic ring gasket resides at least partially within the ring groove 36 of each flange. The seal is achieved by deforming the metallic ring gasket by way of the compressive force supply by bolts in bolt holes 40 . The specification now turns to the illustrative embodiments of a flange seal ring.
[0019] FIG. 3 illustrates an elevation view of a flange seal ring 50 in accordance with at least some embodiments. In particular, FIG. 3 illustrates the flange seal ring 50 comprises a metallic ring 52 , and a plurality of block assemblies 54 . In some embodiments, the metallic ring 52 is made of carbon steel. In other embodiments, such as low pressure applications, other metals may be equivalently used (e.g., aluminum). The metallic ring 52 defines a central bore 56 having an internal diameter 58 . The flange seal ring 50 further comprises a sealing face 60 that defines a plane (in the case of FIG. 3 , the plane is parallel to the page). The central bore 56 is substantially perpendicular to the plane defined by the sealing face 60 (i.e., perpendicular within manufacturing tolerances). Though not visible in FIG. 3 , the metallic ring 52 further comprises a second sealing face on the opposite side of the metallic ring 52 , which sealing face likewise defines a plane. In some embodiments, the plane defined by the first sealing face 60 and the second sealing face are substantially flat (i.e., flat within manufacturing tolerances) and substantially parallel (i.e., parallel within manufacturing tolerances).
[0020] The metallic ring 52 further comprises an o-ring groove 62 that encircles the intersection of the central bore 56 and the sealing face 60 . Again, though not visible in FIG. 3 , the second sealing face on the opposite side likewise has an o-ring groove. In embodiments configured for use with a 0.50 inch (12.7 mm) diameter elastomeric o-ring, each o-ring groove 62 is 0.375 inch (9.525 mm) in depth, 0.560 inch (14.224 mm) in width at the sealing face 60 , and has a 5 degree angle (the groove becoming more narrow with depth into the metallic ring 52 ). O-rings of different diameter may be equivalently used, and the width, depth and/or angle of the o-ring grooves may change accordingly.
[0021] The flange seal ring 50 further comprises a plurality of block assemblies 54 . In the illustrative case of FIG. 3 , three such block assemblies 54 are present at equally spaced radial locations on the outside diameter of the metallic ring 52 . Though three such block assemblies 54 are shown, greater or fewer block assemblies may be equivalently used. Each block assembly comprises a cog portion 64 . Though the relationship of the cog portions 64 to the metallic ring 52 are discussed more below, each of the cog portions extend through the plane defined by the sealing face 60 (i.e., out of the page). In accordance with some embodiments the cog portions 64 of the block assemblies 54 are made of carbon steel, but in other embodiments (e.g., smaller diameter metallic rings) the cog portions 64 may be made of other materials (e.g., aluminum, plastic).
[0022] FIG. 4 illustrates a perspective view of a block assembly 54 in accordance with at least some embodiments. In particular, FIG. 4 illustrates that block assemblies in accordance with at least some embodiments comprise a housing 70 made up of an upper housing 72 and lower housing 74 . The housing defines an interior volume 76 within which resides a lead screw 78 . The lead screw 78 comprises a shaft with external threads, and the cog 80 comprises an aperture with internal threads. As illustrated in FIG. 4 , the cog 80 threadingly couples to the lead screw 78 by way of the aperture. By rotation of the lead screw 78 , as illustrated by arrow 82 , the location the cog 80 may be adjusted, as indicated by arrow 84 . Cog 80 comprises multiple cog portions, but in the perspective view of FIG. 4 only cog portion 64 is visible.
[0023] FIG. 5 is a cross-sectional, elevation view of the block assembly 54 taken substantially along lines 5 - 5 of FIG. 4 . Moreover, FIG. 5 illustrates portions of two flanges having differing sealing features in operational relationship to the block assembly 54 and metallic ring 52 . In particular, FIG. 5 illustrates a portion of raised face flange 90 having a sealing feature in the form of a raised face 92 , and a portion of a RTJ flange 94 having a sealing feature in the form of a ring groove 96 . The inside diameter 98 of the central bore of the metallic ring 52 aligns with the inside diameters 100 and 102 of the raised face and RTJ flanges 90 and 94 , respectively. Two o-rings 104 and 106 reside one each within the o-ring grooves 108 and 110 , respectively. Because of compression force supplied by the bolts through the flanges, the o-rings 104 and 106 compress between the flanges and their respective o-ring grooves, forming a seal.
[0024] Still referring to FIG. 5 , the block assembly 54 housing 70 comprises the upper housing 72 and the lower housing 74 . Having a multiple-piece housing enables insertion of the lead screw 78 and cog 80 within the internal volume during assembly. After insertion of the various internal components, the lower housing 72 is coupled to the upper housing 72 , such as fasteners (e.g., bolts), welding or epoxy. Having the housing 70 separable near its base is merely illustrative. The housing 70 may be equivalently separable at any location that facilitates insertion of the lead screw 78 and cog 80 . Cog 80 comprises a large cog portion 112 , a small cog portion 114 , and an internally threaded aperture 116 . In the illustrative embodiments of FIG. 5 , the large cog portion 112 is configured to extend through a plane defined by the sealing surface 60 A, and the large cog portion 112 interacts or mates with a portion of the sealing feature of the RTJ flange 94 . In particular, mitered portion 118 of the large cog portion 112 contacts and/or couples to the ring groove 96 . The size of the ring groove 96 may change as between RTJ flanges with differing pressure ratings (as illustrated by the dashed lines). In the event the flange seal ring 50 is used with a RTJ flange with larger ring groove 96 but same central passage internal diameter, the position of the cog 80 may be correspondingly changed by virtue of lead screw 78 to ensure contact of the large cog portion 112 to the ring groove 96 wall. In the configuration of FIG. 5 , the small cog portion 114 extends opposite the large cog portion 112 , and resides between the planes defined by the sealing surfaces 60 A and 60 B.
[0025] FIG. 6 is a cross-sectional, elevation view of the block assembly 54 similar to FIG. 5 . Moreover, FIG. 6 illustrates a portion of a raised face flange 120 in operational relationship to the large cog portion 112 . In particular, in addition to the mitered portion 118 , the large cog portion 112 defines a notch 122 . The notch 122 is configured to couple and/or mate to an outside diameter of a raised face 124 of raised face flange 120 . Thus, the illustrative large cog portion 112 may be used in operational relationship to a ring groove of a RTJ flange or the raised face of a raised face flange. In the illustrative case of FIG. 6 , the offset 126 may be 0.25 inches (6.35 mm), and thus the large cog portion 112 is long enough to interact with the ring groove of a RTJ flange ( FIG. 5 ) and define the notch 122 yet short enough to be used with the illustrated raised face flange. However, the offset 126 of a raised face in relation to the bolt face 24 varies depending on the pressure rating of the flange. For lower pressure ratings, the offset 126 may be significantly less than 0.25 inches (6.35 mm), and in such circumstances the large cog portion 112 , if used, may hold the metallic ring 52 and/or o-ring 106 away from the sealing feature of the flange.
[0026] In situations where the large cog portion 112 is too long, the portion of the cog 80 that extends through the plane of the sealing face 60 A may be changed by repositioning of the block assembly 54 . Returning briefly to FIG. 4 , the block assembly 54 is held in place against the metallic ring 52 by way of a plurality of bolts 86 . When the flange seal ring is to be used with a flange where the large cog portion 112 is too long, the block assembly 54 may be removed (by removal of bolts 86 ), turned 180 degrees, and then re-attached to the metallic ring 52 . FIG. 7 illustrates a cross-sectional, elevation view of the block assembly 54 rotated in the metallic ring 52 . In particular, rotation of the block assembly 54 results in the small cog portion 114 extending through the plane defined by sealing face 60 A and large cog portion 112 being between the plane defined by the sealing surface 60 A and plane defined by the sealing face 60 B (the plane illustrated by dashed line 130 ). Small cog portion 114 defines a notch 132 . The depth of notch 132 of the small cog portion 114 is smaller than notch 122 of the large cog portion 112 . The notch 132 is configured to couple and/or mate to an outside diameter 134 of raised face 136 . The offset of the raised face 136 of FIG. 7 is significantly smaller than that of FIG. 6 (e.g., the offset may be 0.06 inches (1.524 mm), thus making use of the large cog portion 112 improper.
[0027] Referring simultaneously to FIGS. 6 and 7 . In FIGS. 6 and 7 , only one flange is shown, the flange that interacts with the cog portion extending through the plane defined by sealing face 60 A. Though a second flange is not shown in either FIG. 6 or 7 , it is noted that either type flange may be in operational relationship to the sealing face 60 B.
[0028] FIG. 8 illustrates a method in accordance with at least some embodiments. In particular, the method starts (block 800 ) and proceeds to placing a flange seal ring against a sealing feature of a first flange (block 804 ). For example, the flange seal ring may be placed against a raised face of a raised face flange, or against the ring groove of a RTJ flange. Next, the seal ring is centered with respect to a central passage through the first flange by adjusting position of one or more cogs coupled to the seal ring (block 808 ). In some embodiments, centering the seal ring comprises adjusting a lead screw coupled to each cog. Finally, a second flange is coupled to the first flange with the seal ring between the flanges (block 812 ), and the method ends (block 816 ). The types of flanges that may be connected in accordance with the method may have central bores having substantially the same diameter, but further may have different pressure ratings and/or different sealing surface types.
[0029] Using a flange seal ring of the various embodiments may eliminate, or at least reduce, the number of adapters or spools a testing laboratory may need to have on hand. Moreover, even in situations where flanges and pressure ratings as between a meter to be tested and the testing laboratory are the same, the expense of gaskets or metallic ring seals (e.g., $1000 for a large diameter gasket or large diameter metallic ring seal) may be eliminated by the reusable nature of the flange seal ring of the various embodiments.
[0030] 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. For example, in some embodiments the sealing faces of the metallic ring define their respectively planes by the entire sealing face lying in a plane; however, the sealing faces need not be planar, and other forms may be equivalently used (e.g., convex (bulging outwardly), or concave). It follows that a plane defined by a sealing face may be based any similar feature of the sealing face (e.g., peak of a convex sealing face, or valley of a concave sealing face). It is intended that the following claims be interpreted to embrace all such variations and modifications. | Method and system of a flange seal ring. At least some of the illustrative embodiments are systems comprising a metallic ring and a plurality of cogs. The metallic ring comprises a central bore that defines an internal diameter, a first sealing face that defines a first plane, a second sealing face that defines a second plane, a first groove in the first sealing face, and a second groove in the second sealing face. The plurality of cogs couple to the metallic ring, each cog extends through the first plane, and the plurality of cogs positioned one each at a plurality of radial positions around the metallic ring. At least one of the plurality of cogs configured to have an adjustable position relative to the central bore, and the cogs configured to align the central bore to a corresponding bore of a flange. | 5 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to an embroidering-frame driving device for a sewing machine, and a method of controlling the device.
2. Discussion of the Related Art
An embroidering-frame driving device has been developed for a sewing machine which moves with respect to the sewing needle an embroidering frame to which a piece of cloth has fastened tight, so that a given pattern is embroidered on the piece of cloth. An embroidering-frame driving device of this type has been disclosed, for instance, by Japanese Patent Examined Publication No. Sho 60-42740, Japanese Utility Model Examined Publication No. Sho 61-40289 and U.S. Pat. No. 5,003,895. The conventional embroidering-frame driving device has an X-axis and Y-axis which are orthogonal with each other. The embroidering frame is moved in the directions of X-axis and Y-axis so that the piece of cloth fastened to the embroidering frame is moved in a horizontal plane with respect to the sewing needle.
The conventional embroidering-frame driving device, being operated on the X- and Y-axes, is unavoidably intricate in structure, and accordingly high in manufacturing cost. In addition, the device is large in frame drive weight, which makes it impossible to increase the sewing speed (rpm). Furthermore, the sewing machine equipped with the device is bulky, requiring a large installation space.
SUMMARY OF THE INVENTION
In view of the foregoing, an object of the invention is to provide an embroidering-frame driving device for a sewing machine which is light in weight, compact, and can be operated at high speed.
The foregoing object of the invention have been achieved by the provision of an embroidering-frame driving device for a sewing machine, which comprises: an embroidering frame for holding cloth stretched tight; an embroidering-frame holder for holding the embroidering frame; a driving motor for driving the embroidering-frame holder in one direction with respect to the sewing needle of the sewing machine; and a rotating motor for rotating the embroidering frame with respect to the embroidering-frame holder.
In the device, the rotating motor is rotated to turn the embroidering frame with respect to the embroidering-frame holder; and the driving motor is turned to move the embroidering-frame holder in one direction with respect to the sewing needle. Thus, the embroidering frame is moved as a composition of rotary motion and linear motion. That is, it is unnecessary to move the embroidering frame in a direction perpendicular to the one direction, and therefore the range of movement of the embroidering frame is reduced to substantially a half of that in the conventional device operating on the X- and Y-axes.
Also, the foregoing object of the invention have been achieved by the provision of a method of controlling the above-described embroidering-frame driving device, in which, for each of sewing points forming an embroidery pattern, the rotating motor is turned until each sewing point comes to a straight line which is extended in the one direction passing through the sewing needle, and the driving motor is driven until each sewing point is moved from the straight line to come under the sewing needle.
In the method, for each of the sewing points, the rotating motor is driven so that the sewing point comes to the straight line. After the sewing point reaches the straight line, the driving motor is operated to move the sewing point until it comes under the sewing needle.
The nature, utility and principle of the invention will be more clearly understood from the following detailed description and the appended claims when read in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
In the accompanying drawings:
FIG. 1 is a perspective view showing a sewing machine equipped with an embroidering-frame driving device according to an embodiment of the invention;
FIG. 2 is a sectional view of the embroidering-frame driving device shown in FIG. 1; and
FIGS. 3, 4 and 5 are sectional views of the embroidering-frame driving device for a description of the operation of the latter.
DETAILED DESCRIPTION OF THE INVENTION
An embroidering-frame driving device for a sewing machine is as shown in FIG. 1, which constitutes an embodiment of the invention.
The sewing machine 10, as shown in FIG. 1, has an arm 11, a base 12, a bed 13, a cloth presser 14, and a needle 15. The bed 13 is set on the base 12. The arm 11 is secured to the bed 13, and has the cloth presser 14 and the needle 15 at the end. The needle 15 is moved up and down with respect to the arm 11, to sew cloth.
The embroidering-frame driving device includes a cylindrical embroidering frame 16, an embroidering-frame holder 17, a timing belt 18, a cylindrical timing pulley, a rotary pulley 20, a rotating motor 21, and a driving motor 22. The driving motor 22 is adapted to drive the embroidering-frame holder 17 in the direction of X-axis (in one direction) with respect to the base 12. The embroidering-frame holder 17 has a cylindrical space in which the cylindrical timing pulley 19 is fitted. The rotating motor 21 is fixedly mounted on the embroidering-frame holder 17, to rotate the rotary pulley 20. The timing belt 18 is laid over the timing pulley 19 and the rotary pulley 20. Hence, as the rotating motor 21 is rotated, the timing pulley 19 is driven through the rotary pulley 20 and the timing belt 18. The cylindrical embroidering frame 16 is fitted in the timing pulley 19. Cloth is held tight between the embroidering frame 16 and the timing pulley 19.
The arrangement of the embroidering-frame driving device will be described with reference to FIGS. 2 and 3 in more detail.
A driving pulley 26 is fixedly mounted on the rotary shaft 33 of the driving motor 22. As shown in FIG. 3, a driven pulley 34 is rotatably mounted on the base 12 of the sewing machine 10, and a timing belt 24 is laid over the driven pulley 34 and the driving pulley 26. The embroidering-frame holder 17 is fixedly fastened to the timing belt at a point with a fixing member 36.
Hence, as the motor 22 is rotated, the timing belt 24 is driven, so that the embroidering-frame holder 17 is moved in one direction with respect to the base 12. The fixing member 36, as shown in FIG. 2, comprises a belt fastener 25, a coupling member 27, a moving stand 28, and a rail 29. The rail is extended in one direction, and fixedly secured to the base 12. The moving stand 28 is slidably mounted on the rail 29. The coupling member 27 is fixedly fastened to the timing belt 24 with the belt fastener 25. The coupling member 27 is further fixedly connected to the embroidering-frame holder 17 and the moving stand 28. Hence, as the motor 22 rotates, the embroidering-frame hole 17 is moved in the one direction along the rail 29 together with the moving stand 29.
As shown in FIG. 2, the timing pulley 19 is rotatably held in the embroidering-frame holder 17 through ball bearings 30. As was described before, the rotary pulley 20 is fixedly mounted on the rotary shaft 35 of the rotating motor 21, and the timing belt 18 is laid over the rotary pulley 20 and the timing pulley 19. Therefore, as the rotating motor 21 is rotated, the timing belt 18 is driven to turn the timing pulley 19 with respect to the embroidering-frame holder 17.
As was described before, the embroidering frame 16 is fitted in the timing pulley 19 with a piece of cloth 23 held tight between them. The bed 32 of the sewing machine, which accommodates a rotating hook 32, is provided immediately below the needle 15.
The operation of the embroidering-frame driving device thus constructed will be described with reference to FIGS. 3, 4 and 5.
The center of the embroidering frame is at a distance of L from the rotary shaft 33 of the driving motor 33 in the direction of the arrow X.
Hereinafter, the axis extended through the center of the embroidering frame in the direction of the arrow X will be referred to as an X-axis. In the case of FIG. 3, the position of the center of the embroidering frame 16 is the same as that of the center P of the needle 15. It is assumed that, by way of example, the character "N" having sewing points A, B, C, D, E, F, G, H, I, J, K and L is to be embroidered on a piece of cloth 23 held by the embroidering frame 16.
First, in order to sew the point A, the rotating motor 21 is turned through an angle θ1 between the X-axis and the straight line extended from the center of the embroidering frame 16 to the point A, to move the point A to a point A1 on the X-axis as shown in FIG. 3. Thereafter, the driving motor 22 is turned so that the embroidering-frame holder 17 is moved as much as the distance X1 between the needle center P and the point A1. As a result, the needle center P reaches the point A as shown in FIG. 4. Thus, the point A can be sewed. Next, the rotating motor 21 is turned again through an angle θ2 formed between the X-axis and the straight line extended from the center of the embroidering frame to the point B, to move the point B to a point B1 on the X-axis. Under this condition, the driving motor 22 is turned so that the embroidering-frame holder 17 is moved as much as the distance X2 between the needle center P and the point B1. As a result, the needle center P reaches the point B. Thus, the point B can be sewed. For the remaining points C through L, the device is operated in the same way. Thus, the character "N" has been embroidered on the piece of cloth.
In the above-described method, in order to sew the point A (or B) the embroidering frame 16 is turned through the angle θ1 (or θ2), and then the embroidering-frame holder 17 is moved as much as the distance X1 (or X2); however, the invention is not limited thereto or thereby. That is, the embroidering-frame driving device may be so modified that the angle θ1 (or θ2) and the distance X1 (or X2) are obtained in advance, and the motors 21 and 22 are turned at the same time.
The embroidering-frame driving device of the invention has the following advantages:
As was described above, in the embroidering-frame driving device of the invention, the embroidering frame is moved only in one direction. Accordingly, the device may be simple in construction, and the sewing machine equipped with the device is small in size. In addition, the device is light in weight, which makes it possible to increase the speed of movement of the embroidering frame and accordingly the sewing speed (rpm) of the sewing machine. Furthermore, it is unnecessary for the device to be so high in the squareness of its X-axis and Y-axis, and therefore its components are not always required to be high in accuracy, and they may be assembled with relatively low precision. Moreover, in the device of the invention, the embroidering frame is smaller in the range of movement than in the conventional embroidering-frame driving device.
While there has been described in connection with the preferred embodiment of this invention, it will be obvious to those skilled in the art that various changes and modifications may be made therein without departing from the invention, and it is aimed, therefore, to cover in the appended claims all such changes and modifications as fall within the true spirit and scope of the invention. | An embroidering-frame driving device for a sewing machine comprises: an embroidering frame for holding cloth stretched tight; an embroidering-frame holder; a driving motor for driving the embroidering-frame holder in one direction with respect to the sewing needle; and a rotating motor for rotating the embroidering frame with respect to the embroidering-frame holder. In the device, for each of the sewing points forming an embroidery pattern, the rotating motor is turned until the sewing point comes to a straight line which is extended in the one direction passing through the sewing needle, and the driving motor is driven until the sewing point is moved from the straight line to come under the sewing needle. | 3 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of the following co-pending patent application:
1. U.S. patent application Ser. No. 08/753,717, filed Nov. 27, 1996, entitled “Method and Apparatus for Improved Tertiary Hydrocarbon Recovery.”
This Application claims the benefit, through the above-identified patent application, of the filing date under 35 USC §§119 and/or 120, and 37 CFR §§1.60 and/or 1.78 to the following U.S. regular patent application and U.S. provisional patent application:
1. U.S. provisional patent application Ser. No. 60/007,846, filed on Dec. 1, 1995, entitled “Method and Apparatus for Tertiary Hydrocarbon Recovery”; and
2. U.S. patent application Ser. No. 08/753,717, filed Nov. 27, 1996, entitled “Method and Apparatus for Improved Tertiary Hydrocarbon Recovery.”
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates generally to the transport of a target substance from an earth formation, and may find commercial application in the recovery of hydrocarbons from a wellbore or in environmental clean-up operations.
2. Description of the Prior Art
Hydrocarbons are likely to remain a critical component of this nation's economy. While the oil and gas industry expends considerable sums in the exploration and development of new fields, the industry also recognizes that a large amount of unproduced hydrocarbons remain in formations which have already been discovered and produced. Many older formations have been subjected to workover operations, wherein the hydrocarbon-bearing formations were fractured, water-flooded, and subjected to various chemical treatments. Even in those formations in which substantial sums have been expended on secondary recovery operations, the industry recognizes that substantial deposits remain. This has given rise to a tertiary recovery industry, wherein various techniques are utilized to stimulate the formation and generate the production of additional hydrocarbons therefrom. For example, a variety of techniques exist in which the formation is subjected to electrical or thermal stimulation which allows for the additional production of hydrocarbons. For example, various prior art techniques include the stimulation of the formation using microwave radiation. Alternatively, electrodes can be placed in the formation in order to stimulate production utilizing electrical currents. Alternatively, a thermal element can be located within the wellbore which elevates the formation temperature, resulting in increased production, in particular in fields which have hydrocarbon deposits which tend to congeal and clog the flow pathways and wellbore.
The present invention is also directed to environmental clean-up operations of both subsurface and surface locations. In the prior art, considerable amounts are expended to contain and clean-up undesirable contamination which may reside in a subterranean or surface location. Contaminates may include extremely hazardous materials, such as toxic substances, as well as less hazardous materials such as petroleum based chemicals. Prior art clean-up operations are often very expensive operations to undertake and may involve the excavation, removal, and replacement of surface earth formations. Such projects are of a massive scale, requiring considerable investment of manpower, equipment, and time. For spills that occur in relatively populous regions, there are very few options, since the contaminate soil may present long term hazards to the aquifer or other water supplies adjacent or beneath the contaminated soil. Any improvement in technology that may reduce the investment in dollars, manpower, equipment, and time would be welcome in the industry.
SUMMARY OF THE PRESENT INVENTION
It is one objective of the present invention to provide a method for utilizing the piezoelectric effect for aiding in the transporting of target substances within an earth formation.
It is yet another objective of the present invention to provide a method which utilizes either or both of the direct and the converse piezoelectric effect to mechanically stimulate at least one earth formation to increase the permeability of the medium, increase the local temperature in the medium, and to enhance the permeability of a preselected volume of the medium.
Additionally, it is another objective of the present invention to provide a method for piezoelectric-induced transport within a particular earth formation, in a manner which allows an operator to control the directional is orientation of an enhanced permeability within the earth formation.
Yet another objective of the present invention is to provide a method of utilizing a piezoelectric effect to sequentially deform an earth medium and produce the effect of a peristaltic fluid pump to directionally transport fluids within a target formation.
These and other objectives are achieved as is now described. A method is provided for enhancing the transport of a target substance in a particular surface and/or subsurface earth formation. The method includes a number of method steps. An earth formation is identified which has a particular, desirable piezoelectric property. The earth formation bears a target substance which is to be separated or removed from the earth's formation. In one commercial implementation, the target substance may include hydrocarbons or other downhole substances which are commercially valuable or which should be removed for other reasons. Either both of the direct and converse piezoelectric effects are utilized. When the converse piezoelectric effect is utilized, a voltage is applied to at least a particular portion of the earth formation. The voltage develops mechanical stress in the particular earth formation utilizing the piezoelectric property, in particular utilizing the converse piezoelectric effect. The mechanical stress causes changes in the earth's formation which facilitate removal of the target substance. Alternatively, or supplementally, the direct piezoelectric effect may be utilized by supplying a vibration or sonic energy source mechanically coupled to the earth formation. Finally, at least one removal process is utilized in combination with utilization of the piezoelectric property to transport at least a portion of the target substance away from the particular earth formation. In the context of the commercial implementation of hydrocarbon recovery, the removal process may be any conventional or novel process for directing hydrocarbons to the surface, and may include pumping or water flooding operations.
In one preferred embodiment of the present invention, the utilization of the converse piezoelectric effect generates mechanical stress in the earth formation which alters the permeability of the earth formation. Additionally, the mechanical stress develops a local temperature increase in the affected formation. The impact of the electrical field, mechanical stress, and the temperature increase results in changes which affect the permeability of the target substance and which result in an advantageous increase in the permeability which allows the target substance to be removed from the earth formation. This may be supplemented by the application of vibratory or sonic energy to the formation.
In alternative embodiments of the invention, the piezoelectric effect may be applied to the earth formation in a manner which develops permeability which has a controllable directional orientation. This is accomplished by applying either a stimulating voltage and/or a vibration or sonic source to the earth formation in a manner which either varies the piezoelectric effect with respect to time or location within the surface or subsurface earth formation. In this manner, the permeability may be controlled in time and direction in order to allow for preferential flow of subterranean fluids which may carry the target substance. Additionally, and alternatively, a plurality of stimulating energies may be applied in a predetermined pattern with respect to time to a plurality of portions of surface or subsurface earth formations in order to sequentially deform the earth formations in a manner which evacuates fluid due to a resulting peristaltic pump fluid action.
In the preferred embodiment of the present invention, analysis is performed of the surface or subsurface earth formation which contains a target substance in order to determine the presence of a piezoelectric effect and the magnitude of the piezoelectric effect within the formation. Additionally, the earth formation which contains the target substance may be studied in order to determine the one or more resonant frequencies associated with the material. The resonant frequencies may be utilized during stimulation operations in order to maximize the application of the piezoelectric effect to the earth formation. The determination of the optimum frequency or frequencies of operation can be performed in a classical scientific manner by applying a range of energizing frequencies to the target substance in order to determine the optimum frequency of operation.
Additionally, and alternatively, the optimization of the piezoelectric excitation of surface or subsurface earth formation may be conducted during stimulation operations, in a relatively conventional feedback system. In accordance with this alternative embodiment, the amount of target substance released from the formation is monitored during stimulation operations in order to determine the one or more optimum frequencies of stimulation. The stimulation process is adjusted in response to this feedback to change the frequency of stimulation in order to optimize the production of target substance from the earth formations.
In yet another embodiment, contaminated soil (such as sand) may be placed in a centrifuge-type device and water may be added. The resulting mixture may be subjected to a direct and/or converse piezoelectric energizing source while the centrifuge is being operated. The piezoelectric effect weakens the cohesive forces at the sand-oil interface. The combination of mechanical and electrical stress further enhances a separation of oil, sand, and water.
BRIEF DESCRIPTION OF THE DRAWINGS
For a better understanding of the invention as well as other objectives and features, reference is made to the following description which is to be read in conjunction with the accompanying drawing wherein:
FIG. 1 is block diagram representation of the testing process utilized to determine the operating attributes of an energizing source for a converse piezoelectric effect which optimizes production of hydrocarbons from a particular formation.
FIG. 2 is a pictorial and block diagram representation of utilization of the converse piezoelectric effect in order to increase the temperature of hydrocarbon bearing formations.
FIG. 3 is a graphical depiction of the capability of the process of the present invention to operate on a preselected volume of formation in order to alter or enhance the recovery of hydrocarbons;
FIGS. 4 and 5 depict particular fault configurations, and are utilized to explain how the present invention exploits the faults;
FIGS. 6 and 7 are utilized to explain utilization of the present invention as a peristaltic pump;
FIG. 8 is utilized to explain utilization of the present invention for environmental clean-up operations;
FIG. 9 is a pictorial representation an equivalent circuit which is utilized to explain the resonance of a piezoelectric material.
FIG. 10 is a flowchart representation of one preferred application of stimulating energy to an earth formation.
FIG. 11 is a flowchart representation of the implementation of the present invention in order to log particular formations.
FIG. 12 is a flowchart representation of the testing process utilized in accordance with the preferred embodiment of the present invention.
FIG. 13 is a flowchart representation of a primarily mechanical embodiment of the piezoelectric transport method of the present invention.
FIG. 14 is a flowchart representation of the process of testing samples to determine mechanical resonance.
FIG. 15 is a flowchart representation of the utilization of the present invention for environmental clean-up operations.
DETAILED DESCRIPTION OF THE INVENTION
This invention relates to a method which facilitates the movement of any fluid through any geologic or earth formation or medium that possesses piezoelectric properties. Application of the process to such a medium results in the following:
1. An increase in the permeability of the medium.
2. An increase in the temperature of the medium.
3. The capability to enhance the permeability of any preselected volume of the medium.
4. The capability to control the directional orientation of the enhanced permeability within the medium.
5. The capability to sequentially deform the medium in effect making the medium a peristaltic fluid pump.
6. The capability to mechanically and electrically agitate the medium to overcome the cohesive forces between the fluid and the medium.
7. The capability to log the medium in terms of the type and amount of fluid within it.
The process operates on the piezoelectric components of the medium by using the direct and/or converse piezoelectric effect singly or in combination. The application of a mechanical stress to a piezoelectric crystal produces an electric polarization which is proportional to this stress. If the crystal is isolated, this polarization manifests itself as voltage across the crystal, and if the crystal is short-circuited, a flow of charge can be observed during loading. Conversely, application of a voltage between certain faces of the crystal produces a mechanical distortion of the material. This reciprocal relationship is known as the piezoelectric effect. The phenomenon of generation of a voltage under mechanical stress is referred to as the “direct piezoelectric effect,” and the mechanical strain produced on the crystal under electric stress is called the “converse piezoelectric effect.” In general, this electromechanical coupling is very sensitive as to how the crystal is oriented with respect to the orientation of the applied electric field or mechanical stress. This property is also exploited by the process of the present invention.
The piezoelectric strains that can be induced by a static electric field are small. Larger strains can be obtained when a piezoelectric crystal is driven by an alternating voltage, the frequency of which is equal to a mechanical resonance frequency of the crystal. The vibrating crystal reacts back on itself through the direct piezoelectric effect. Further increases in the amplitude of vibration are realized by stimulating the vibrating crystal with additional electromagnetic or sonic radiation tuned to match the achieved resonant frequency of the crystal. Sonic radiation is a one method to cause mechanical deformation of the piezoelectric crystal. The amplitude of vibration is maximized causing fatigue fractures either within the structure of the crystal or along grain boundaries.
The necessary condition for the piezoelectric effect is the absence of a center of symmetry in the crystal structure. Of the 32 crystal classes, 21 lack a center of symmetry, and with the exception of one class, all of these are piezoelectric. In the crystal class of lowest symmetry, any type of stress generates an electric polarization, whereas in crystals of higher symmetry, only particular types of stress can produce a piezoelectric polarization. For a given crystal, the axis of polarization depends upon the type of the stress. There is no crystal class in which the piezoelectric polarization is confined to a single axis. In several crystal classes, however, it is confined to a plane.
The converse piezoelectric effect is a thermodynamic consequence of the direct piezoelectric effect. When a polarization P is induced in a piezoelectric crystal by an externally applied electric field E, the crystal suffers a small strain S which is proportional to the polarization P. In crystals with a normal dielectric behavior, the polarization P is proportional to the electric field E, and hence the strain is proportional to this field E.
The relation of the six components T j of the stress tensor (three compressional components and three shear components) to the three components P i of the polarization vector can be described by a matrix of 18 piezoelectric moduli d ij . The same scheme (d ij ) also relates the three components E i of the electric field to the six components S j of the strain.
The direct effect is then given by Eq. (1).
P i =−Σ j=1 6 d ij T j i=1,2,3 (1)
The converse effect is given by Eq. (2).
S j =Σ i=1 3 d ij E i j=1,2, . . . ,6 (2)
An analogous matrix (e ij ) relates the strain to the polarization as in Eq. (3)
P i =Σ j=1 6 e ij S j i=1,2,3 (3)
and the electric field to the stress as in Eq. (4).
T j =−Σ i=1 3 e ij E j j=1,2, . . . ,6 (4)
The matrices (d ij ) and (e ij ) are not independent, but are related by expressions involving the elasticity tensor c jh E (for constant electric field E), as in Eq. (5).
e mh =Σ j=1 6 d mj c jh E m=1,2,3h=1,2, . . . ,6 (5)
The number of independent matrix elements d ij or e ij depends upon the symmetry elements of the crystal. For the lowest symmetry, all 18 matrix elements are independent, whereas piezoelectric classes of higher symmetry can have as few as one independent element in the matrix (d ij ). The matrix takes its simplest form if the natural symmetry axes of the crystal are chosen for the coordinate system. The most likely piezoelectric medium for this application is quartz or silicon dioxide. Quartz belongs to the trigonal system, and the point group is 32. Components of the d-constant are d 11 =−d 12 , d 14 =−d 25 , and d 26 =−2d 11 ; those of the e-constant are e 11 =−e 12 , e 14 =−e 25 , and e 26 =−e 11 . There are two independent components in either d or e. For quartz, these values are d 11 =2.3 pCN −1 , d 14 =−0.067 pCN −1 , e 11 =0.17 Cm −2 , e 14 =0.04 Cm −2 .
One excellent resource for obtaining an overview of piezoelectrinc principle is the publication entitled “An American National Standard: IEEE Standard on Piezoelectricity” ANSI/IEEE Publication No. Std. 176-198. Another resource which provides an overview of the constants of various crystals is the publication entitled “The Constants of Alpha Quartz” by Roger Ward, which is reprinted in the 38th Annual Frequency Control Symposium, 22-31, by the IEEE.
The direct piezoelectric effect makes a crystal a generator, and the converse effect makes it a motor. Consequently, a piezoelectric crystal has many properties in common with a motor-generator. For example, the electrical properties, such as the dielectric constant, depend upon the mechanical load; conversely, the mechanical properties, such as the elastic constants, depend upon the electric boundary conditions. The electromechanical coupling factor k can be defined as follows. Suppose electrodes are attached to a piezoelectric crystal and connected to a battery, the ratio of the energy stored in mechanical form to the electrical energy delivered by the battery is equal to k 2 . In general, k ranges from below 1 to about 30%. In quartz, the coupling is roughly 10%.
In quartz, a stress of 1 newton/m applied along the diad axis produces a polarization of about 2×10 −12 coulombs/m 2 along the same axis. Conversely, an electric field of 10 4 volts/m produces a strain of about 2×10 −8 . The piezoelectric strains that can be induced by a static electric field are very small. Much larger strains can be obtained when a piezoelectric crystal is driven by an alternating voltage, the frequency of which is equal to the mechanical resonance frequency of the crystal. The vibrating crystal reacts back on the circuit through the direct piezoelectric effect. When resonance occurs, the frequency of excitation matches the natural mechanical resonance of the piezoelectric medium giving rise to a huge increase in response in terms of strain and, therefore, stress within the medium.
In the range of mechanical resonance, this reaction is equivalent to the response of the network shown in FIG. 9 provided that the series resonance frequency of the network is equal to a mechanical resonance frequency of crystal as in Eq. (6). W R = 1 2 π LC ( 6 )
An important difference between equivalent series network of FIG. 9 and the piezoelectric resonator is that the latter has many discrete modes of vibration, whereas the network has only one resonance frequency.
The network elements L, C, and C o of the equivalent network can be calculated from the physical constants of the crystal. For a typical piezoelectric crystal such as quartz, resonating at about 10 5 Hz, typical values for the elements of the equivalent network are L=10 2 henrys, C=0.02 picofarad and C o =5 picofarad.
The process of the present invention utilizes these principles in the following manner to facilitate the movement of fluid through a piezoelectric medium. The piezoelectric characteristics of the medium are determined from samples including any pattern of recurrent orientation of the crystals other than random within the medium. These samples are subjected to an alternating voltage to force the vibrating crystals to resonance. Approximate values of voltage and frequency are known from mathematical modeling. The values of voltage and frequency are experimentally refined by transducers on the stimulated sample which determine the resonant frequency when the amplitude of vibration is maximal. Sonic and or additional electromagnetic radiation at this frequency is then used to further stimulate the sample. Conventional tests for permeability of the medium are done before and after the experiment and are compared. The tests are repeated altering the orientation of the input energy sources with respect to the medium sample. Results of this series of tests on the representative medium sample yields values for input alternating voltage, resonant frequency and the influence of orientation of the input energy sources on the overall effect. Thus, these parameters are determined experimentally from a representative sample of the medium. Note that the initial resonant vibration can also be achieved by mechanical stimulation using the direct piezoelectric effect.
FIG. 1 illustrates the testing process on a sample 11 from the piezoelectric medium. The sample is stimulated with an alternating voltage causing the piezoelectric crystals to vibrate at frequency w. A vibration transducer 13 senses this frequency and the amplitude of the vibration and feeds back this information to the beginning of the loop. The alternating voltage input of the voltage generator 15 is adjusted in this negative feedback loop until the amplitude of vibration becomes maximal. The frequency is now the resonant frequency w, of the sample. If additional response is needed, the sample is then bombarded with sonic and/or electromagnetic radiation from source 17 which is tuned to match the resonant frequency of the sample. This testing process gives information regarding input voltage characteristics which result in resonant vibration of the piezoelectric crystals in the medium.
The process is then applied to the medium itself using these experimentally derived parameters. Stimulation of the medium is done from any point within, on or outside the medium. If the sample testing demonstrated any recurrent orientation of the piezoelectric crystals in the medium other than random, the stimulating foci are placed to maximize the effect. As with the sample testing operations, vibration transducers are used to feedback amplitudes and frequencies of vibration of the medium. When the frequency of vibration of the medium reaches resonance, the medium is further stimulated by high amplitude sonic or electromechanical energy at the same frequency. Fatigue fractures occur throughout the medium thus increasing the fracture porosity and permeability of the medium in general which facilitates the movement of fluid through it. The friction caused by the vibration increases the temperature of the medium lowering the viscosity of the fluids within it allowing for easier extraction.
FIG. 2 illustrates the process applied to a piezoelectric medium which is penetrated by a wellbore. The equipment shown consists of a voltage generator 23 which stimulates the piezoelectric crystals within the medium to vibrate. The amplitude and frequency of the vibration are sensed by transducers 19 on or within the medium. This information is fed back to the voltage generator 23 . When the amplitude of vibration is maximized, the resonant frequency is defined. At this point, a sonic and/or electromagnetic wave generator source 21 is activated to bombard the medium with energy at this frequency.
Certain physical characteristics of the target medium determine the degree of ease of application and thus the success of this process. Foremost among these is that the medium must possess piezoelectric properties. Quartz, or silicone dioxide, is piezoelectric and contributes significantly to the makeup of the earth's crust. The shear abundance of this material and its intimate relationship with hydrocarbons, either naturally or man made, makes it the most likely medium for application of this process. Also, it is known that electromagnetic radiation penetrates rock less when higher frequencies are implemented. This is also true to a lesser extent with sonic radiation. This limitation thus makes the process more amenable to application near or on the surface as access to the medium for both stimulation and instrumentation is easier. Finally, an ionic environment such as the presence of saline is less desirable as this would tend to short circuit the desired electrical effects.
This process has the capability to operate on a preselected volume of the target medium. This is realized by stimulating the preselected volume from multiple foci as shown in FIG. 3 . In general, the predetermined volume in the medium to be operated on by this process results from any combination of intersecting geometrical shapes that are generated from the stimulating foci, which are placed strategically to define this specific volume. The overall desired effect is maximized within this volume by stimulating the volume from multiple orientations as the piezoelectric effect is sensitive to relative orientation as noted above. One application of this particular aspect of the process is the ability to weaken a preselected portion of the medium in a controlled fashion by strategic placement of the stimulating foci as shown in FIG. 3 . More conventional fracturing techniques, which utterly lack directional control, could then be used and would now have a predetermined path to follow. The resulting fracture enhances fluid movement in the medium.
FIG. 3 demonstrates the capability of the process to operate on a preselected volume of the piezoelectric medium. In this example, points E and F represent different points in two separate well bores that penetrate the medium from the surface. They serve as foci from which an alternating voltage of appropriate frequency emanate, stimulating the volume of the medium between these two points to vibrate at resonant frequency. However, only those piezoelectric crystals aligned properly will be stimulated in this volume. In order to stimulate crystals of different orientations within this volume, the orientation of the input electric field must be different. As illustrated, this could be accomplished from the surface. Points AB and CD represent origins of electric fields from the surface oriented to intersect line EF which is the common line of intersection of all stimulating foci. Thus, the crystals in this volume are maximally stimulated to vibrate at resonant frequency. An infinite number of resulting volumes are possible and are dependent on the location and orientation of the input electric fields and voltages. After resonance is achieved, the vibrating crystals are further stimulated with electromagnetic and/or sonic energy as described above.
This same process also has the capability to control the orientation of the enhanced permeability by capitalizing on the sensitivity of the piezoelectric effect with regard to the orientation of the crystal with respect to the stimulating field. The net orientation of the micro fractures produced by this process could be manipulated to give the resultant fluid flow in the medium a specific direction. This is accomplished by aligning the stimulating field along the desired orientation of the fractures so that only those crystals within the medium that are aligned properly will be effected. For example, the net orientation and direction of the micro fractures could be manipulated to be parallel to facilitate movement of fluid toward a known fault in the medium as shown in FIG. 4, or radial from a hole in the medium as shown in FIG. 5 .
In addition, this process can be used to make the medium itself behave like a peristaltic fluid pump. This is accomplished by stimulating a portion of the piezoelectric medium utilizing the above techniques. By the piezoelectric effect, this portion of the medium deforms causing the net movement of fluid within. Next, an immediately adjacent portion of the medium is identically stimulated while allowing the previous volume to relax. This process is repeated sequentially along a selected direction effectively creating a standing wave of deformation within the medium which pushes fluid ahead of it. The characteristics of the standing wave are adjusted to accommodate the dynamics of the fluid flow in order to maximize it. Again, the necessary parameters are determined experimentally from a medium sample.
FIG. 6 is an example of the ability of this process to stimulate the piezoelectric medium in such a manner that it causes the medium to behave like a peristaltic pump. In this figure, the piezoelectric medium is divided into n different target volumes such that a line drawn through the center of each volume represents the desired net direction of fluid flow. The necessary values of input electrical energy to achieve the maximum desired effect are determined experimentally using the above techniques. The first volume is then stimulated causing a net deformation of this volume which results in movement of the fluid within it. As this volume is allowed to relax, the immediately adjacent volume is stimulated. This process is continued, sequentially deforming each volume in turn, which pushes fluid in the net direction defined above. FIG. 7 demonstrates this process graphically, showing the changing pressure gradient in each volume over time. The characteristics of the wave of deformation are adjusted to allow maximal flow of fluid.
Additionally, this process can be used to mechanically and electrically agitate the medium and fluid within it. In this case, the medium is stimulated by either sonic or electromagnetic radiation. The resultant piezoelectric effect creates both mechanical and electrical stress within the medium. This energy then weakens the cohesive forces between the medium and fluid facilitating fluid movement within the medium. Initially, the most efficient parameters to achieve this are determined experimentally with a sample of the medium and its resident fluid.
FIG. 8 demonstrates the process applied to an environmental disaster such as an oil spill on a beach. In this case, the piezoelectric medium is sand or silicone dioxide and the target fluid is the spilled oil. Following the steps above, a sample of the contaminated sand is tested to obtain the values of electromagnetic or sonic radiation necessary to achieve either resonance or that which maximizes the desired effect of separating the oil from the sand. The contaminated sand is then placed in a container and mixed with water. The sand is then stimulated with electromagnetic radiation and or sonic radiation. The resultant piezoelectric effect creates both mechanical and electrical stress in the individual sand grains. Specifically, the cohesive forces between the oil and the sand are disrupted by this induced agitation. The separation of the oil from the sand grains during this process is enhanced by the presence of water which is a more polar molecule. The changing electric dipole of the stimulated silicone dioxide crystals both attracts and repulses the polar water molecules increasing the agitation at the sand-oil interface. Final separation of the oil from the sand is realized from gravitational forces acting on the basic difference between the density of water and the density of oil. The gravitational force could be dramatically increased by centrifuging the sand, oil and water. After separation of the oil from the sand is complete, the oil is separated from the water, and the sand is returned to the beach.
Finally, this process has the capability to log the medium in terms of the extent and concentration of fluid within it. When stimulated with electromagnetic energy or mechanical energy, the piezoelectric medium will vibrate yielding both sonic and electromagnetic radiation at a certain frequency. This frequency is dependent on the overall mechanical properties of the medium which is in turn influenced by the type and amount of fluid within it. Given the same electrical or mechanical input, a dry piezoelectric medium will emit a different signal than the same medium containing fluid. The exact relationship between the frequency of the emitted sonic or electromagnetic signal and type and amount of fluid within the medium is again determined experimentally first and then applied to the medium itself. This phenomenon can be further exploited to determine the type of fluid in a piezoelectric medium by determining the sonic or electromagnetic signature that is emitted when the medium is stimulated. This aspect of the process can also be used to monitor the status of the fluid flow within the medium as influenced by the process in general.
In conclusion, this invention facilitates the movement of fluid through any medium that possesses piezoelectric properties. The process increases the permeability of the medium in general or can be used to increase the permeability of a preselected portion of the medium. It has the capability to control the net orientation of the enhanced permeability and to increase the temperature of the medium through frictional effects. It also has the capability to turn the medium into a peristaltic fluid pump and lends itself as a logging tool for piezoelectric media. The process also has the capability to overcome the cohesive forces at the piezoelectric media and fluid interface. These different effects can be used singly, in combination with each other, or in combination with any other commercial technique or natural process to maximize the movement of fluid within the target medium.
FIG. 10 is a block diagram representation of the application of an alternating energizing source (either or both of the direct piezoelectric effect and converse piezoelectric effect) in broad overview form. The process begins at block 151 , and continues at block 153 , wherein alternating voltages applied to the piezoelectric formation. In accordance with block 155 , mechanical strain is developed in the formation which increases temperature and increases permeability of the target substance within the formation. In accordance with block 157 , monitoring devices are utilized to monitor the vibration of the formation. In accordance with block 159 , the flow is also monitored of the target substance from the formation. In accordance with the present invention, fluids may be lifted from the earth formation utilizing conventional technologies such as artificial or gas lift technologies to lift fluid and hydrocarbons to the surface for further processing. Alternatively, and supplementally, conventional water flooding technologies may be utilized to direct the flow of hydrocarbon bearing fluids within a hydrocarbon bearing zone. In accordance with block 161 , the frequency of the alternating voltage is adjusted in order to increase the vibration induced within the wellbore and to increase flow of the target substance. Preferably, but not necessarily, the frequency of maximum excitation and maximum flow of the target substance is likely to be the resonant frequency of the piezoelectric material in the formation. In accordance with block 163 , the electrical stimulation of the formation is supplemented by mechanical and/or sonic stimulation of the formation utilizing an alternating vibration or sonic source. In accordance with blocks 165 and 167 , sensors are utilized to monitor the amount of vibration within a formation and the amount of flow the target substance from the earth formation. In accordance with block 169 , the frequency of the mechanical and/or sonic stimulation of the formation is adjusted to increase and optimize vibration which is induced in the formation and flow of the target substance of the formation. Once again, the frequency of optimum operation is likely to be the resonant frequency of the piezoelectric material. The processing ends at block 171 .
FIG. 11 is a high level flowchart representation of the utilization of the method and apparatus of the present invention for logging the content of a particular formation. The process begins at block 201 , and continues at block 203 , wherein core samples are tested to determine the hydrocarbon content. Next, in accordance with block 205 , the hydrocarbon content is recorded. Then, in accordance with block 207 , the core sample is stimulated to determine its resonant frequency. In accordance with block 209 , the resonant frequency is recorded in memory. Then, in accordance with block 211 , the hydrocarbon content of the sample is changed. According to block 213 , the hydrocarbon content of the sample is examined to determine whether it falls within the range of zero through a particular index content. If so, control returns to block 207 ; if not, control passes to block 215 , wherein a plot is generated of all the values of resonant frequency versus hydrocarbon content in order to create a logging curve, such as logging curve 216 .
The process continues at block 217 , wherein the petroleum bearing formation, from which the sample has been taken and studied, is istimulated in order to obtain the resonant frequency. In accordance with block 219 , the resonant frequency is recorded. Then, in accordance with block 221 , the formation is logged by obtaining hydrocarbon content which corresponds to the resonant frequency from the logging curve created above. In accordance with block 223 , analysis is performed to determine whether there is on-going hydrocarbon recovery; if so, control passes to block 217 , for further stimulation; however, if not, control passes to block 225 , wherein the process ends.
FIG. 12 is a block diagram depictions of testing in accordance with the present invention of samples as part of the implementation of the method and apparatus for piezoelectric transport of target substances. The process begins at block 251 , and continues at block 253 , wherein a core sample of a formation of interest is obtained. Next, in accordance with block 255 , the core sample is examined to determine the extent of recurrent crystal orientation. In accordance with block 257 , if recurrent orientation is present, control passes to block 259 ; however, if recurrent orientation is not present, control passes to block 261 .
In accordance with block 259 , the stimulating energy to be employed with that particular formation is randomly oriented. This is in contrast with block 251 , wherein the stimulating energy is positioned to maximize the effect in view of the existence of recurrent orientation in the target formation. In accordance with block 263 , the sample is tested with electrical stimulation at a frequency estimated by mathematical modeling. In accordance with block 265 , the vibration of the sample is monitored. In accordance with block 267 , the frequency of stimulation is changed. In accordance with block 269 , the vibration is monitored to determine maximum vibration. This process is utilized to determine the particular stimulating frequency which produces a maximum vibration in a sample. Once a maximum vibration is detected, control passes to block 271 , wherein the resonant frequency is recorded and the electrical input characteristics of the stimulator frequency also recorded. Next, in accordance with block 273 , the sample is examined to determine permeability and microfractures. If permeability and microfractures have been optimized, as determined at block 275 , the process passes control to block 277 , wherein it ends; however, if it is determined that block 275 that optimum permeability and microfractures have not been obtained, control passes back to block 261 , wherein the position of the stimulating energy is determined. In practice, the position of the stimulating energy will be altered in view of the existing data set, and the testing of blocks 263 through 275 will continue until the maximum effect of the stimulating energy position is determined.
FIG. 13 is a block diagram representation of the application of an alternating mechanical energizing source in broad overview form. The process begins at block 351 , and continues at block 353 , wherein alternating mechanical stress is applied to the piezoelectric formation. In accordance with block 355 , mechanical strain is developed in the formation which increases temperature and increases permeability of the target substance within the formation. In accordance with block 357 , monitoring devices are utilized to monitor the vibration of the formation. In accordance with block 359 , the flow is also monitored of the target substance from the formation. In accordance with the present invention, fluids may be lifted from the earth formation utilizing conventional technologies such as artificial or gas lift technologies to lift fluid and hydrocarbons to the surface for further processing. Alternatively, and supplementally, conventional water flooding technologies may be utilized to direct the flow of hydrocarbon bearing fluids within a hydrocarbon bearing zone. In accordance with block 361 , the frequency of the alternating mechanical stress is adjusted in order to increase the vibration induced within the welibore and to increase flow of the target substance. Preferably, but not necessarily, the frequency of maximum excitation and maximum flow of the target substance is likely to be the resonant frequency of the piezoelectric material in the formation. In accordance with block 363 , the mechanical stimulation of the formation is supplemented by electrical stimulation of the formation utilizing an alternating voltage source. In accordance with blocks 365 and 367 , sensors are utilized to monitor the amount of vibration within a formation and the amount of flow the target substance from the earth formation. In accordance with block 369 , the frequency of the mechanical and/or sonic stimulation of the formation is adjusted to increase and optimize vibration which is induced in the formation and flow of the target substance of the formation. Once again, the frequency of optimum operation is likely to be the resonant frequency of the piezoelectric material. The processing ends at block 371 .
FIG. 14 is a flowchart representation in broad overview of the preferred process of determining resonance of particular samples. The process begins at block 391 and continues to block 392 , wherein core samples of the earth's formation of interest are obtained. Then, in accordance block 393 , the samples are tested under variable mechanical stimulation. In accordance with block 394 , the permeability of the samples is monitored. Additionally, in accordance with block 395 , the sample is monitored with sensors to determine whether the sample is in resonance. If not, control returns to block 393 , wherein the frequency and/or amplitude of the mechanical stimulation is altered in a predetermined manner; however, if it is determined in block 395 that resonance is occurring, in accordance with block 396 , the resonant frequency is recorded, and the process ends at block 397 .
FIG. 15 is a flowchart representation of the utilization of the present invention to remove contaminates from soil. This has particular applicability of the clean-up of oil spills on sandy soils, such as beaches. The process commences at block 401 , wherein samples of the contaminated soil or sand are obtained. Then, in accordance with block 403 , water is added to the sample. Next, in accordance with block 405 , the sample is tested for optimum frequency of stimulation in order to separate the oil from the sand utilizing electrical and/or mechanical energy. In accordance with block 407 , the resonant frequencies are recorded. In accordance with block 409 , contaminated sand and water are added together in a container. Then, in accordance with block 411 , electrical and/or mechanical stimulating energy is applied to the container at the optimum excitation frequency. Next, in accordance with block 413 , the container is mechanically agitated in a gross manner. This may be obtained by utilizing any number of conventional shaking or mixing devices. Next, in accordance with block 415 , heat is added to the container. Then, in accordance with block 417 , the container is subjected to a centrifuge motion which helps to separate, in accordance with block 419 , the oil, sand, and water. In accordance with blocks 421 , 423 , 425 , the oil and water are collected, and the sand is returned to the beach area. | The present invention is directed to a method of utilizing the piezoelectric effect to transport a target substance within an earth formation. An earth formation is identified which bears a target substance. The piezoelectric properties of the earth formation are examined in order to determine the extent of the piezoelectric effect and to determine any optimum frequency of excitation. A voltage is applied to a particular portion of an earth formation in order to develop mechanical stress in the earth formation utilizing the piezoelectric property. The mechanical stress effects the local temperature and permeability of the target substance within the earth formation. A combination of excitation due to the electric field, mechanical stress, the temperature increase, serves to alter the permeability in a desired manner in order to liberate greater amounts of target substance from the earth formation, and to facilitate removal of the target substance utilizing conventional technologies such as pumps. Alternatively, and supplementally, a mechanical vibration and/or sonic energy source may be utilized to develop mechanical and electrical forces on the subsurface earth formation, to alter permeability of a target substance. | 4 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to adaptive modulation and coding methods and apparatus for use, for example, in wireless communication systems.
2. Description of the Related Art
FIG. 1 shows parts of a wireless communication system 1 . The system includes a plurality of base stations 2 , only one of which is shown in FIG. 1 . The base station 2 serves a cell in which a plurality of individual users may be located. Each user has an individual user equipment (UE). Only the user equipments UE 2 , UE 11 and UE 50 are shown in FIG. 1 . Each UE is, for example, a portable terminal (handset) or portable computer.
As is well known, in a code-division multiple access (CDMA) system the signals transmitted to different UEs from the base station (also known as “node B”) are distinguished by using different channelisation codes. In so-called third generation wireless communication systems a high speed downlink packet access (HSDPA) technique has been proposed for transmitting data in the downlink direction (from the base station to the UEs). In this technique a plurality of channels are available for transmitting the data. These channels have different channelisation codes. For example, there may be ten different channels C 1 to C 10 available for HSDPA in a given cell or sector of a cell. In HSDPA, downlink transmissions are divided up into a series of transmission time intervals (TTI) or frames, and a packet of data is transmitted on each different available channel to a selected UE. A new choice of which UE is served by which channel can be made in each TTI.
FIG. 2 shows an example of the operation of the HSDPA technique over a series of transmission time intervals TTI 1 to TTI 9 . As shown in FIG. 2 , in TTI 1 it is determined that two packets will be sent to UE 50 , four packets will be sent to UE 11 and four packets will be sent to UE 2 . Accordingly, two channels are allocated to UE 50 and four channels each are allocated to UE 11 and UE 2 . Thus, as shown in FIG. 1 , UE 50 is allocated channels C 1 and C 2 , UE 11 is allocated channels C 3 to C 6 , and UE 2 is allocated channels C 7 to C 10 .
In the next transmission time interval TTI 2 a new user equipment UE 1 is sent one packet, and the remaining UEs specified in TTI 1 continue to receive packets.
Thus, effectively the HSDPA system employs a number of parallel shared channels to transmit data in packet form from the base station to the different UEs. This system is expected to be used, for example, to support world wide web (WWW) browsing.
In the HSDPA system, channel state information (CSI) is made available to both the transmitter and the receiver, in order to realise a robust communication system structure. The HSDPA system is intended to increase the transmission rates and throughput, and to enhance the quality of service (QoS) experienced by different users. It transfers most of the functions from the base station controller (also known as the radio network controller or RNC) to the base transceiver station (node B).
The HSDPA system may also use a control technique referred to as an adaptive modulation and coding scheme (AMC) to enable the base station to select different modulation and/or coding schemes under different channel conditions.
The signal transmission quality for a channel between the transmitter and a receiver (UE) varies significantly over time. FIG. 3 shows an example of the variation of a signal-to-interference ratio (SIR) a downlink channel for four different users over a series of 5000 TTIs. This plot was obtained by a simulation. As illustrated, for a given UE the range of SIR values may be as much as from around +12 dB to −15 dB. The SIR value varies due to shadowing, Rayleigh fading, and change in distribution of the mobile UEs, as well as cellular area specifications including the propagation parameters and speeds of UEs.
FIG. 4 is a graph illustrating a relationship between a data transmission rate (throughput) and signal-to-interference ratio for four different modulation and coding combinations, also referred to as modulation-and-coding scheme (MCS) levels. The first three levels (MCS 8 , MCS 6 and MCS 5 ) are all quadrature amplitude modulation (QAM) schemes which differ from one another in the number (64 or 16) of constellation points used. The fourth level (MCS 1 ) uses quadrature phase shift keying (QPSK) as its modulation scheme.
Each level uses coding defined by a coding parameter which, in this example, is expressed as a redundancy rate R. For the first two levels MCS 8 and MCS 6 the redundancy rate R is 3/4, and for the third and fourth levels MCS 5 and MCS 1 the redundancy rate is 1/2.
As can be seen from FIG. 4 , for SIR values lower than around −4 dB MCS 1 (QPSK, R=1/2) is the best available option. The characteristic of this level is plotted with circles in the figure.
For SIR values in the range from around −4 dB to around +2 dB, MCS 5 (16QAM, R=1/2) provides the best transmission rate. The characteristic for this MCS level is illustrated by crosses in the figure.
For SIR values between around +2 dB and +8 dB MCS 6 (16QAM, R=3/4) provides the best transmission rate. The characteristic for this MCS level is illustrated by diamond points in the figure.
Finally, for SIR values greater than around +8 dB, MCS 8 (64 QAM, R=3/4) provides the best transmission rate. The characteristic of this combination is illustrated by square points in the figure.
In the HSDPA system a technique such as adaptive modulation and coding (AMC) is used to adapt the MCS level in accordance with the variations of the channel condition (e.g. SIR value).
According to the HSDPA standard (3GPP TS 25.214 V5.5.0 (2003-6)), each UE holds a channel quality indicator (CQI) mapping table. An example of the mapping table is shown in FIG. 5 . As the table shows, for each CQI value various parameters are defined including a transport block size, a number of codes, a modulation type, and a reference power adjustment Δ. The transport block size represents a maximum number of bits which can be received in one TTI. The number of codes is the number of channelisation codes which are sent simultaneously to a single user within one TTI. The modulation type represents the type of modulation scheme, eg QPSK or 16QAM. The reference power adjustment Δ is a reduction to be applied to the transmitted power if the transmitted power is greater than that necessary for the signal to be receivable at the CQI value.
Each UE produces a measure of the quality of a downlink channel from the base station to the UE. Based on this measure and on the CQI mapping table the UE reports the highest CQI value for which a signal having the transport block size, number of codes and modulation for that value is receivable with a transport block error probability (also referred to as a Packet Error Rate (PER)) below a certain target value.
There may be a one-to-one correspondence between the CQI values and MCS levels, so that if desired the base station may directly take the reported CQI value as the MCS level to apply. For example, in one proposal (3GPP TSGR1-02-0459, “HSDPA CQI proposal”, 9-12 Apr. 2002, Paris, France), there are CQI values 1 to 30 which are intended to provide approximately a 1 dB step size between adjacent MCS levels at 10% PER. Alternatively, the base station may employ the reported CQI value for each UE, as well as information relating to the system limitations and available MCS levels, to identify the most efficient MCS level for the particular UE.
Thus, based on the reported CQI values, UEs that have better channels or are located in the vicinity of the base station can employ higher levels of MCS and therefore enjoy higher transmission rates. Effectively, the result is a classification of the transmission rates based on the channel quality of each UE.
Ideally, each UE reports a CQI value in every TTI and the base station is capable of setting a new MCS level for each available channel in every TTI.
The HSDPA system may also employ a hybrid automatic repeat request (H-ARQ) technique.
FIG. 6 is a schematic diagram for use in explaining how the H-ARQ technique works. In this example, the technique is a so-called stop-and-wait (SAW) version of the technique. The figure shows packet transmissions in a single downlink channel HSPDSCH 1 over a series of successive TTIs, TTI 1 to TTI 9 . In TTI 2 a first packet is transmitted to UE 1 . Upon receiving a packet, each UE checks whether the transmission was error-free. If so, the UE sends an acknowledge message ACK back to the base station using an uplink control channel such as the dedicated physical control channel (DPCCH). If there was an error in the transmission of the received packet, the UE sends a non-acknowledge message NACK back to the base station using the uplink channel.
In the example shown in FIG. 6 , the first packet transmitted to UE 1 in TTI 2 fails to be received error-free, and accordingly some time later, in TTI 4 , UE 1 sends the NACK message to the base station. In the H-ARQ technique it is permitted for the next packet destined for a particular UE to be transmitted without waiting for the acknowledge or non-acknowledge message of a packet previously transmitted to the same UE. Thus, none of the transmission timeslots can go idle in the case of error-free channels, which gives the ability to schedule UEs freely. System capacity is saved while the overall performance of the system in terms of delivered data is improved.
For example, as shown in FIG. 6 , before the NACK message for the first packet of UE 1 is received by the base station, the base station transmits a second packet to UE 1 in TTI 4 . Thus, this second packet for UE 1 is transmitted before the first packet for UE 1 is retransmitted in TTI 7 in response to the NACK message for the first transmission of the first packet.
In the H-ARQ technique, an erroneously-received packet (failed packet) is subject to a so-called chase combining process. In this process a failed packet is resent by the transmitter and subsequently the receiver “soft” combines (for example using maximal ratio combining) all received copies of the same packet. The final SIR is determined as the sum of the respective SIRs of the two packets being combined. Thus, the chase combining process improves the SIR of the transmitted packets.
Further information regarding AMC and HARQ techniques may be found in 3GPP TR 25.848 V 4.0.0 (2001-03), Third Generation Partnership Project; Technical Specification Group Radio Access Network; Physical Layer Aspects of UTRA High Speed Downlink Packet Access (release 4), March 2001, the entire content of which is incorporated herein by reference.
The switching between different MCS levels has been recognised as a very critical task, and recently there have been various proposals for optimising this switching. For example, in TSG R1-1-0589, TSG-RAN Working Group 1 meeting no. 20, Busan, Korea, May 21 to 25, 2001, NEC and Telecom MODUS jointly proposed an AMC technique in which the thresholds for switching between different MCS levels are adjusted based on the ACK/NACK signalling from the UE. If NACK is signalled, the base station increases the thresholds by an upward amount S 1 . If ACK is signalled, the base station decreases the thresholds by a downward amount S 2 . The adjustments to the thresholds are limited and, for simplicity, the differences between thresholds may be fixed. The ratio between the upward amount S 1 and the downward amount S 2 may be determined based on the target error rate.
This AMC method adjusts the thresholds between MCS levels to try to take into account different operating conditions in the wireless communication system. In particular, the optimum MCS levels under any particular signal conditions depend on the Doppler frequency (i.e. the speed at which the UE is moving) and the multi-path propagation conditions. For example, FIG. 7 shows the effect of the UE speed on the throughput-vs.-SIR characteristic for each of the different MCS levels in FIG. 4 . Three lines are plotted per MCS level: the highest line corresponds to a low UE speed of 3 km/h (Doppler frequency Fd=5.555 Hz), the middle line corresponds to a medium UE speed of 60 km/h (Fd=111.112 Hz), and the lowest line corresponds to a high UE speed of 120 km/h (Fd=222.24 Hz). FIG. 7 shows that throughput declines as UE speed increases. It can also be seen that the optimum thresholds for switching between MCS levels are also changed as the UE speed changes.
FIG. 7 relates to a single-path Rayleigh fading mode. FIG. 8 shows the effect of different UE speeds under path conditions of two equal-gain paths. It can be seen that the characteristics are very different from FIG. 6 , and it is clear that the optimum thresholds are changed as the path conditions change.
The method proposed by NEC/Telecom MODUS changes the thresholds as the operating conditions change but the method does not provide a satisfactory solution as it increases or decreases the threshold each time an ACK or NACK message is received, i.e. every frame. When the step size between thresholds for switching MCS levels is significant (eg a few dB) this appears to result in relatively poor performance at lower MCS levels for path conditions in which there is effectively a single dominant path, for example in open countryside.
In another AMC method proposed by NEC and Telecom MODUS in TSG R1-1-0589 the base station selects a MCS level based on the ACK/NACK signalling from the UE. For example, the base station lowers the MCS level if NACK is received, and increases the MCS level if ACK is received successively for a certain number of TTIs. This method has the advantage that it does not rely on results of measuring the channel quality to select the MCS levels. Thus, problems of measurement accuracy and reporting delay are avoided. However, this method appears to have relatively poor performance at high SIR values when there are two paths of comparable strength, for example in an urban environment.
SUMMARY OF THE INVENTION
According to a first aspect of the present invention there is provided an adaptive modulation and coding method. The method comprises holding one or more adjustable values, each corresponding to at least one of a plurality of available modulation and coding levels applicable to a signal transmitted from a transmitter to a receiver, and each representing a change to the or each level to which it corresponds. One or more of the adjustable values is/are adjusted in dependence upon whether or not the signal is received successfully by the receiver. One of the available modulation and coding levels is selected to apply to the signal based on such an adjustable value.
Such an adaptive modulation and coding method can enable the appropriate modulation and coding level to be selected even when the path and channel conditions vary.
In one preferred embodiment, the holding, adjusting and selecting steps are carried out by the transmitter. Alternatively, however, the holding, adjusting, and selecting steps may be carried out by the receiver, with the receiver informing the transmitter of the selected modulation and coding level.
When the adjusting step is carried out in the transmitter, the receiver may transmit to the transmitter an indication of whether or not the signal was received successfully. The indication may be, for example, an ACK/NACK signal. The transmitter then adjusts one or more of the adjustable values in dependence upon the received indication.
In one embodiment, the adjustable values are held in a table which stores adjustable values corresponding respectively to all of the plurality of available modulation and coding levels. The table may be “seeded” by simply making each adjustable value equal to its corresponding one of the available modulation and coding levels. Thereafter, the adjustable values may be adjusted in dependence upon whether or not the signal is received successfully by the receiver.
With such a table, it is possible for each one of the adjustable values to be adjusted by a different amount, if desired, in the adjusting step. Alternatively, it is possible to adjust only some of the adjustable values in the adjusting step whilst leaving other values unchanged. Also, because all the adjustable values are held in the table, retrieval and updating of the values can be quick and efficient. For example, in a preferred embodiment, the receiver proposes one of the available modulation and coding levels based on a signal transmission quality, and the final modulation and coding level is selected based on the adjustable value corresponding to the proposed modulation and coding level. In this case, the proposed modulation and coding level can be used as an index to the table to simplify the selection of the corresponding adjustable value.
It is not necessary to use a table to hold the adjustable values. In another embodiment, one or more shared adjustable values are held. The or each adjustable value may correspond to more than one of the plurality of available modulation and coding levels. For example, one group of available modulation and coding levels sharing the same basic modulation type (e.g. QPSK) may have the same corresponding adjustable value, whereas another such group (e.g. levels having another modulation type such as 16QAM) may have another corresponding adjustable value. In this case, the or each adjustable value may be an offset value, with the final modulation and coding level being selected by applying the offset value to the modulation and coding level proposed by the receiver. The or each adjustable value may be set to 0 in an initialisation step, and thereafter be subject to adjustment in dependence upon whether or not the signal is received successfully by the receiver.
If the transmitter and receiver operate repetitively, for example on a time slot by time slot or frame by frame basis, then the adjusting and selection steps may be carried out per time slot or per frame. In this way, based on whether or not the signal was received successfully by the receiver in one time slot or frame, the adjustable values may be adjusted and a new modulation and coding level selected to apply to the signal transmitted in the next time slot or frame.
In one embodiment, the adjusting step comprises increasing one or more of the adjustable values when the signal is received successfully and decreasing one or more of the adjustable values when the signal is not received successfully.
In the adjusting step, at least one of the adjustable values may be increased by an amount different from an amount by which another one of the corresponding adjustable values is adjusted. This can be useful if, for example, the modulation and coding levels comprise two or more groups of levels such as one group of levels for QPSK modulation and another group of levels for 16QAM modulation. In this case, the adjustment amounts applied to one group may be made different from those applied to the other group.
Preferably, the or each adjustable value is a non-integer value. In the selecting step, a rounded version of the adjustable value may be employed to select the modulation and coding level to apply to the signal, the rounded version representing the nearest integer value to the non-integer adjustable value. In this way, although it is of course necessary to produce an integer value for the final selected modulation and coding level, the adjustable values can be maintained with a higher precision so that the most appropriate modulation and coding level is selected based on the prevailing path and channel conditions.
The receiver may produce a measure of signal transmission quality, for example a signal-to-interference and noise ratio. A fixed mapping may then be employed, either in the receiver or in the transmitter, to map this measure to a proposed modulation and coding level. For example, in one embodiment, the receiver produces a CQI value which it reports to the transmitter. This CQI value may have a one-to-one correspondence with the available MCS levels. In this case, the reported CQI value is used by the transmitter to select the adjustable value, and the selected adjustable value is then used to derive the final modulation and coding level.
The method may be used in a wireless communication system, in which case the transmitter may be a base station and the receiver may be a user equipment of the wireless communication system. The signal transmitted from the base station to the user equipment may be a downlink packet access signal. Alternatively, the transmitter may be a user equipment and the receiver may be a base station, and the signal transmitted from the user equipment to the base station may be an uplink packet access signal.
According to a second aspect of the present invention there is provided adaptive modulation and coding apparatus. The apparatus comprises an adjustable value holding unit which holds one or more adjustable values, each corresponding to at least one of a plurality of available modulation and coding levels applicable to a signal transmitted from a transmitter to a receiver, and each representing a change to the or each level to which it corresponds. The apparatus also comprises an adjusting unit which adjusts one or more of the adjustable values in dependence upon whether or not the signal is received successfully by the receiver. A selecting unit selects one of the available modulation and coding levels to apply to the signal based on such an adjustable value.
According to a third aspect of the invention there is provided a transmitter for use in a wireless communication system. The transmitter comprises an adjustable value holding unit which holds one or more adjustable values, each corresponding to at least one of a plurality of available modulation and coding levels applicable to a signal transmitted from the transmitter to a receiver of said system, and each representing a change to the or each level to which it corresponds. An adjusting unit adjusts one or more of the adjustable values in dependence upon whether or not the signal is received successfully by the receiver. A selecting unit selects one of the available modulation and coding levels to apply to the signal based on such an adjustable value.
The transmitter may be part of a base station or part of a user equipment of a wireless communication system.
According to a fourth aspect of the present invention there is provided a receiver for use in a wireless communication system. The receiver comprises an adjustable value holding unit which holds one or more adjustable values, each corresponding to at least one of a plurality of available modulation and coding levels applicable to a signal transmitted from a transmitter of the system to the receiver, and each representing a change to the or each level to which it corresponds. An adjusting unit adjusts one or more of the adjustable values in dependence upon whether or not the signal is received successfully by the receiver. A selecting unit selects one of the available modulation and coding levels based on such an adjustable value. A level informing unit transmits to the transmitter information specifying the selected modulation and coding level.
The receiver may be part of a base station or part of a user equipment of a wireless communication system.
According to a fifth aspect of the present invention there is provided an operating program which, when run on a processor in a transmitter of a wireless communication system, causes the transmitter to carry out the steps of: holding one or more adjustable values, each corresponding to at least one of a plurality of available modulation and coding levels applicable to a signal transmitted from the transmitter to a receiver of the system, and each representing a change to the or each level to which it corresponds; adjusting one or more of the adjustable values in dependence upon whether or not the signal is received successfully by the receiver; and selecting one of the available modulation and coding levels to apply to the signal based on such an adjustable value.
According to a sixth aspect of the present invention there is provided an operating program which, when run on a processor in a receiver of a wireless communication system, causes the receiver to carry out the steps of: holding one or more adjustable values, each corresponding to at least one of a plurality of available modulation and coding levels applicable to a signal transmitted from a transmitter of the system to the receiver, and each representing a change to the or each level to which it corresponds; adjusting one or more of the adjustable values in dependence upon whether or not the signal is received successfully by the receiver; selecting one of the available modulation and coding levels based on such an adjustable value; and transmitting to the transmitter information specifying the selected modulation and coding level.
In the fifth and sixth aspects of the invention, one of the transmitter and the receiver may be part of a base station of a wireless communication system, and the other of the transmitter and the receiver may be part of a user equipment of the system.
An operating program embodying the fifth or sixth aspect of the present invention may be provided by itself or may be carried by a carrier. The carrier may be a recording medium such as a disk or CD-ROM or may be a transmission medium such as a signal. The appended claims are to be interpreted accordingly.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 , discussed hereinbefore, shows parts of a wireless communication system employing a HSDPA technique for downlink transmissions;
FIG. 2 , also discussed hereinbefore, shows an example of the operation of the HSDPA technique in the FIG. 1 system;
FIG. 3 , also discussed hereinbefore, is a graph illustrating an example variation in signal-to-interference ratio of a downlink channel over a series of transmission time intervals for four different UEs in a wireless communication system;
FIG. 4 , also discussed hereinbefore, is a graph for use in explaining an adaptive modulation and coding technique;
FIG. 5 , also discussed hereinbefore, shows an example of a CQI mapping table;
FIG. 6 , also discussed hereinbefore, is a schematic diagram for use in explaining an automatic repeat request process;
FIG. 7 , also discussed hereinbefore, is a graph corresponding to FIG. 4 for illustrating how a UE speed affects operation of an adaptive modulation and coding technique;
FIG. 8 , also discussed hereinbefore, is another graph for illustrating how different path conditions affect the operation of an adaptive modulation and coding technique;
FIG. 9 is a schematic view of parts of a wireless communication system for explaining signalling used therein;
FIG. 10 is a schematic view of a table employed in a first embodiment of the present invention;
FIG. 11 is a flowchart for use in explaining an AMC method according to a first embodiment of the present invention;
FIG. 12 is a timing diagram relating to the operation of the first embodiment;
FIG. 13 is a schematic representation of a simulation model used for simulating performance of an embodiment of the present invention;
FIGS. 14 to 17 are graphs illustrating throughput versus channel quality characteristics for comparing operation of an AMC method embodying the present invention with conventional methods under different UE speed and path conditions;
FIG. 18 is a flowchart for use in explaining an AMC method according to a second embodiment of the present invention; and
FIG. 19 is a schematic representation of an AMC apparatus according to a third embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Before describing embodiments of the invention, reference is made to FIG. 9 which is a schematic view for explaining signalling in an HSDPA system.
For downlink signalling, three channels are used. A common pilot channel (CPICH) is used to broadcast a signal to all UEs in the cell served by the base station, in order to enable each UE to measure a downlink channel quality based on the CPICH signal. A high-speed downlink shared channel HS-DSCH is used to transmit packet data to a UE. A high-speed shared control channel HS-SCCH is used to carry transport format and resource related information (TFIR). This TFIR is, for example, 8 bits and includes information regarding a channelisation code, a MCS level, and a transport block size. The HS-SCCH also carries HARQ related information. This HARQ information is, for example, 12 bits and includes a HARQ process number, a redundancy version, a new data indicator, and a UE ID.
Uplink signalling is carried out using a high-speed dedicated physical control channel (feedback channel) HS-DPCCH. This channel is used to transmit a channel quality indicator (CQI) value and an HARQ acknowledgement (ACK/NACK).
An AMC method according to a first embodiment of the present invention will now be explained with reference to FIGS. 10 to 12 . This embodiment is used to adapt the MCS level of a downlink packet access signal in an HSDPA system. Thus, in this embodiment the transmitter is part of the base station and the receiver is part of the user equipment.
In the first embodiment the base station maintains, for each UE in its cell, a table of so-called “soft” MCS values. An example of the soft MCS value table is shown in FIG. 10 . The table 10 has an upper row 12 and a lower row 14 . The table is also divided into a QPSK region 16 made up of the first 16 columns of the table, and a 16QAM region 18 made up of the remaining 7 columns of the table.
The upper row 12 of the table contains the set of available CQI values. These CQI values correspond to the values 0 to 22 described previously with reference to FIG. 5 . In this embodiment, CQI values 23 to 30 are not available.
For each CQI value in the upper row 12 , there is a corresponding adjustable MCS value in the lower row 14 . For example, in FIG. 10 the soft MCS value 15.22 corresponds to the CQI value 16 .
The soft MCS values in the lower row 14 are adjustable in use of the base station in dependence upon the channel conditions experienced by the UE, as will now be explained with reference to FIG. 11 .
When a UE joins the cell served by the base station, in step S 1 a table of soft MCS values is created at the base station for the joining UE. The soft MCS values in the lower row 14 are initially set equal respectively to the corresponding CQI values in the upper row 12 . After the initialisation step S 1 is completed, the AMC method according to the first embodiment operates on a frame-by-frame basis, and in each downlink frame (TTI of 2 ms) steps S 2 to S 8 are carried out. Incidentally, the 3 GPP specifications also refer to a sub-frame as a period of 3 time slots (2 ms). In this case, steps S 2 to S 8 can be carried out per sub-frame.
In step S 2 , the UE produces a measure of downlink channel quality for the latest frame. This measure is, for example, based on the CPICH and represents a ratio of a received power Î or of the CPICH signal to background noise including interference I oc . The ratio Î or /I oc is a signal-to-interference ratio.
Using an internal mapping table such as that described previously with reference to FIG. 5 , the UE identifies the highest CQI value for which a single HS-DSCH sub-frame formatted with the transport block size, number of HS-PDSCH codes and modulation corresponding to the CQI value could be received with a transport block error probability not exceeding a target value. For example, the target transport block error probability may be 0.1.
For example, to identify the highest CQI value the measure of downlink channel quality may be compared with a set of values held by the UE for CQI value determination. There is one such threshold value for each pair of adjacent CQI values. These threshold values correspond to the threshold values Th 01 , Th 02 and Th 03 described above with reference to FIG. 4 . Based on the comparison, the highest available CQI value at which the transport block error probability target is achieved is identified.
Also in step S 2 the UE carries out a cyclic redundancy check (CRC) on the latest frame of the HS-DSCH signal. The CRC result (pass or fail) is needed to generate the ACK/NACK message but, as described below, it is also used for another purpose in the present invention.
The CRC result and the CQI value are reported by the UE to the base station using the HS-DPCCH.
In step S 3 , it is determined whether the reported CRC result was a pass (ACK) or fail (NACK). If the CRC result is a pass, processing proceeds to step S 4 . In step S 4 , each of the soft MCS values in the QPSK region 16 of the table is increased by a first upward adjustment amount ΔUpQPSK. Similarly, each of the soft MCS values in the 16QAM region 18 of the table is increased by a second upward adjustment amount ΔUp16QAM. Processing then proceeds to step S 6 .
If, on the other hand, in step S 3 the CRC result was a fail, then in step S 5 each of the soft MCS values in the QPSK region 16 of the table is decreased by a first downward adjustment amount ΔDownQPSK and each of the soft MCS values in the 16QAM region 18 of the table is decreased by a second downward adjustment amount ΔDown16QAM. Processing then proceeds to step S 6 .
In step S 6 , the CQI value reported by the UE in step S 2 is used as an index to the table 10 so as to identify the soft MCS value corresponding to the reported CQI value. For example, as shown in FIG. 10 , the soft MCS value 15 . 22 corresponds to the CQI value 16 . In step S 6 this soft MCS value is selected and rounded to the nearest integer, which in this case is 15. This value is taken as the next MCS level to be applied.
In step S 7 it is checked whether the next MCS level is within the permitted range of MCS levels. If the next MCS level chosen in step S 6 is lower than the lowest permitted MCS level then the next MCS level is simply set to the lowest permitted MCS level. Similarly, if the next MCS level selected in step S 6 is higher than the highest permitted MCS level then the next MCS level is set to the highest permitted MCS level.
Finally, in step S 8 the next MCS level determined in steps S 6 and S 7 is applied to the downlink signal transmitted to the UE in the next subframe.
FIG. 12 is a timing diagram for explaining the timing of the operations in FIG. 11 . As shown in FIG. 12 , in a first subframe n the UE receives data via the HS-DSCH using an initial or default MCS level. The UE then has a period of 7.5 time slots in which to process the data to produce the CRC result and the CQI value. Then, in an uplink subframe k, the CRC result (ACK/NACK) and the CQI value are reported to the base station via the HS-DPCCH.
The base station receives the reported ACK/NACK and CQI value for subframe n, and determines the next MCS level before the start of the next frame n+1. The base station then transmits the next data to the UE via the HS-DSCH in the next HS-DSCH subframe n+1 for that UE. As in the preceding frame, the UE has 7.5 time slots to process the received data to produce the CRC result and the CQI value. These are then reported back to the base station in the HS-DPCCH subframe k+1, and so on for subsequent subframes.
In steps S 4 and S 5 , ΔUp16QAM may be set in dependence upon a target packet error rate PER (transport block error probability). For example, if the target PER is 0.1,
Δ
Up
16
QAM
=
PER
1
-
PER
=
0.1
0.9
=
0.11
.
It was found empirically that suitable values for the other adjustment amounts are:
ΔDown16QAM=3*ΔUp16QAM=0.33
ΔUpQPSK=ΔUp16QAM/10
ΔDownQPSK=3*ΔUpQPSK
Next, some simulation results will be described to show how the performance of an AMC method embodying the present invention compares with that of previously-proposed techniques. The first previously-proposed technique which will be considered is the adaptive threshold technique described in the introduction in which the thresholds for switching between different MCS levels are adjusted based on the ACK/NACK results (hereinafter “prior art technique (1)”). The second previously-proposed technique is the further technique described in the introduction in which the base station selects a MCS level based on the ACK/NACK signalling from the UE (hereinafter “prior art technique (2)”).
The assumptions made in the simulations are set out in Table 1 below.
TABLE 1
Parameters
Values
Propagation conditions
1-Path Rayleigh/2-Path Rayleigh
Fading
Vehicle Speed for Fading
3,120 Kmph
CPICH power
10% of Tx Power at NodeB
DSCH power
80% of Tx Power at NodeB
HSDPA frame Length
2 ms
Spreading factor (SF)
16
Îor/Ioc
Variable
MCS update
1 frame (2 ms)
CPICH measurement delay
1 frame
MCS selection delay
1 frame
CPICH measurement error
Perfect Ch. Estimation
CPICH measurement report error rate
Perfect
Channel Estimation
Perfect Ch. Estimation
Fast fading model
Jakes spectrum
Channel coding
Turbo coding with 22 MCS levels
Tail bits
6
No. of iterations for Turbo Coder
8
Metric for Turbo Coder
Max
Input to Turbo Decoder
Soft
Number of Rake fingers
Equals number of Paths
Hybrid ARQ
None
Information Bit Rates (Kbps)
As shown in FIG. 5
Number of Multicodes Simulated
As shown in FIG. 5
STTD
Off
FIG. 13 is a schematic representation of the model used in the simulations. In particular, it is assumed that the fading is Rayleigh fading, the channel noise is Additive White Gaussian Noise (AWGN), the receiver measures the channel quality (Î or /I oc ) perfectly, and the reporting of the CQI value and CRC result is error-free.
FIGS. 14 to 17 each show a throughput versus downlink channel quality characteristic for an AMC method embodying the present invention (solid line), the prior art technique (1) (dot-dash line) and the prior art technique (2) (dashed line).
FIG. 14 assumes that the UE is moving at a low speed of 3 kph. It is also assumed that the path conditions prevailing between the base station and the UE are such that there is a single dominant path. This kind of path condition arises, for example, in open countryside, as opposed to urban environments.
FIG. 15 shows the corresponding results for the three techniques, again under single path conditions, but with the UE moving at a high speed of 120 kph. It can be seen from FIGS. 14 and 15 that the three techniques have more or less comparable performance under single-path conditions.
FIGS. 16 and 17 show results corresponding to those of FIGS. 14 and 15 but under two-equal-gain path conditions, as might prevail in an urban environment where there are many reflectors such as buildings. In FIG. 16 , the UE is assumed to be moving at the low speed of 3 kph, whereas in FIG. 17 the UE is assumed to be moving at the high speed of 120 kph. It can be seen that under two-equal-gain path conditions, a method embodying the present invention significantly outperforms both the prior art techniques (1) and (2). In particular, compared to the prior art technique (2) a method embodying the present invention provides approximately 118% throughput improvement at a UE speed of 3 kph and 230% throughput improvement at 120 kph when the received signal power to interference and noise ratio is 20 dB (Î or /I oc =20 dB).
From simulations it is believed that the prior art technique (1) tends to track the fading much more tightly than a method embodying the present invention which means that the spread of the distribution of selected MCS levels is larger in prior art technique (1) than in an embodiment of the present invention. Also, the mean selected MCS level in a method embodying the present invention was higher than that of prior art technique (1) in the two-path simulation at 120 kph with mean SINR of 25 dB, even though the PER was the same, so that a greater throughput is achieved in the embodiment.
In the first embodiment described with reference to FIGS. 10 to 12 , the UE reports the CRC result and the CQI level to the base station, and the base station holds the soft MCS values table, updates the table based on the CRC result and decides the next MCS level. However, it is not necessary for the soft MCS values to be held or updated in the base station, nor is it necessary for the next MCS level to be decided by the base station. It is possible for these operations to be carried out in the UE, as will now be described in relation to a second embodiment of the present invention shown in FIG. 18 .
In the second embodiment, the steps are the same as the steps S 1 to S 8 of the first embodiment except for the step S 2 which is replaced by a step S 12 and the step S 8 which is replaced by a step S 18 .
As in the first embodiment, in step S 1 a soft MCS values table is created when the UE joins the cell. In the second embodiment, this table is created inside the UE, rather than in the base station. In step S 12 , the UE produces the CRC result and a CQI value based on the latest received packet. Instead of reporting these to the base station at this stage, the UE itself carries out the steps S 3 to S 7 to select the MCS level for the next frame. Then, in step S 18 the UE reports the selected MCS level and the CRC result to the base station using the HS-DPCCH.
Incidentally, in order to avoid delay in the CRC result reaching the base station, it is possible for the UE to report the CRC result to the base station in step S 12 , prior to carrying out the processing of steps S 3 to S 7 .
In the first and second embodiments described above, the soft MCS values are produced using a table of soft MCS values as shown in FIG. 10 . The use of such a table has some significant advantages. Firstly, because the table stores the corresponding soft MCS value for each CQI value, it is possible to adjust the soft MCS values by different amounts, if desired. Thus, for example, instead of having a single upward and a single downward adjustment amount for all of the soft MCS values in the QPSK region 16 it would be possible to have individual adjustment amounts for each such soft MCS value. Alternatively, it would be possible to adjust only some of the soft MCS values in reaction to a particular CQI value, and leave others unchanged. Also, because all the soft MCS values are held in the table, retrieval and updating of the values can be quick and efficient. This is important as the processing power available may be limited, particularly in the case in which the table is held in the UE.
Nonetheless, despite these advantages, the requirement to hold the soft MCS values in table form may lead to an increased memory requirement, especially given that the soft MCS values are non-integer values. This disadvantage is overcome in a third embodiment of the present invention shown in FIG. 19 .
In FIG. 19 , in place of the soft MCS values table, two parameters OFFSET_QPSK and OFFSET — 16QAM are held and updated in respective offset units 22 and 24 . The offset unit 22 has an input connected to an output of a first selection switch 26 . The switch 26 has first and second inputs for receiving the first upward adjustment amount ΔUpQPSK and the first downward adjustment amount ΔDownQPSK respectively. The second offset unit 24 has an input connected to an output of a second selection switch 28 . The switch 28 has first and second inputs connected for receiving the second upward adjustment amount ΔUp16QAM and the second downward adjustment amount ΔDown16QAM respectively. Each of the switches is controlled by the CRC result from the UE (ACK/NACK). In particular, each selection switch 26 and 28 selects its first input when the CRC result is a pass (ACK) and selects its second input when the CRC result is a fail (NACK).
Each of the first and second offset units 22 and 24 also has a RESET input and an output. The output of the first offset unit 22 is connected to a first input of a third selection switch 30 . The output of the second offset unit 24 is connected to a second input of the switch 30 . An output of the switch 30 is connected to input of an adder 32 .
A CQI value receiving unit 34 is provided for receiving the latest CQI value produced by the UE. The latest received value is output by the unit 34 to another input of the adder 32 . The CQI value receiving unit 34 also produces a control signal QPSK/16QAM which controls the selection switch 30 . For example, when the latest CQI value held by the unit 34 is in the range from 0 to 15, the control signal QPSK/16QAM causes the switch 30 to select its first input, whereas when the latest CQI value is in the range from 16 to 22 the control signal QPSK/16QAM causes the selection switch 30 to select its second input.
An output of the adder 32 is supplied to an input of an MCS level range check/limit unit 36 . The unit 36 outputs the next MCS level.
Operation of the third embodiment shown in FIG. 19 will now be described.
Firstly, when the UE joins the cell, the RESET inputs of the first and second offset units 22 and 24 are activated so that the parameters OFFSET_QPSK and OFFSET — 16QAM are both reset to 0.
Then, in each frame, the CRC result is used to control the selection switches 26 and 28 so that either the upward adjustment amounts or the downward adjustment amounts are delivered to the inputs of the first and second offset units 22 and 24 . Each offset unit 22 or 24 adds the received adjustment amount to the parameter OFFSET_QPSK or OFFSET — 16QAM it holds. Note that the downward adjustment amounts are negative values in this embodiment.
Once the CQI value for the latest frame has been calculated, this is received in the CQI value receiving unit 34 . In dependence upon the received value, the CQI value receiving unit 34 generates the appropriate control signal QPSK/16QAM to control the selection switch 30 . Accordingly, the adder 32 either outputs the CQI value plus OFFSET_QPSK or the CQI value plus OFFSET — 16QAM. The MCS level range check/limit unit 36 checks whether the output value from the adder is within the permitted range (as in step S 7 of FIG. 11 ), limits the output value as appropriate, and outputs the value as the next MCS level.
Thus, in the third embodiment, even though there is no table of soft MCS values, each available MCS level still has a corresponding adjustable value (the parameter OFFSET_QPSK corresponding to MCS levels 0 to 15 , or the parameter OFFSET — 16QAM corresponding to MCS levels 16 to 22 ).
Although the embodiments described above have referred to only two types of modulation scheme, namely QPSK and 16 QAM, by way of example, it will be appreciated that embodiments of the present invention can be used with any suitable modulation schemes, including eight phase shift keying (8 PSK) and 64 quadrature amplitude modulation (64 QAM). The soft MCS values table can have as many regions as there are different modulation types. Alternatively, in the FIG. 23 embodiment, there can be as many offset units as there are different modulation types.
In the embodiments described above the transmitter was part of the base station and the receiver was part of the user equipment. However, in future networks it is likely that the user equipment will be capable of applying an AMC method to the uplink signals it transmits to the base station, in which case the methods of any of the preceding embodiments can be carried out with the transmitter being part of the user equipment and the receiver being part of the base station.
Although an example of the present invention has been described in relation to a wideband CDMA network having an asynchronous packet mode, it will be appreciated that the present invention can be applied to any other networks in which AMC can be used. These networks could be, or could be adapted from, other CDMA networks such as an IS95 network. These networks could also be, or be adapted from, other mobile communication networks not using CDMA, for example networks using one or more of the following multiple-access techniques: time-division multiple access (TDMA), wavelength-division multiple access (WDMA), frequency-division multiple access (FDMA) and space-division multiple-access (SDMA).
Those skilled in the art will appreciate that a microprocessor or digital signal processor (DSP) may be used in practice to implement some or all of the functions of the base station and/or user equipment in embodiments of the present invention. | In an adaptive modulation and coding method one or more adjustable values are created (S 1 ), each corresponding to at least one of a plurality of available modulation and coding levels applicable to a signal transmitted from a transmitter to a receiver, and each representing a change to the level(s) to which it corresponds. One or more of said adjustable values is/are adjusted in dependence upon whether or not the signal is received successfully by the receiver (S 2 -S 5 ). One of said available modulation and coding levels is selected (S 6 -S 8 ) to apply to the signal based on such an adjustable value. Such a method can enable the appropriate modulation and coding level to be selected even when the path and channel conditions vary. The method is applicable to selecting modulation and coding levels in a high-speed downlink packet access system of a wireless communication network. | 7 |
FIELD OF THE INVENTION
The present invention relates to a method of separating metal ions from pulps of lignocellulose-containing material. More particularly, the present invention relates to such methods in connection with the bleaching of such pulps with hydrogen peroxide or ozone, in which methods a main flow of pulp is treated with a chelating agent and washed prior to such bleaching.
BACKGROUND OF THE INVENTION
In present pulp mills, as well as those contemplated in the future, there are and will be liquid flows which are contaminated by various metal ions, which can disturb the bleaching reactions which take place during bleaching with hydrogen peroxide or ozone. These liquid flows occur, for example, during totally chlorine-free bleaching, so-called TCF-bleaching (TCF=Totally Chlorine Free), when the pulp is treated with chelating agents, such as EDTA or DTPA, in order to substantially reduce the metal ion content of the pulp prior to its bleaching with peroxide or ozone. This type of bleaching, in order to yield high ISO-brightness, requires that both the pulp and the process water be free or substantially free of certain metal ions since otherwise the charged hydrogen peroxide will effectively disintegrate to water and oxygen gas, and the charged ozone to oxygen gas, without having any simultaneous bleaching effect.
Particularly at those times when the pulp mill is closed, for example for environmental reasons, these liquids containing metal ions can be very difficult to deal with in order to prevent their contact with the bleaching step which would then deteriorate bleaching efficiency.
SUMMARY OF THE INVENTION
These and other objects have now been realized by the invention of a method of separating metal ions from a metal-ion and lignocellulose-containing material comprising treating the metal-ion and lignocellulose-containing material with a chelating agent in order to produce a flow of lignocellulose-containing material containing dissolved metal ions, washing the flow of lignocellulose-containing material containing the dissolved metal ions to produce a first washed flow of lignocellulose-containing material and a first liquid stream containing the metal ions, bleaching the first washed flow of lignocellulose-containing material with a bleaching agent selected from the group consisting of hydrogen peroxide and ozone so as to produce a flow of bleached lignocellulose-containing material, mixing the first liquid stream containing the metal ions with a second flow of lignocellulose-containing material so as to bind the metal ions to the second flow of lignocellulose-containing material, washing the second flow of lignocellulose-containing material to produce a second washed flow of lignocellulose-containing material and a second liquid stream substantially free of the metal ions, and washing the second wash flow of lignocellulose-containing material at a pH of less than about 3 to produce a third washed flow of lignocellulose-containing material in a third liquid stream containing the metal ions.
In accordance with one embodiment of the method of the present invention, the method includes separating the flow of bleached lignocellulose-containing material into a primary flow of bleached lignocellulose-containing material and a secondary flow of bleached lignocellulose-containing material, and the second flow of lignocellulose-containing material comprises the secondary flow of bleached lignocellulose-containing material.
In a preferred embodiment of the method of the present invention, the method includes combining the third washed flow of lignocellulose-containing material with the primary flow of bleached lignocellulose-containing material.
In accordance with another embodiment of the method of the present invention, the second flow of lignocellulose-containing material comprises the flow of bleached lignocellulose-containing material.
In accordance with another embodiment of the method of the present invention, the second flow of lignocellulose-containing material comprises a separate flow of lignocellulose-containing material circulated separately from the flow of bleached lignocellulose-containing material.
In accordance with another embodiment of the method of the present invention, the method includes recycling the liquid stream as a washing liquid in the method.
The aforementioned problems are solved by the present invention in that both the pulp and the process water are purified of metal ions in connection with the bleaching of the pulp with hydrogen peroxide or ozone.
According to the present invention, undesired metal ions, in a concentrated state, are ejected from the bleach plant, and at the same time the bleached pulp is substantially free of metal ions. Furthermore, process water separated from the pulp can be used as washing water without disturbing the bleaching process. A liquid flow containing the undesired metal ions in a concentrated state is separated and can be treated separately, or it can be discharged without causing serious damage to the environment. The metal ion content can thus be as low as about 100 g of manganese per ton of pulp. This corresponds to the metal amount normally discharged from pulp mills producing TCF-pulp.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention can be more fully appreciated with reference to the following detailed description, which, in turn, refers to the Figures in which:
FIG. 1 is a schematic flow chart of a method according to the present invention;
FIG. 2 is a schematic flow chart of another embodiment of the method of the present invention; and
FIG. 3 is a schematic flow chart of another embodiment of the method of the present invention.
DETAILED DESCRIPTION
Referring to the Figures, in which like reference numerals refer to like elements thereof, in the embodiment according to FIG. 1, a main flow 1 of unbleached pulp is supplied to a pre-treatment step 2 where the pulp is treated with a chelating agent such as EDTA or DTPA. Metal ions, preferably manganese, are thereby dissolved out of the pulp. In a subsequent first washing step 3, for example in the form of a washing press or washing filter, a liquid flow 4 is separated out containing the metal ions dissolved out of the pulp. The main flow 1, from which the metal ions are removed, is directed to a bleaching step 5 for bleaching with hydrogen peroxide or ozone. After the bleaching step, a partial flow 6 of the pulp is separated. This partial flow 6 constitutes a small portion, preferably from about 5 to 20%, and more preferably about 10% of the main flow 1.
To this partial flow 6 of the pulp, the liquid flow 4 containing metal ions is admixed, for example in a mixing device 7. By maintaining the pH above about 7, preferably above about 10, and most preferably at about 11 and 12, the metal ions are bonded to the pulp. Thereafter, the pulp in the partial flow 6 is washed in a second washing step 8, whereby the liquid phase 9 washed-out and free of the liquid can be re-used as washing water in the process. This liquid phase 9 will also contain the originally added chelating agent, because it is not bound by the pulp, but follows along with the liquid.
The partial flow 6 of the pulp, which now contains bound metal ions, is directed to a third washing step 10. Before washing, the pH is lowered to below about 3, and preferably to about 2.5, which can be brought about by the addition of sulfuric acid. The main part of the metal ions is hereby again released from the pulp and washed-out in the form of metal-containing waste water 11, which can be treated separately or be emitted to the recipient. This waste water corresponds to from about 1 to 2 m 3 per ton of pulp, based upon the total amount of the main flow of pulp. A special advantage from an environmental point of view is that the waste water 11 does not contain any chelating agent, because this material follows along with the liquid phase 9.
The main flow 1 of pulp is bleached with hydrogen peroxide or ozone in the bleaching step 5. After such bleaching, the pulp is washed in a washing step 12, whereafter the partial flow 6 of pulp free of metal ions is reunited with the main flow 1.
The liquid phase 9 free of metal ions can be used as washing liquid in the washing step 12. The waste water 13 from this washing step 12 can be recycled by being directed in a counter flow to the process, for example to a washing step 14 before the pre-treatment step 2.
EXAMPLE
The manganese content in a pulp delignified with oxygen gas was measured before and after the pre-treatment step 2, whereby the pH was varied by sulfuric acid addition during the treatment. The pulp concentration was 5%, the temperature 90° and the treatment time was 1 hour. The manganese content before the treatment was 61 g/ton of pulp. After the treatment, the following values were measured.
______________________________________pH 2.6 3.5 7.2 9.6 H.sub.2 SO.sub.4, kg/ton 10 5 2 0 Mn-content, g/ton 4.4 20 45 48______________________________________
It can thus be seen that the capability of the pulp to bind manganese ions varies with the pH value. According to the present invention, this relationship is being utilized to solve the problems encountered with metal ions in connection with peroxide and ozone bleaching.
The embodiment according to FIG. 2 is similar to the embodiment shown in FIG. 1, with the exception that no partial flow is separated from the main flow 1 of pulp. Instead, a separate pulp flow 15 is used in this case. This pulp flow 15 is directed in a separate circulation with second and third washing steps 8 and 10, whereby the pulp takes up the metal ions out of the liquid flow 4 and then emits the metal ions into the waste water 11.
A further embodiment of the present invention is shown in FIG. 3. In this case, the main flow 1 of the pulp is used for separating metal ions. The liquid flow 4 separated in the washing step 3 after the pre-treatment step 2 is recycled to the main flow of pulp in the washing step 16 downstream of bleaching step 5. In this case, the metal ions are bonded to the pulp in the manner described above in connection with FIG. 1. The liquid phase 17 washed out and free of metal ions can thus be re-used as washing liquid in the process, for example by being returned to the washing step 14 upstream of the pre-treatment step 2.
The main flow 1 of pulp thereafter passes through a further washing step 18 where the metal ions are separated from the pulp in the manner described above in connection with FIG. 1. The waste water 19 thereby washed out can be treated separately or be emitted to the recipient.
According to the last-mentioned embodiment, only one extra washing step 18 is required, compared with a conventional plant. The metal ion concentration in the waste water 19, however, is lower than that according to embodiments 1 and 2.
Although the invention herein has been described with reference to particular embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of the present invention. It is therefore to be understood that numerous modifications may be made to the illustrative embodiments and that other arrangements may be devised without departing from the spirit and scope of the present invention as defined by the appended claims. | Methods for separating metal ions from pulp material are disclosed including treating the pulp with a chelating agent to produce a pulp flow with dissolved metal ions, washing that pulp flow prior to bleaching with hydrogen peroxide or ozone and mixing the washed liquid containing metal ions with another flow of lignocellulose-containing material in order to bind the metal ions to that flow, washing that flow, and subsequently washing that flow at a reduced pH to produce a wash flow containing metal ions. | 3 |
BACKGROUND OF THE INVENTION
This invention relates to tobacco smoking and more particularly to an improved apparatus and method serving to achieve the effect of smoking without releasing second hand smoke into the surrounding area.
Tobacco was in use in the New World well before the arrival of Christopher Columbus. It is normally smoked in cigarettes or in a pipe or chewed or used in powder form as snuff. All of these modes of using tobacco are distasteful in some way or other, especially to non-smokers, due to second hand smoke, spitting of tobacco and its juices, etc. An important constituent of tobacco, nicotine, is also available as a drug and may be delivered in a chewable gum or as an arm patch, both by a physician's prescription. These systems for delivering the nicotine are not distasteful and they assist smokers to quit using tobacco but they are not satisfying as there is no associated pleasure as when the concentration of nicotine rises sharply in the bloodstream. The rapid transfer of any substance into the bloodstream is most quickly effected by a directed injection and inhalation is a close second, with eating and transdermal absorption tied for third place for speed of transfer. Often the rate at which the bloodstream concentration rises is critical to the perceived effect. This is why it is often difficult for cigarette smokers to switch to any other form of nicotine delivery. Cigarette smoke, unlike pipe or cigar smoke, is fully inhaled into the lungs so the effect is felt almost immediately. An unfortunate side effect of smoking cigarettes is that the smoker inhales into the lungs tars and other products of combustion which are subsequently exhaled as "second hand smoke". There is ample documentation that the smoking of cigarettes as well as prolonged exposure to second hand smoke makes the human body vulnerable to emphysema, heart disease and cancer.
Electric heating of tobacco for smoking is well known. U.S. Pat. No. 5,269,327 issued Dec. 14, 1993 to Mary E. Counts, et al. discloses a cigarette shaped article containing a plurality of charges of tobacco flavored medium equal to an average number of puffs per cigarette. The charges are individually heated electrically as the smoker puffs on the unit. The complexity of this device as well as the need for specialized tobacco charges are serious practical drawbacks.
It would be preferable if a compact and easy to use smoking article could employ tobacco in commonly available forms such as that provided for cigarettes, pipe tobacco, etc.
SUMMARY OF THE INVENTION AND OBJECTS
In accordance with this invention, there is provided a nicotine vaporizer for delivering to a consumer a volume of vapor containing nicotine, not more than the capacity of the consumer's lungs, derived from a microcharge of tobacco. The vaporizer comprises a housing configured in size to fit comfortably in the user's hand and serving to mount therein an electric battery power source. A compartment within the housing contains a supply of tobacco for consumption with the tobacco being metered into a firebox member having a cavity for receiving a microcharge of tobacco. An air suction tube extends into the housing with the inner end proximate to the firebox and electrical resistance wire means are arranged in the firebox cavity for engagement with the microcharge of tobacco. An electric circuit couples the resistance wire means with the power source for heating the microcharge of tobacco to a temperature serving to vaporize the nicotine such that the user's suction breath applied through the suction tube removes the nicotine vapors from the housing resulting from the tobacco's heating.
An object of the invention is to provide an electrical smoking article which operates to combust a microcharge of tobacco to produce a relatively consistent volume with each puff.
Another object of the invention is to provide such an article which consistently for each puff reaches its operating temperature quickly and remains at that temperature long enough to release the desired nicotine vapor while at the same time minimizing the consumption of energy.
Another object of the invention is to provide such an article which is self contained.
A further object of the invention is to provide such an article which has an appearance unlike a conventional cigarette or pipe and which generates neither second-hand smoke nor exterior ash, and is not hot between puffs.
A further object of the invention is to allow a smoker to achieve the pleasurable effects of smoking without annoying other people nearby or in locations where smoking is reserved.
Yet another object of the invention allows a cigarette smoker to enjoy the flavor of cigarette tobacco without expelling harmful or offensive smells such that when a person seated adjacent to a user of our invention will not be harmed even though such person may be allergic to cigarette smoke.
We have observed in the prior art for alternative smoking devices a good deal of effort has been made to avoid burning the tobacco with the objective to vaporize the nicotine having a boiling point of about 246° C. This we believe to be neither necessary or a useful step to avoid creation of second hand smoke. Second hand smoke is that smoke which a cigarette emits when it is not being inhaled upon as well as that smoke which remains in a smoker's windpipe and mouth following inhalation. Smoke which actually flows into the smoker's lungs is effectively filtered by the vast surface area of the lungs and is retained there. Thus it is an object of our invention that we provide a quantity of tobacco for burning whose smoke can be held in the lungs and contained entirely therein with no offensive vapor created upon exhalation.
Another object of the invention is to provide a nicotine vaporizer which meters the tobacco so that the puff of smoke created each time is no more than the lungs can process in one breath.
A further object of the invention is to provide a device of the type described which will deliver to the user just enough tobacco smoke to fill the lungs with each puff, the smoke produced giving the enjoyable effect to the user while preserving a smoke-free environment for bystanders.
Yet another object of the invention is to provide a device of the type described which is sized to fit the hands and has a general configuration and dimension of the conventional package of cigarettes.
The above and other objects and advantages of the invention will be apparent upon consideration of the following detailed description taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of the battery powered nicotine vaporizer of the present invention;
FIG. 2 is a sectional view taken in the direction of the arrows 2--2 in FIG. 1 but on a somewhat smaller scale and illustrating the vaporizer with its contents in place;
FIG. 3 is an elevational view of the nicotine vaporizer of FIG. 1 shown in the "open door contents removed condition";
FIG. 4 is a sectional view taken in the direction of the arrows 4--4 in FIG. 3;
FIG. 5 is an enlarged fragmentary sectional view of the lower portion of the vaporizer shown with the electric batteries removed and the firebox carrying slider member in the position for tobacco charging;
FIG. 6 is a view like FIG. 5 but with the firebox carrying slider member positioned in the condition for tobacco burning;
FIG. 7 is a view of the firebox carrying slider member taken in the direction of the arrows 7--7 in FIG. 5; and
FIG. 8 is an enlarged perspective view of the firebox carrying slider member.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
A battery powered nicotine vaporizer 10 made in accordance with and embodying the principles of the present invention is shown in FIGS. 1, 2 and 3 of the drawings. The nicotine vaporizer 10 includes a housing 11 containing a compartment 12 fitting a pair of AA size batteries 13 and a compartment 14 for receiving and holding a supply of tobacco 16. As shown in FIGS. 3 and 4, the housing 11 is equipped along one side with a closure or door 11a facilitating introduction of the batteries 13 and tobacco 16 into their respective compartments. The tobacco compartment 14 is also equipped with a pivotable closure door 17 with its open condition indicated in FIG. 4 by the broken line and arrows 18.
Preferably the housing 11 is fabricated from a metallic material so as to be electrically conductive being that the housing serves in the circuit which uses the power from the AA cells 13, arranged in parallel, to heat the tobacco in a manner to be discussed below to a combustion temperature. The closure 11a of the housing pivots to the open condition as shown in FIG. 4 and as indicated by the broken line and arrows 15. The closed position is shown in FIG. 1.
The battery compartment 12 is configured to retain snugly the batteries 13 and to this end there is provided a medial partition 19 arranged as shown in FIGS. 2 and 4, an electrically insulating spacer member 20, a spring mounted lower battery support 21 and an upper battery support 22. The battery supports 21 and 22 are formed from electrically conductive materials such as copper, brass or aluminum as is well understood by those skilled in the field and a flexible fabric strap 23 serves to assist in the removal of the batteries from their snug fit within the compartment 12. A non-conductive spacer member 24 arranged above the upper battery support 22 is provided with a conductive contact plate 26 positioned for engagement with a second contact plate 27 fixed at one end only to the housing 11 so as to be resiliently biased to remain out of contact with the first contact plate 26 when not urged there against through a finger-force applied through an actuation button 28, shown best in FIGS. 1 and 2. It will be understood that when the actuation button 28 is pressed the second contact plate 27 pivots into contact with the first contact plate 26 which is in circuit with the negative terminals of the battery pair 13.
A bulkhead 31 formed from non-conductive materials extends laterally of the housing 11 and defines the lower portion of the tobacco compartment 14, as shown in FIGS. 2, 5 and 6. The bulkhead 31 may be secured to the side walls of the housing 11 by fasteners 32. A vertical bore 33 extends between upper and lower surfaces of the bulkhead 31 and serve to receive a lower suction tube 34 which extends therefrom upwardly through the top wall of the housing 11, as shown in FIG. 2. An upper suction tube 36 equipped with a wooden mouth piece 37 is slidably received within the lower suction tube 34 in a substantially air-tight fit and as to be movable between an extended position as shown in FIGS. 1 and 2 to a retracted or out of the way position as shown in FIG. 3.
At the lower end of the bore 33 and downwardly from the end of the lower suction tube 34 a screen 38 is mounted in an associated recess in the bulkhead 31, as shown in FIGS. 5 and 6. The purpose of the screen 38 is to prevent burning embers from being sucked into the lower suction tube 34. A funnel-shaped tobacco delivery hole 39 is formed between the upper and lower surfaces of the bulkhead 31 so that by an external tap, tap, tap impulse tobacco may be urged downwardly through the delivery hole 39 into a slider member 41 so as to charge a firebox cavity 42 arranged therein. The tobacco delivery hole 39 is tapered preferably from about one centimeter at the top to about 5 mm diameter at the bottom so that if the slider member 41 is moved so that the firebox 42 is in registration therewith, tobacco falls through into the firebox fairly readily. The firebox 42 is preferably about 4 mm in diameter and about 2 mm deep and holds a microcharge of tobacco on the order of 3 mg. The slider 41 is preferably formed from a hard wood such as a maple burl from which pipe bowls are normally formed. A tongue 43 extends outwardly from a wall of the slider, as shown in FIG. 8, and is adapted to protrude from the housing 11 through a slot 44 arranged in one wall thereof, FIG. 1. The slot 44 forms a guideway for movement of the tongue when shifting the slider from the position of FIG. 5 for loading tobacco in the firebox 42 to the position shown in FIG. 6 where the tobacco in the firebox 42 is caused to combust by the heating coil 46 shown in FIG. 7. The slider 41 is guided in its movements along the bulkhead 31 by means of a bolt and washer 51 mounted in a slot 52 and secured at its end into the bulkhead 31 as shown in FIGS. 5 and 6. The bolt 51 ensures that the slider remains in contact with the bulkhead 31 in both the tobacco receiving and tobacco burning positions.
A combustion chamber 53 is defined at its bottom by the slider member 41 is in the position as indicated in FIG. 6 with the combustion chamber in communication through the screen 38 with the suction tube 34. A current of air is supplied into the combustion chamber 53 when a user is sucking air through the mouth piece 37, there being a plurality of apertures 54 in the wall of the housing 11 so that a draft of outside air enters the housing through the apertures 54 and course through the battery compartment 12 to the combustion chamber 53, the apertures 54 being clearly shown in FIG. 1.
It will be understood that the heater coil 46 mounted in the firebox 42 forms the grate of the combustion chamber 53 and the coil is formed preferably from a high resistance wire such as 0.4 mm diameter nichrome wire of about 2.5 cm in length. The heater coil 46 is wound into a tight double coil 56 and is coupled to an insulated copper conductor 57 which is grounded to the metallic housing 11 as shown in FIGS. 5 and 6. A second lead 58 from the coil 46 is in electrical contact with the lower battery support 21 which is held vertically from the bulkhead 31 by the spring 59. Pressure applied to the outside button 28 will cause the contact plate 27 to be depressed into engagement with contact plate 26 which is in circuit with the negative terminals of the batteries 13 thus supplying current to the heater coil 46 for combustion of the microcharge of tobacco for inhalation to the extents of approximately just less than the full lungful by the user of the vaporizer 10.
To use our invention, the smoker first extends the upper suction tube 36 from the housing and then shifts the protruding tongue 43 to the position shown in FIG. 1 wherein the slider 41 and the firebox 42 is positioned below the tobacco delivery hole 39. The smoker taps the unit 10 once or twice which causes tobacco leaves 16 to fall into the firebox 42 to the extent of approximately 3 mg. The smoker uses the tongue 43 to shift into the position at the end of the slot 44 thus moving the firebox to define a combustion chamber under the lower suction tube 34. The smoker then presses the button 28, pauses for a short period to preheat the charge, and then sucks on the mouthpiece 37. The heating coil 46 heats the charge in the combustion chamber as an air current moves past and through it and past the wire mesh screen caused by the smoker's inhalation through the screen 38 and suction tubes 34, 36. As the temperature of the tobacco leaves rise, water and other volatile organic compounds including nicotine vaporize. This is the beginning of smoke. Eventually combustion will occur but only if the smoker desires. Heating can be controlled by the smoker manipulating the button 28 and it should be noted here that since tobacco leaves only burn at the end of the process, the nicotine is already driven off by the time combustion occurs. Thus efficient and effective delivery of the nicotine is effected to the lungs. In ordinary cigarettes a substantial amount of nicotine just serves as fuel and burns partially creating noxious tars. In the vaporizer subject of the present invention, most of the nicotine reaches the lungs pure and in an unburned state.
When the smoker has finished the puff, he turns the vaporizer and taps the side nearest the suction tube. This empties the spent tobacco or ash into the ash pan cavity 59 below the bulkhead 31. The smoker then moves the tongue 43 to the position shown in FIG. 1 and taps the bottom of the unit to refill the firebox cavity with leaves. The vaporizer is now ready to provide the next puff.
While a particular embodiment of the present invention has been illustrated and described, it will be obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit of the scope of the invention. It is intended to cover in the appended claims all such modifications that are within the scope of this invention. | A nicotine vaporizer is provided with a housing with a battery compartment size for a pair of AA dry cells and a compartment for containing tobacco, a lower portion of which has a hole for passing tobacco into a firebox cavity arranged there below and shiftable from a tobacco receiving to a tobacco burning position. Electric coil means are set in the firebox cavity and energized to bring the tobacco to combustion temperature. A mouth piece equipped suction tube extends into the housing so that as air is withdrawn through the suction tube with the coil energized the tobacco will combust as to the microcharge contained in the firebox cavity. The microcharge of tobacco is of such volume that no more smoke is created than can be processed by the lungs in one breath. | 0 |
BACKGROUND OF THE INVENTION
The present invention relates to an apparatus for instructing an operator to displace a gearshift to its optimum shift position so that the gears in a manual transmission are located in an optimum position, and more particularly to an apparatus for instructing an operator to displace a gearshift to its optimum upshift position so that the gears in a manual transmission are located in an optimum position in accordance with various running conditions of the vehicle.
It has been proposed that to achieve minimum fuel consumption in a vehicle equipped with a manual transmission, an operator should determine when to shift the transmission in accordance with observed values from a speedometer or a tachometer. A proposed apparatus instructs an operator to upshift to an optimum gearshift position to achieve the goal of minimum fuel consumption. According to this proposed apparatus, an upshift zone is predetermined by the parameters of engine speed (RPM) and an engine load. The apparatus is designed to detect the engine speed and the engine load, and subsequently instruct an operator to shift the manual transmission to its optimum location by using an indicator means when the parameters of engine speed and engine load fall within the upshift zone. This upshift zone comprises an area where the actual engine speed is greater than a predetermined engine speed and the actual engine load is less than a predetermined engine load. An apparatus which uses the aforementioned upshift zone instructs the operator to upshift when the vehicle is started or when the vehicle is accelerating. Further, when the vehicle is decelerating or idling, the apparatus is designed to instruct an operator that an upshift would be improper. Additionally, when a throttle valve opens only slightly, the apparatus is designed to instruct an operator that an upshift is necessary.
However, the aforementioned apparatus has the following disadvantages. When a vehicle maintains a certain vehicle speed, such as when coasting on a gentle downhill grade, an engine brake may take effect to slow the vehicle, resulting in the throttle valve slightly opening. Hence, the apparatus detects the slight opening of the throttle valve and instructs the operator that the transmission should be upshifted even though the engine is acting as a brake for the vehicle.
Further, according to the aforementioned apparatus, an improper upshift instruction issues at other specific running conditions, such as when the load on the engine is large (created by, for example, the vehicle climbing an incline) or when the vehicle is accelerating. Additionally, when a stroke of an accelerator pedal temporarily decreases to lower the speed of the vehicle, the engine speed slowly decreases, but results in a rapid decrease of the engine load. This causes the apparatus to issue an upshift signal because the engine operating parameters are within the upshift zone. However, if an uphill incline was to continue, the upshift instruction would be improper.
SUMMARY OF THE INVENTION
The present invention was made in view of the foregoing background and to overcome the foregoing drawbacks. It is accordingly an object of this invention to provide an apparatus for instructing an operator to place a gearshift in an optimum position under various operating parameters including when the vehicle experiences a gentle downhill grade or when the vehicle is accelerating under a large engine load.
To attain the above objects, an apparatus according to the present invention instructs an operator to place a gearshift of a manual transmission in an optimum position in accordance with various operating parameters. An upshift zone is formulated by predetermined parameters of engine speed (RPM) and parameters representing engine load. The upshift zone is stored in a memory means. When operating parameters of the vehicle fall within the memorized upshift zone, a counter begins to count a predetermined amount of time from the time when the operating parameters first fall within the upshift zone. After the predetermined amount of time lapses, an indicator means instructs the operator to upshift the manual transmission if the actual operating parameters are still within the predetermined upshift zone.
BRIEF DESCRIPTION OF THE DRAWINGS
The above objects, features and advantages of the present invention will become more apparent from the following description of the preferred embodiments taken in conjunction with the accompanying drawings, wherein:
FIG. 1 is a schematic view of an electric circuit employed in an apparatus according to the present invention;
FIG. 2 is a diagrammatic view illustrating an electric pulse for controlling the amount of fuel injected into the engine;
FIG. 3 is a diagrammatic view illustrating an upshift zone for a vehicle utilizing a manual transmission;
FIG. 4 is a flow chart of a main routine employed in the apparatus according to the present invention;
FIG. 5 is a detailed flow chart determining a gearshift position according to a first embodiment of the present invention;
FIG. 6 is a detailed flow chart for determining when to issue an upshift instruction according to the first embodiment of the present invention;
FIG. 7 is a detailed flow chart determining a gearshift position according to a second embodiment of the present invention; and
FIGS., 8a and b are a detailed flow chart for determining when to issue an upshift instruction according to the second embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention is described in detail with reference to the accompanying drawings which illustrate different embodiments of the present invention.
Referring to FIG. 1, a battery 2, which is installed as an electric power source in a vehicle, has a negative terminal connected with a ground in the vehicle and a positive terminal connected through an ignition switch 4, a reversing light lamp switch 8 and a reversing light lamp 10 to the ground of the vehicle. The reversing light lamp switch 8 is actuated by an operator selecting a reverse gear in a manual transmission installed in a vehicle. The ignition switch 4 is connected through an indicator lamp 12 to a collector of a transistor 14. An emitter of the transistor 14 is connected to an outlet port of a microcomputer 16. The microcomputer 16 calculates the proper time for shifting the manual transmission. The microcomputer 16 is connected with an interface 18 which outputs data into the microcomputer 16. The interface 18 is fed by at least six inputs, a first of which is connected with a point positioned between the reversing light lamp switch 8 and the reversing light lamp 10. A second input comes from a clutch switch 20, a third from an engine idle switch 22, a fourth from a vehicle speed sensor 24, a fifth from an engine coolant temperature switch 26 and a sixth from a computer 28, which electronically controls the fuel injection system.
The reversing light lamp switch 8 is mounted at a position adjacent to a gearshift lever (not shown in drawings) for the manual transmission, and is actuated when the shift lever is positioned in reverse gear. When the engine is running, and the reversing light lamp switch 8 is actuated, an ON signal is inputted through the battery 2, the ignition switch 4 and the reversing light lamp switch 8, to the interface 18. The clutch switch 20 is connected to the ground of the vehicle at one end thereof and to the interface 18 at another end thereof, when a clutch pedal (not shown in drawings) is depressed, the clutch switch 20 is actuated. The engine idle switch 22 is connected to the ground of the vehicle at one end thereof and to the interface 18 at another end thereof and is actuated when a throttle valve 32 mounted in a throttle body 30, is fully closed. The vehicle speed sensor 24 has a rotary magnet 24A and a lead switch 24B therein. The rotary magnet 24A is fixed to a speedometer cable (not shown in drawings). The lead switch 24B is connected to the ground of the vehicle and opens and closes four times for every revolution of the speedometer cable. The engine coolant temperature switch 26 is connected to the ground at one end thereof and is mounted within an engine cylinder block (not shown in drawings). The engine coolant temperature switch 26 is actuated when the engine coolant temperature is less than or equal to a predetermined temperature, for example, 50° C. The output from the engine coolant temperature switch 26 is fed into the interface 18.
An air flow meter 34, a first crank angle sensor 38 and a second crank angle sensor 40 are connected to the computer 28. The air flow meter 34 detects the amount of air suctioned into the engine. The first and second crank angle sensors 38 and 40 are provided on a distributor 36. The computer 28 calculates a basic amount of an injected fuel based upon the amount of air taken into the engine and the engine speed, and adjusts the basic amount of fuel injected into the engine, in accordance with the engine coolant temperature and the intake air temperature to obtain a final adjusted amount of fuel to be injected. The final adjusted amount of injected fuel is injected through a fuel injection valve, according to a pulse generated by the computer 28. The amount of fuel needed to be injected is determined by the pulse width generated by the computer 28. This fuel injection pulse controls the fuel injection valve per every predetermined crank angle. A pulse width signal (TP) for the fuel injection is inputted to the interface 18. The pulse width signal TP has a waveform such as that shown in FIG. 2. The pulse width is in approximate proportion to the amount of load experienced by the engine. An interval L between pulses is equivalent to a period for revolution of the engine. Hence, the load on the engine is small when a narrow pulse width is inputted and conversely, the load on the engine is large when a wide pulse width is inputted.
The microcomputer 16 includes a read-only memory (hereinafter referred to as ROM). The ROM has a memory which stores a map illustrating an upshift zone, such as the one shown in FIG. 3, specific gear ratios of the manual transmission and various other programs assisting in the operation of the vehicle.
The upshift zone shown in FIG. 3, is determined by the engine speed (RPM) and the pulse width, which corresponds to the amount of load on the engine. The upshift zone is defined in an area where the engine speed is greater than or equal to 1500 RPM.
FIG. 4 shows a main flow chart of a program employed in the first and second embodiments of the present invention. FIGS. 5 and 6 show flow charts of programs employed in the first embodiment of the present invention. In FIG. 4, a step 42 initiates various kinds of timers such as T G , T A , T B , T C , T M and T up upon the actuation of the ignition switch 4. The timer T G counts the amount of elapsed time from the moment when a gearshift position of a manual transmission is determined. The timer T A counts the amount of elapsed time from the moment when the vehicle commences to accelerate under a large engine load. The timer T B counts the amount of elapsed time from the moment when the throttle valve commences to be fully closed. When the throttle valve is fully closed, the engine brake is effected. The timer T C counts the amount of elapsed time from the moment when the engine brake is released. The timer T M counts the amount of elapsed time from the moment when the throttle valve commences to be opened from the fully closed position within the upshift zone. The timer T up counts the amount of time that the operative parameters of the vehicle place the manual transmission in the upshift zone.
The program then proceeds to a step 43, wherein the frequency f TP of the engine speed is calculated from the interval between consecutive TP signal pulses. The program proceeds to a step 44, wherein the frequency f v of the vehicle speed signal is calculated by counting the pulse signal of the vehicle speed sensor 24. The program then proceeds to a step 45, wherein the ON or OFF signal from the reversing light lamp switch 8, the clutch switch 20, the engine idle switch 22 and the engine coolant temperature switch 26 are read. The program proceeds to a step 46, wherein the present gear ratio R of the manual transmission is calculated from the frequency f TP of the engine speed and the frequency f v of the vehicle speed signal. Further, the actual gear ratio is calculated and compared with the specific gear ratios stored in the memory of the ROM, and the position of the gearshift is determined. The program proceeds to a step 47, wherein the engine load is determined by measuring the width of the pulse signal TP, and the determination is made of whether the present driving condition is positioned within the upshift zone shown in FIG. 3, as determined by the measured pulse width. The program proceeds to a step 48, wherein the determination is made of whether the actual driving condition is located within the memorized upshift zone based on the frequency f TP of the engine revolution and the pulse width signal TP as was measured in the step 47. The frequency f TP of the engine revolution is equal to the engine speed. Further, the determination of whether an instruction to upshift the transmission should be made, and an upshift flag F up is either set or reset. The program proceeds to a step 49, wherein according to the condition of the upshift flag F up , a high or low level signal is outputted to the transistor 14. When a high level signal is outputted to the transistor 14, a base electric current flows in the transistor 14 and the indicator lamp 12 is actuated. This indicator lamp 12 instructs the operator to upshift the manual transmission. Conversely, when a low level signal is outputted to the transistor 14, the base electric current does not flow in the transistor 14 and the indicator lamp 12 is not actuated.
FIG. 5 shows a detailed flow diagram of the functions performed in step 46 of FIG. 4 which determines the appropriate position for the gearshift. In a step 51, the gear ratio R is calculated by the following equation:
R=a·(f.sub.TP /f.sub.V) (1)
where, "a" is a contant
In steps 52 through 56, the calculated gear ratio R is compared with the specific gear ratios (1st through 5th) stored in the memory of the ROM. If the value of the calculated gear ratio R is within the predetermined permissible scope (for example, ±5%) of the stored specific gear ratios of the manual transmission, the actual gearshift position (one of 1st-5th) is stored in a register P in any one of the appropriate steps 57 through 61. Thus, when the value of the actual calculated gear ratio R is within the predetermined permissible scope, the gearshift position is determined.
If the position of the gearshift cannot be determined by the above-mentioned steps, the program proceeds to a step 62, wherein the timers T G and T B are reset to zero. The timer T G counts the amount of time elapsed from the moment when the gearshift position of the manual transmission is determined. The timer T B counts the amount of time elapsed from the moment when the throttle valve commences to be fully closed. The program proceeds to a step 63, wherein the value stored in the register P is converted to a predetermined value, for example, zero. When the register P is caused to store the predetermined value, this procedure means that the gearshift position has not been determined for the presently occurring driving conditions. However, when the gearshift position is determined by any one of the steps 57 through 61, the program proceeds to a step 64. In the step 64, the determination is made of whether or not the counted value of time on the timer T G is greater than a predetermined value (for example, 0.1 seconds). If the counted value of time on the timer T G is greater than the predetermined value, the program proceeds to a step 65, wherein the determination is made of whether or not the throttle valve is fully closed. When the throttle valve 32 is fully closed, the engine brake is effected. However, if the counted value of time on the timer T G is less than or equal to the predetermined value in the step 64, the program proceeds to the step 63, wherein the value stored in the register P is converted to a predetermined value, for example, zero. But, when the step 65 determines that the throttle valve 32 is at least partially open, the program proceeds to a step 66, wherein the timer T B is reset to zero. The program proceeds to a step 68, wherein the timer T C , which counts the amount of elapsed time from the moment when the engine brake is released, is reset to zero. The program then proceeds to a step 69. In the step 69, it is determined whether or not the counted value of time on the timer T B is greater than a predetermined value, for example, 0.5 seconds. If the counted value of time on the timer T B is greater than the predetermined value, the program proceeds to a step 70. In the step 70, an engine brake flag F B is set. The engine brake flag F B is set in such condition that after a predetermined amount of time elapses after the gearshift position has been determined, and after a predetermined amount of time elapses with the throttle valve being fully closed for the entire period, it is determined that the effect of the engine acting as a brake has occurred. The program then proceeds to a step 72.
However, if the step 65 has determined that the throttle valve was not fully closed, it would have proceeded to a step 67. In the step 67, the determination is made of whether or not the counted value of time on the timer T C is greater than a predetermined value (for example, 0.5 seconds). If the counted value of time on the timer T C is greater than the predetermined value, the program proceeds to a step 71. In the step 71, the engine brake flag F B is reset. If the counted value of time on the timer T C is less than or equal to the predetermined value, the program proceeds to a step 72. In the step 72, the value of the register P is stored in a predetermined area M P of the RAM.
FIG. 6 discloses a detailed flow diagram of the functions performed in the step 48 of FIG. 4, according to the first embodiment, which determines whether the actual driving condition is located within the memorized upshift zone. In a step 81, it is determined whether actual present pulse width signal TP and the actual engine speed fall within the upshift zone shown in FIG. 3. If the present driving conditions do not fall within the upshift zone, the program proceeds to a step 82, wherein the timer T up , which counts the amount of time that the operating parameters of the vehicle cause it to be in the upshift zone, is reset to zero. The program then proceeds to a step 83. In the step 83, the timer T M , which counts the amount of elapsed time from the moment when the throttle valve 32 commences to be opened from the fully closed position within the upshift zone, is reset to zero and the program proceeds to a step 84. The timer T M is adjusted to count an amount of time elapsed from the moment when the throttle valve 32 is first opened from the fully closed position with the engine brake flag F B being set in the upshift zone. However, if the actual present driving conditions fall within the upshift zone, the program proceeds from the step 81 to a step 80. In the step 80, it is determined whether or not the throttle valve 32 is fully closed. If the throttle valve 32 is not fully closed, the program proceeds to a step 85. In the step 85, it is determined whether or not the counted value of time on the timer T up is greater than a predetermined value (for example, 0.2 seconds). If the counted value of time on the timer T up is less than the predetermined value, the program proceeds to a step 83. In the step 83, the timer T M is reset to zero and the program proceeds to a step 84. However, if the counted value of time on the timer T up is greater than the predetermined value, the program proceeds from the step 85 to a step 86. In the step 86, it is determined whether or not the engine brake flag F B is not equal to 1. If the engine brake flag F B is not equal to 1, the program proceeds to a step 87. In the step 87, the timer T M is cleared, and the program proceeds to a step 91. However, if the engine brake flag F B is equal to 1, the program proceeds to a step 88. In the step 88, it is determined whether or not the pulse width signal TP is greater than a predetermined value (for example, 1.6 milliseconds) at its upper limit of the upshift zone. If the pulse width signal TP is greater than or equal to the predetermined value at its upper limit thereof, the program proceeds to a step 89, wherein it is determined whether or not the counted value of time on the timer T M is greater than a first predetermined value (for example, 1 second). However, if the pulse width signal TP is less than the predetermined value at its upper limit of the upshift zone, the program proceeds from the step 88 to a step 90. In the step 90, it is determined whether or not the counted value of time on the timer T M is greater than or equal to a second predetermined value (for example, 2 seconds). The second predetermined value is larger than the first predetermined value. If it is determined that the counted value of time on the timer T M is less than the second predetermined value, in the step 90, the program proceeds to a step 96, wherein the value of the timer T C is reset to zero. The program proceeds from the step 96 to a step 84. In the step 84, the upshift flag F up is reset.
When the pulse width signal TP is narrow, this condition may mean that the operator has temporarily opened the throttle valve 32, while still maintaining the effect of the engine brake and the operator desires to maintain the effect of the engine brake. Conversely, when the pulse width signal TP is wide, this condition may means that the pedal has been depressed a large amount and the operator does not desire the effect of the engine brake any longer. Hence, the first predetermined value is designed to be smaller than the second predetermined value. When a short amount of time elapses from the condition when the throttle valve 32 is opened within the upshift zone, the upshift flag F up is reset.
The reason why the timer T C is cleared in the step 96 is to prohibit the engine brake flag F B from being lowered when the timer T M commences to count the amount of time when the value of the engine brake flag F B being equal to 1, and to recount the amount of time counted by the timer T C after the predetermined time has elapsed, and to lower the engine brake flag F B unless the throttle valve 32 is fully closed during 0.5 second time period.
In the step 91, the upshift flag F up is set. When the engine brake is not effected within the upshift zone, or when the predetermined time elapses with the throttle valve 32 open, the upshift flag F up is set. As apparent from the above-described explanation, the upshift flag F up does not set whenever the throttle valve 32 temporarily opens.
In a step 92, it is determined whether the present gearshift position is in the position of the highest gear ratio (for example, 5th position) in view of the gearshift position memorized in the predetermined area M P stored in the RAM. When the actual present gearshift position is not in the position of the highest gear ratio, the program proceeds to a step 93, wherein it is determined whether or not the detected engine coolant temperature is lower than a predetermined temperature (for example, 50° C.). If the engine coolant temperature is not lower than the predetermined temperature, the program proceeds to a step 94. In the step 94, it is determined whether or not the vehicle speed detected by the vehicle speed sensor is less than or equal to a predetermined speed (for example, 5 km/h). If the detected vehicle speed is greater than the predetermined speed, the program proceeds to the step 49. The rationale for providing the steps 92 through 94 is as follows: When the actual present gearshift position is in the position of the highest gear ratio in the step 92, the manual transmission cannot obtain any higher gearshift positions. When the vehicle speed is less than the predetermined speed, in the step 94, it becomes apparent that the present driving condition is not in the upshift zone, regardless of any other parameters which are calculated. Further, when the engine coolant temperature is lower than the predetermined temperature set in the step 93, it also is not proper to upshift the transmission because the engine coolant temperature is too low. According to the first embodiment, the instruction of the upshift is not made when the reversing light lamp switch 8 is actuated or when the clutch swing 20 is actuated, because an upshift would not be proper in either of these circumstances.
FIG. 7 discloses a detailed flow diagram of the functions performed in the step 46 of FIG. 4, according to a second embodiment of the present invention, which determines the appropriate position for the gearshift. In a step 151, the gear ratio R is calculated by the steps shown in equation (1). In steps 152 through 156, the calculated gear ratio R is compared with the specific gear ratios (1st through 5th) stored in the memory of the ROM. If the calculated gear ratio R is a value within a predetermined permissible scope (for example, ±5%) of the specific gear ratios for the manual transmission stored in the actual ROM, gearshift position (one of the 1st-5th) is memorized in a register P in any one of the steps 157 through 161. Thus, when the calculated gear ratio R is a value within the predetermined permissible scope, the gear shift position is positively determined.
If the gearshift position is not positively determined by any of the above steps, the program proceeds to a step 162, wherein the timers T G and T A are reset to zero. The timer T G counts the amount of elapsed time from the moment when a gearshift position of the manual transmission is determined. The timer T A counts the amount of elapsed time from the moment when the vehicle commences to accelerate under a large engine load. The program then proceeds to a step 163. In the step 163, the value stored in the register P is converted to a predetermined value, for example, zero. When the register P is caused to store the predetermined value, this procedure means that the gearshift position has not been determined for the presently occurring driving conditions. However, when the gearshift position is determined by any one of the steps 157 through 161, the program proceeds to a step 164. In the step 164, the determination is made of whether or not the counted value of time on the timer T G is greater than a predetermined value (for example, 0.1 seconds). If the counted value of time on the timer T G is greater than the predetermined value, the program proceeds to a step 165. In the step 165, it is determined whether or not the pulse width signal TP is greater than a predetermined time (for example, 2.2 milliseconds). Because the pulse width signal TP is proportional to the load on the engine, the step 165 predetermines whether or not the engine load is greater than a predetermined value. If the counted value of time on the timer T G is less than or equal to the predetermined value in the step 164, the program proceeds to a step 163. If the pulse width signal TP is less than the predetermined value set forth in the step 165, the program proceeds to a step 166, wherein the timer T A is reset to zero. The program then proceeds to a step 167. When the determination is made in the step 165, that the pulse width signal TP is greater than or equal to the predetermined value, the program proceeds to a step 168. In the step 168, the timer T C , which counts the amount of elapsed time from the moment when the engine brake is released, is reset to zero. The program proceeds to a step 169, wherein it is determined whether or not the counted value of time on the timer T A is greater than a predetermined value (for example, 1 second). If the counted value of the timer T A is greater than the predetermined value, the program proceeds to a step 170, wherein the acceleration flag F acc is set. The program then proceeds to a step 172. However, if the counted value of time on the timer T A is less than or equal to the predetermined value in the step 169, the program directly proceeds to the step 172 and by-passes the step 170.
In the step 167, which can be reached after either of the steps 163 or 166, the determination is made of whether or not the amount of time on the timer T C is greater than a predetermined value (for example, 0.5 seconds). If the counted amount of time on the timer T C is greater than the predetermined value, the program proceeds to a step 171. In the step 171, the acceleration flag F acc is reset. If the amount of counted time on the timer T C is less than or equal to the predetermined value, the program proceeds to a step 172, wherein the value of the register P is stored in the predetermined area M P .
FIG. 8 discloses a detailed flow diagram of the functions performed in the step 48 of FIG. 4, according to the second embodiment, which determines whether the actual driving condition is located within the memorized upshift zone. In a step 181, it is determined whether the actual present pulse width signal TP and the actual engine speed fall within the upshift zone shown in FIG. 3. If the present driving conditions do not fall within the upshift zone, the program proceeds to a step 182, wherein the timer T up , which counts the amount of time that the operating parameters of the vehicle cause it to be in the upshift zone, is reset to zero. The program then proceeds to a step 183. In the step 183, the timer T M , which counts the amount of elapsed time from the moment when the throttle valve 32 commences to be opened from the fully closed position within the upshift zone, is reset to zero and the program proceeds to a step 184. The timer T M is adjusted to count an amount of time elapsed from the moment when the throttle valve 32 is first opened from the fully closed position with the engine brake flag F B being set in the upshift zone. However, if the actual present driving conditions fall within the upshift zone, the program proceeds from the step 181 to a step 185. In the step 185, it is determined whether or not the amount of time counted on the timer T up is greater than a predetermined value (for example, 0.2 seconds). If the counted amount of time on the timer T up is less than or equal to the predetermined value, the program proceeds to a step 183. However, if the counted value of the timer T up is greater than the predetermined value, the program proceeds from the step 185 to a step 186. In the step 186, it is determined whether or not the amount of the acceleration flag f acc is equal to 1. If the amount of the acceleration flag F acc is not equal to 1, the program proceeds to a step 187. In the step 187, the timer T M is reset to zero and the program proceeds to a step 191. If the amount of the acceleration flag F acc is equal to 1, the program proceeds from the step 186 to a step 188. In the step 188, it is determined whether the pulse width signal TP is less than or equal to a predetermined value (for example, 1.6 milliseconds) at an upper limit of the upshift zone. If the pulse width signal TP is less than or equal to the predetermined value at the upper limit of the upshift zone, the program proceeds to a step 189. In the step 189, it is determined whether or not the counted value of time on the timer T M is greater than a first predetermined value (for example, 1 second). If the pulse width signal TP is greater than the predetermined value at its upper limit of the upshift zone, the program proceeds from the step 188 to a step 190. In the step 190, it is determined whether or not the counted value of the time on the timer T M is greater than or equal to a second predetermined value (for example, 2 seconds). The second predetermined value is greater than that of the first predetermined value. If it is determined that the counted value of the amount of time on the timer T M is less than the second predetermined value, in the step 190, the program proceeds to a step 196. In the step 196, the timer T C is reset to zero. The program proceeds from the step 196 to a step 184, wherein the upshift flag F up is reset. When the counted value of the amount of time on the timer T M is small, this indicates that the acceleration stage is temporarily cleared. Further, in this condition, the operator may want to continue the vehicle in the acceleration stage. This varies in accordance with the pulse width signal TP which corresponds to the load experienced by the engine. The greater the engine load the greater the possibility of the fact that a vehicle is accelerating. When the pulse width signal is large, the counting time is adjusted to be of a longer duration than when the pulse width signal is short. When the vehicle speed is temporarily decreased within the area of the upshift zone, the upshift flag F up is reset. The reason why the timer T C is reset to zero in the step 196 is to prohibit the acceleration flag F acc from being lowered when the timer T C commences to count the time at the condition F acc =1, and recounts the timer T C after the predetermined time has elapsed, and to lower the acceleration flag F acc , unless the pulse width signal TP becomes greater than or equal to 5 milliseconds during a predetermined time. In the step 191, the upshift flag F up is set. As apparent from the above-described explanation, the upshift flag F up is not set even if the vehicle is in the upshift zone because the acceleration of the vehicle is lowered by a temporarily large engine load.
In a step 192, it is determined whether the present gearshift position is in the highest gear ratio (for example, 5th position) in view of the gearshift position of the predetermined area M P stored in the RAM. When the present gearshift position is not the position of the highest gear ratio, the program proceeds to a step 193. In the step 193, it is determined whether or not the throttle valve 32 is fully closed. If the throttle valve 32 is not fully closed, the program proceeds to a step 194. In the step 194, it is determined whether or not the engine coolant temperature is less than a predetermined temperature (for example, 50° C.). If the engine coolant temperature is not less than the predetermined temperature, the program proceeds to a step 195. In the step 195, it is determined whether or not the vehicle speed detected by the vehicle speed sensor is less than or equal to a predetermined speed (for example, 5 Km/h). If the detected vehicle speed is less than or equal to the predetermined speed, the program proceeds to the step 49, equivalent to the step 49 in FIG. 4. The rationale for providing the steps 192 through 195 is as follows: When the actual present gearshift position is the position of the highest gear ratio in the step 192, the manual transmission cannot obtain any higher gearshift positions. When the throttle valve is fully closed, the engine is idling and therefore it is not proper to upshift the gears of the manual transmission. Further, when the engine coolant temperature is less than the predetermined temperature, it also is not proper to upshift the transmission because the engine coolant temperature is too low. When the vehicle speed is less than the predetermined speed, in the step 195, it becomes apparent that the present driving condition is not in the upshift zone, regardless of any other parameters which are calculated.
According to the present second embodiment, the instruction of the upshift is not made when the upshift is not proper in such circumstances.
While the present invention has been described in its preferred embodiments, it is to be understood that the invention is not limited thereto, and may be otherwise embodied within the scope of the following claims. | An apparatus for instructing an operator to place a gearshift of a manual transmission in an optimum position in accordance with various operating parameters. An upshift zone is formulated and stored in a memory means and when operating conditions of the vehicle fall within the upshift zone, a plurality of timers begin counting for a predetermined amount of time and if operating conditions still fall within predetermined parameters, an upshift signal is issued. The apparatus recognizes if the engine is acting as a brake and if the engine is under a heavy load when accelerating and does not issue an upshift signal. | 5 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to air-to-surface antipersonnel/antimaterial cluster weapons.
2. Description of the Prior Art
While there exists in the prior art, bomblets which discriminate between hard and soft targets, there are none which are able to discriminate between hard and soft targets and have a pop-up ability as does the present invention.
Furthermore there exists no air-to-ground weapon which arms itself by a combination nozzle and flutter mechanism as does the present invention.
SUMMARY OF THE INVENTION
The present invention is a bomblet of an air-to-surface cluster weapon capable of arming itself by air flow via a nozzle and flutter mechanism combination. Furthermore the nozzle-flutter combination will not begin the arming process unless a given minimum velocity has been reached. Additionally, the arming process is such that a given amount of time will elapse from the onset of an arming velocity to a fully armed condition.
Upon striking a target the bomblet is able to distinguish between a hard and soft target. Upon striking a hard target, shear rivets are sheared allowing immediate detonation of the warhead. Upon striking a soft target, a firing pin is inertially thrust into a stab primer setting off a propellant charge. The propellant charge propels the bomblet back into the air where it is detonated via a pyrotechnic delay extending from the stab primer.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view in partial cross section of the stacking arrangement of the cluster bomb;
FIG. 2a shows the bomblet in the soft target mode;
FIG. 2b shows the bomblet in the hard target mode;
FIG. 3 is an elevation view in partial cross section of the bomblet;
FIG. 4 is an elevation view of the forward end of the bomblet taken in the direction of arrows IV -- IV of FIG. 3;
FIG. 5 is a perspective view of the bomblet in partial section;
FIGS. 6a, b, c, and d, e, f, and g show the flutter mechanism in elevation and demonstrate in sequence the operation principles;
FIG. 7a shows a graph of the flutter mechanism in an uncontrolled mode;
FIG. 7b shows a graph of the flutter mechanism in a mode controlled by the nozzle;
FIG. 8 is an elevation view showing the nozzle in its recessed, safe position;
FIG. 9 is an elevation-section view of the bomblet;
FIG. 10 is an elevation-section view of the bomblet; and
FIG. 11 is an elevation-section view of the bomblet.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The antipersonnel/antimaterial (APAM) weapon is a cluster bomb of the 750-pound category and includes a dispenser as shown in FIG. 1 and a payload of 717 target discriminating, shaped charge, airburst bomblets. The bomblets are packaged in 17 wafers lengthwise of the dispenser. One wafer of 37 bomblets is placed in the nose of the dispenser followed by alternate wafers of 44 and 41 bomblets, respectively.
When the weapon is released from the bomb rack, two wires are pulled on the dispenser. The forward wire is a conventional arming wire which initiates the action of the dispenser fuze. The rear wire is the fin release lanyard. When pulled, the rear wire allows the fins at the rear of the dispenser to deploy. At some specified time after aircraft release, the dispenser fuze fires a linear shaped charge network which cuts the dispenser in half lengthwise causing the dispenser to open in clam-shell fashion. The bomblet cargo is released into the airstream and continues to fly in an expanded cone of bomblets along a trajectory approximating that of the complete weapon.
The bomblets arm at a fixed time from dispenser opening. During their period of flight, the bomblets free-fall, fin stabilized. At bomblet impact, the bomblet fuze will initiate one of the two modes of functioning. If a bomblet impacts an earth target such as mud, clay, sand, etc., the bomblet warhead will be propelled rearward (into the air) followed by an airburst of the warhead. This action will subject a wide area to high speed case fragments. If a bomblet impacts armor plate, sheet metal, or other hard surface, the warhead will fire in the super-quick mode subjecting the target to shaped charge action and the local area to high speed case fragments.
Thus, referring to FIG. 5, the bomblet is nose fuzed and contains a controlled fragmenting warhead case with a conical shaped charge. A pyrotechnic cup of zirconium metal is fitted to the outside of the warhead case at its base. The fuze is surrounded by a mortar-like housing and striker assembly. A nozzle interlock sleeve is placed over the striker housing to insure retraction of the fuze nozzle when the bomblet is packaged into the dispenser. The bomblet fin is made as one piece of unbreakable plastic. An aerodynamic spoiler plate is fitted between the warhead case and fin.
The external configuration of the bomblet is designed to produce maximum aerodynamic drag. This factor contributes to bomblet shaped charge performance against armor and lessens the structural requirements imposed on the fuze during soft target impact and subsequent bomblet pop-up. The bomblet terminal velocity is 245 feet per second indicated air speed. The principal drag producing feature on the bomblet is a result of the sharp corner on the leading edge of the major body diameter. This edge is formed by the terradynamic brake which surrounds the housing. A more detailed description of the terradynamic brake may be found in U.S. Pat. Application Ser. No. 203,564 filed Dec. 1, 1971. Aerodynamic drag forces on the bomblet are further increased through the use of the spoiler plate at the base of the warhead and the integrally molded hollow wedges on the tips of the plastic fin.
The terradynamic brake aids the bomblets' deceleration in soft soils thereby lessening the depth of hole in soft soils from which the bomblet must be propelled. Brake function occurs on soils softer than about 150 psi cone penetrometer reading (standard point). Impact with soft soils causes the brake to peel back, exposing a larger frontal area on the leading edge of the housing.
BOMBER FUZE
The APAM bomblet fuze uses a new technique for powering the fuze rotor into line and sensing safe arming thresholds (air speed discrimination). A flutter oscillator is used to perform these functions.
The fundamental operational principals of the APAM flutter oscillator are shown in FIGS. 6a, b, c, d, e, f and g. A rectangular flat plate (flutter) with a shaft through the mid-cord is supported between two journal bearings. One end of a leaf spring is staked to one end of the shaft and the other end of the spring is held in place between two hard points in the fuze housing. Ram air is directed over the leading edge of the flutter at a zero angle-of-attack. Aerodynamic turbulence causes the flutter to rotate. After a slight angle-of-attack has been reached the flutter acts like a wing with respect to the airstream. Under these conditions a lift force will be produced on the front upper (or lower) surface of the flutter, causing the flutter assembly to rotate. During its period of rotation a vortex is established under the leading edge of the flutter. Additionally, the spring is being flexed. When the flutter angle-of-attack approaches about 20° an aerodynamic stall condition is reached which causes the lift force to greatly diminish. The energy fed into the spring is now great enough to cause rotation in the opposite direction. During this period of reverse rotation the vortex has progressed to the rear of the flutter, providing further restoring power. The effect of the return spring and the vortex is to drive the flutter into a negative angle-of-attack whereupon the process is repeated.
FIGS. 7a and 7b depict flutter frequency as a function of air speed for an uncontrolled and controlled flutter. Flutter frequency in both cases is taken as positive indexing of a ratchet wheel driven by a pawl finger attached to the oscillator shaft. In the uncontrolled case, flutter frequency is not uniform as a function of air speed. When the flutter is mounted inside of a rectangular converging/diverging nozzle, flutter oscillation does not occur until a threshold velocity is reached. The system may be tuned in the case of APAM to be the minimum safe arming velocity. When this velocity is reached, oscillation frequency remains fairly constant and is predictable. This in effect allows the flutter to be used as a clock motor.
When the bomblet is packaged in the dispenser, the spring loaded fuze nozzle is depressed into the fuze housing and is held there by the base of a preceeding bomblet or packing spacer. FIG. 8 depicts this nozzle-flutter vane arrangement. This action insures that the fuze is fully locked. The throat of the nozzle traps the flutter preventing oscillation regardless of weapon vibration or other cyclic load. Further, an integral die cast boss on the side of the nozzle cam interfaces with a flat on the end of the rotor. This insures against rotor rotation toward the armed condition under any circumstance. When the bomblet is deployed into the air the nozzle extends, unlocking the flutter and rotor.
Referring to FIG. 11 it can be seen that upon impact with a hard target the striker which is pinned to the nose shears two shear rivets, allowing the striker to plunger into the fuze. As the striker moves rearwardly into the fuze it encounters a lever plate with an integral firing pin. The striker depresses the firing pin into the stab detonator. Initiation of the stab detonator ultimately results in an initiation of an acceptor explosive charge fastened to a mild detonation transfer line. The detonation signal is then conducted through the transfer line back to a booster charge which is fastened to the line. Initiation of the booster results in a detonation of the explosive charge causing the warhead case to fragment and the conical shaped charge to jet into the target. The sequence of events in the super-quick mode from impact to warhead detonation occurs within 65 microseconds.
Upon impact with a soft target, the forces of impact acting on the striker are not great enough to cause the rivets to shear. In this event the soft target firing mechanism, positioned above a stab primer in the rotor, plunges a stab pin into the primer. It will be noted that the soft target firing mechanism is of the hemi omnidirectional type. The output of the primer simultaneously side ignites two pyrotechnic time delays. The pop-up delay burns for 30 milliseconds and then ignites an output charge. The burning products of the output charge flash through a conduit in the fuze housing and ignite a heavily canned black powder expulsion charge. The expulsion charge propels the fuze, warhead and fin assembly back into the air as shown in FIGS. 2a and 2b. The long pyrotechnic time delay ultimately ignites an output charge while the bomblet is in the air. This delay output initiates the stab detonator by flash and shock. The balance of the detonation sequence then continues in the same manner as described for the hard target sequence.
BOMBLET WARHEAD
The APAM bomblet warhead consists of a fragmentation warhead case, conical shaped charge liner, end cap assembly, aerodynamic spoiler, pyrophoric cup, and a main explosive load. The APAM warhead case has been designed to produce 5.5 grain (nominal weight) steel fragments. The selection of this fragment size is consistent with performance requirements for personnel and light material. Fragment velocities range from 3384 to 5250 feet per second depending on the charge to metal ratio at any given zone along the case.
The APAM conical shaped charge liner is a 50°, 3 percent, 1.37-inch diameter, non-precision copper cone with an integral spit-back tube. The spit-back tube is used to fasten the transfer line booster assembly to the cone. | A target discriminating antipersonnel/antimaterial cluster weapon capable distinguishing between hard and soft targets. Upon striking a hard target such as armor or concrete, shear rivets are defeated causing a striker to plunge a firing pin into a stab detonator which through an explosive transfer train causes immediate detonation of the bomblet. Upon hitting a soft target such as sandy soil, the shear rivets will not be sheared, however, an inertia firing weight plunges a firing pin assembly into a stab primer which leads to a propellant charge causing the bomblet to pop back up into the air. The bomblet then is detonated through a pyrotechnic delay in the air. The bomblet is armed during its descent via a flutter plate giving oscillatory motion which is transferred into rotary motion. The rotary motion is employed to align the primer and detonator with the firing pins. | 5 |
CROSS REFERENCES
This application discloses subject matter similar to that previously disclosed by U.S. application Ser. No. 07/856,365, filed Mar. 23, 1992 and abandoned for lack of prosecution, by the same applicant.
BACKGROUND OF THE INVENTION
This invention relates to new and useful improvements in tooth brushes, and the primary object of the present invention is to provide a rotating head tooth brush with fewer parts than previous rotating head tooth brushes with resultant ease of cleaning and ease of manufacture.
DESCRIPTION OF RELATED ART
A rotating head tooth brush is described in U.S. Pat. No. 22,340 to Grau. The invention disclosed therein provides a tooth brush, the brush head of which is rotatively mounted on the handle by means of a rivet passing through the tooth brush head and the handle. The tooth brush head and handle are maintained at a spaced relationship to each other by a washer placed between them and through which the rivet passes. A spring mounted in the handle just below the head of the rivet exerts pressure on the washer thus holding the tooth brush head and handle at any desired orientation to each other.
A rotating head tooth brush with an improved pivot is described in U.S. Pat. No. 1,188,614 to Bowen. The invention disclosed therein provides a tooth brush, the tooth brush head of which is rotatively mounted on the handle by means of a rivet-like arrangement in which additional frictional engagement is provided flanges and disks recessed in both the brush head and the handle.
A rotating head tooth brush with a clamp-carrying handle is described in U.S. Pat. No. 1,752,393 to Rawson. The invention disclosed therein provides a tooth brush, the tooth brush head of which is rotatively mounted on the handle by means of a pin passing through the brush head and a looped terminal attached to the handle. Friction to hold the brush head in the desired orientation with respect to the looped terminal by a convex spring disk.
A rotating head tooth brush with recessed corrugated disks is described in U.S. Pat. No. 2,047,613 to Brown. The invention disclosed therein provides a tooth brush, the tooth brush head of which is rotatively mounted on the handle by means of a stud. Countersunk into both the brush head and the handle end adjacent to the brush head are corrugated spring disks whereby the brush head is held in the desired orientation to the brush handle.
A root and gum stimulator with a rotating brush head is described in U.S. Pat. No. 2,618,801 to Hibbs. The invention disclosed therein provides a tooth brush, the tooth brush head of which is rotatively mounted on the handle by means of a rivet which passes through the handle and through the channel shaped retaining member which holds the brush head. Conical recesses in the end of the handle to which the brush head is rotatively attached contact protuberances along the upper face of the channel retaining member as it is rotated thus holding the brush head in the desired orientation with respect to the handle. One would rotate the brush head until it clicks into the desired orientation with respect to the handle.
Each of these inventions utilizes fairly complicated mechanism to hold the brush head in the desired orientation with respect to the brush handle. The Grau patent utilizes a spring which will tend to become clogged with tooth paste in time thus providing an ideal breeding ground for bacteria. The Bowen patent has a tubular post which will quickly become clogged with tooth paste. The Rawson patent utilizes a complicated spring arrangement to provide the proper friction. The corrugated disks of the Brown patent will eventually become clogged with toothpaste and become a breeding ground for bacteria. The arrangement of the conical recesses and protuberances of the Hibbs patent provide only a limited number of orientations of the brush head with respect to the handle.
SUMMARY OF INVENTION, OBJECTS AND ADVANTAGES
Accordingly, the above problems and difficulties are obviated by the present invention which provides for a simple friction disk between the brush head and the handle. Due to only having two moving parts, the instant invention will be easy to clean and manufacture. The friction disk is made typically of an elastomeric polymer and is in a somewhat compressed state in the instant invention. The optimum amount of friction between the brush head and the handle is provided by having the friction disk under sufficient pressure in the instant invention that the desired orientation of the brush to the handle is maintained under ordinary use but not under such pressure that the brush head would be overly difficult to rotate with respect to the handle, when the user so desires. A less preferred embodiment provides that it is the handle rather than the friction disk which is in a compressed state, the handle thus exerting pressure on the friction disk and thus on the brush head. Having pressure exerted on it, the friction disk provides sufficient resistance to rotation of the brush head with respect to the handle that these two can be maintained in any desired orientation with respect to each other. Another less preferred embodiment provides that it is the brush head rather than the friction disk which is in a compressed state, with the same effect as in the other less preferred embodiment.
It is therefore an object of the present invention to provide a tooth brush with a rotating head wherein only two parts interface between the brush and handle: a friction disk and a rivet. It is a further object of this invention to provide a simple easily manufactured and easily cleaned rotating head toothbrush without springs to get clogged, without hidden voids where sanitary problems can arise. It is a further object of this invention to provide means to rotate the head 360 degrees with respect to the handle without snaps or detents. It is a further object of this invention to provide a toothbrush with a handle grip which makes it easy to hold in all positions.
The characteristics of this invention result in a rotating head toothbrush which is simpler, easier to clean, and more economical to manufacture than any of the prior art rotating head toothbrushes.
Further scope of applicability of the present invention will become apparent from the detailed description given hereafter. However, it should be understood that the drawings and the detailed description, 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
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:
FIG. 1 is a diagrammatic plan elevational view of the instant invention.
FIG. 2 is a side elevational view taken in the direction of arrow 2 in FIG. 1.
FIG. 3 is a diagrammatic elevational view with parts broken away taken in the direction of arrow 3 in FIG. 2 from the direction of the bristles, but with the head rotated 90 degrees from the position illustrated in FIG. 1.
FIG. 4 is a diagrammatic enlarged view with parts broken away taken in the area of the dotted ellipse indicated by arrow 4 in FIG. 1 illustrating that the head can be rotated a full 360 degrees.
FIG. 5 is an enlarged diagramatic cross sectional view with parts broken away taken on line 5--5 of FIG. 1.
FIG. 6 is an enlarged diagrammatic cross sectional view illustrating the rotational pivot structure in greater detail.
FIG. 7 is an enlarged diagrammatic cross section view of the terminal per se with parts broken away and with the rivet and friction disk removed so that the recess in which the rivet rests can be clearly distinguished.
FIG. 8 is an exploded and enlarged diagrammatic cross section view of the brush head with the rivet removed to more clearly illustrate the interface between the bristled and nonbristled sections of the brush head.
DESCRIPTION OF PREFERRED EMBODIMENT
The rotating head toothbrush is generally shown in FIG. 1 as 10. The toothbrush handle has two ends, a hand grip end 20 and a brush head end 22. The hand grip end 20 has spaced peaks 18 and valleys 26, so spaced as to provide a comfortable hand grip, thus making it easy to hold the tooth brush in any position. The brush head end of the handle terminates in a circularly shaped terminal 24 in the center of which is a circular hole shown as 26 in FIG. 7 for holding a rivet shown as 28 in FIG. 5. The terminal 24 has an upper surface 30 which is remote from the brush head 32 and a lower surface 34 which is proximate to the brush head 32. The lower surface 34 of the terminal 24 is provided with a wide circular opening shown as 36 in FIG. 7 which is formed with a circular step or shoulder to accommodate a circular friction disk 38. In the center of the step surface 39 of the wide circular opening 36 is a smaller circular hole 37 which is the extension of circular hole 26 and corresponds to the diameter of rivet 28. FIG. 3 shows the brush bristles 35 extending outward from the brush head 32.
The head of the tooth brush is generally shown as numeral 32 in FIG. 5. The brush head 32 is comprised of two sections, a nonbristled section 32a and a bristled section 32b, which are laminated together. The nonbristled section 32a of the brush head is that portion of the brush head closes to the handle. The bristled section 32b of the brush head is that portion of the brush head which holds the bristles 35. FIGS. 5 and 6 show that the finished or closed head 41 of the rivet 28 is countersunk into the upper surface 30 of the terminal 24. FIG. 6 shows that the open end 43 of the rivet 28 has been hammered and firmly holds the nonbristled section 32a of the brush head against the friction disk 38 which rests in the step 36 of the terminal 24. The bristled section 32b of the brush head has an inner surface 40 and an outer surface 42. The inner surface 40 of the bristled section 32b of the brush head is laminated or glued to the nonbristled section 32a of the brush head thus covering the compressed end 43 of the rivet 28. The outer surface 42 of the bristled section 32b bears the brush bristles 35.
FIG. 8 is an exploded and enlarged cross sectional view of the brush head with the rivet removed and clearly shows the interface between the nonbristled and bristled sections of the brush head and that there is a small indentation 45 in the bristled section to accommodate the head 43 formed on the open end of the rivet 28 when it is headed. The rivet 28 with flared head 43 is shown in FIG. 6.
The operation and use of the preferred embodiment of the instant invention can be described referring to FIG. 1. One would adjust the brush head 32 to the desired orientation with respect to the handle, and commence to brush one's teeth. When a different orientation is desired for a different cleaning effect, one could either hold the brush head 32 with one's teeth and rotate the handle to a new orientation, or remove the tooth brush from one's mouth and adjust the brush head by hand to the desired orientation.
Whether it is the friction disk, the nonbristled section of the brush head, or the handle which is wade of a compressible material, the method of manufacture is the same. Well known techniques would be utilized to manufacture the brush handle, and the bristled and nonbristled sections of the brush head 32. A suitably sized hole 26 is formed through the center of the terminal 24 of the brush handle and the nonbristled section 32a of the brush head. The outer surface 30 of the terminal 24 would have the hole widened at the surface to accommodate the closed end of a rivet 28 to be countersunk therein. The inner surface 34 of the terminal 24 in the vicinity of the hole 26 would have a circular step 36 cut into its surface to accommodate a friction disk 38 to be placed therein. The friction disk 38 would then be placed into the circular step 36 in the terminal 24, the inner surface 34 of the terminal would be placed flush with the upper surface 44 of the nonbristled section 32a of the brush head so that the holes in each lined up. The open end 43 of the rivet 28 would successively be passed through the outer surface 30 of the terminal 24, the friction disk 38, and the upper surface 44 of the nonbristled section of the brush head 32. The open end 43 of the rivet 28 would then be headed, thus causing the open end 43 protruding through the lower surface 46 of the nonbristled section 32a of the brush head, to flare outward. The rivet 28 thus tightly binds together the terminal 24, the friction disk 38, and the nonbristled section 32a of the brush head. The inner surface 40 of the bristled section 32b of the brush head would then be laminated or ultrasonically fused to the lower surface 46 of the nonbristled section 32a of the brush head.
Preferably the rivet would be made of an inert material such as plastic, stainless steel, tin, titanium, or a gold plated metal. If it is the handle or the brush head which is to be compressible, they will be made from a firm, rigid, compressible plastic which is not subject to cold flow under pressure.
From the foregoing, it will be seen that I have provided a tooth brush which utilizes material under pressure to provide the proper frictional characteristics to provide a rotating head tooth brush with a minimal number of parts, and which is easily cleaned and manufactured.
CONCLUSION, RAMIFICATIONS, AND SCOPE OF INVENTION
Thus the reader will see that my invention supplies a long felt need for a toothbrush which can have the brush head maintained at any desired orientation with respect to the handle, with a minimum number of parts, and which is easily cleaned and manufactured. There are many variations of this tooth brush which can be made without departing from the inventive concepts expressed herein. For example, the rivet could be replaced by a threaded pin and nut. Or, the friction disk could be replaced by two friction disks, one embedded in the brush head and the other embedded in the handle in order to vary the amount of friction. Accordingly, the scope of my invention should be determined not by the embodiments described, but by the appended claims and their legal equivalents. | A manually rotatable head toothbrush with a minimum number of parts and utilizing properties of an elastomeric material in the construction thereof, so as to thus providing suitable resistance to rotation such that any desired orientation of brush head to handle can be maintained when the toothbrush is in use. | 8 |
RELATED APPLICATIONS
This application is a continuation-in-part of patent application Ser. No. 07/771,625, filed Oct. 4, 1991, now U.S. Pat. No. 5,135,304, which is a continuation-in-part of patent application Ser. No. 07/522,533, filed May 11, 1990, now U.S. Pat. No. 5,153,671, by inventor Scott Miles, and entitled "Gas Analysis System Having Buffer Gas Inputs To Protect Associated Optical Elements".
FIELD OF THE INVENTION
The invention relates to a gas analysis cell, and, in particular, to a gas analysis cell for containing a gas sample in a laser Raman gas analysis system.
BACKGROUND OF THE INVENTION
Raman light scattering has been successfully used in critical care situations to continuously monitor a patient's respiratory gases. This technique is based on the effect which occurs when monochromatic light interacts with vibrational/rotational modes of gas molecules to produce scattered light which is frequency shifted from that of the incident radiation by an amount corresponding to the vibrational/rotational energies of the scattering gas molecules. If the incident light photon loses energy in the collision, it is re-emitted as scattered light with lower energy and consequently lower frequency than the incident photon. In a similar manner, if the incident photon gains energy in the collision, it is re-emitted as scattered light with higher energy and higher frequency than the incident photon. Since these energy shifts are species-specific, analysis of the various frequency components present in the Raman scattering spectrum of a sample provides chemical identification of the gases present in the scattering volume. The intensity of the various frequency components or Raman spectral lines provides quantification of the gases present, providing suitable calibrations have been made. In this manner, Raman light scattering can be employed to determine the identity and quantity of various respiratory and anesthetic gases present in a patient's breath in operating room and intensive care situations.
In addition to critical care situations, Raman light scattering gas analysis can also be used in many industrial applications such as stack gas analysis for combustion control, process control, fermentation monitoring, and pipeline gas mixture control. This analysis technique can also be extended to meet environmental monitoring needs in many areas such as escaped anesthetic agents in the operating room, air pollution, auto emissions testing and submarine atmosphere monitoring.
Systems developed for analysis of gases in critical care situations utilizing Raman scattering typically employ gas cells which contain a sample of the patient's respiratory gas to be analyzed. The gas sampling cell is located either within the resonant cavity of a laser or outside the cavity. In an intracavity system, a laser beam is directed through the resonant cavity such that it intercepts the gas within the sampling cell. Raman scattered light from the gas analysis region within the cell is collected by a collection optic and directed through one or more interference filters. The collection optics and interference filters and possibly focusing optics in turn transmit the Raman scattered light to appropriate detectors for quantitating each specific Raman signal, and thus, each specific gas comprising the respiratory sample.
Windows are commonly provided on either end of the gas sampling cell to protect surrounding optical elements and filters from contaminants which may be present in the gas sample. The windows further serve to confine the gas sample within the chamber, minimizing the volume of the sample and thus improving response time. In some systems, the gas cell windows can be oriented at Brewster's angle to select and improve the transmission of a particular polarization of light passing through the sample. In this manner, optical losses in the laser beam which passes through the cell are minimized. However, the gas sample, in combination with particulates often carried with the sample, contaminates the cell windows and degrades the performance of the system. For example, this contamination may result in undesirable light scattering, and thus, the corresponding laser power may drop significantly. If untreated and uncorrected, the system will cease to function properly. Current respiratory gas analysis systems require periodic replacement or cleaning of the gas cell to compensate for the accumulation of contaminants. This is generally a time-consuming process which involves not only the replacement or cleaning of the cell, but also, recalibration of the system, both at substantial expense in both time and money.
An improved apparatus for confining a gas sample within an analysis region can be provided by removing the windows from the ends of the gas sampling cell and forming air dams or curtains of air between the sample gases and the optical elements or the surrounding optical elements. Such a system is described in commonly assigned copending application Ser. No. 522,533. These systems are quite adequate in applications where the index of refraction of the sample gases does not change. However, in applications where the index of refraction of the sample gases is variable, it is often difficult to maintain optimum laser power in the resonant cavity. This is because index of refraction differences can cause laser beam movement and alignment changes, which affect the optical characteristics of the resonant cavity as well as the detection optics. In cases where the changes in index of refraction are predictable or known, it is possible to compensate by an appropriate calibration procedure. However, in many applications these changes are not predictable or known. For example, in a respiratory gas analysis system, the index of refraction of the gases being drawn into the gas cell changes with each breath taken by the patient.
When the laser beam passes through the interfacial regions or interfaces P and P' (shown in FIG. 4) formed between the air dam buffer gas and the gas being analyzed in the gas cell, it is "steered" by that interfacial region between the gases to a greater or lesser extent (as shown in FIG. 4). The extent to which the beam is "steered" is dependent on at least two things: 1) the difference between the refractive index of the analyte gas in the analysis portion of the gas cell (n A ) and the refractive index of the air dam buffer gas (n S ); and 2) the angles formed by the intersection of the laser beam axis with the interfacial regions P and P'.
The composition, and thus the index of refraction (n S ), of the air dam buffer gas does not normally change during use. However, the index of refraction (n A ) of the analyte gas mixture inside the gas cell often changes as the makeup of that gas changes. For example, in medical applications, the index of refraction of the gas/agent mixture changes appreciably when the gas in the gas cell changes from simple room air to a mixture with a high concentration of Nitrous Oxide. Furthermore, if the gas/agent mixture comprises respiratory gases from a patient, the index of refraction of the sample gas changes as the patient inhales and exhales.
At least two significant problems can occur when these index of refraction changes/beam steering effects occur. First, when the gas composition changes, the index of refraction changes, and therefore the path of the laser beam through the resonant cavity is altered. When the beam path changes, it changes the location at which the beam reflects off the mirror at the other end of the resonator. When this alignment change occurs, the lasing efficiency can drop significantly, thus causing loss in laser power which in turn causes the intensity of the Raman scattered light going to the detectors to drop. This loss of Raman signal reduces the signal to noise ratio of the system and is therefore undesirable. Secondly, when the path of the laser beam through the gas analysis cell changes, it may cause the laser beam to move out of the location which optimizes the efficiency of the detector system. The Raman scattered light which is coming from the laser beam and being focused on the detectors is used to identify and quantify the analyte gases. A shift of the laser beam location relative to the detector system changes the amount of light falling on the detectors and therefore changes the measurements being made in unpredictable ways. The present invention dramatically reduces these undesirable effects caused by varying gas composition and fluctuations in the index of refraction of the gases in the gas analysis cell.
Another factor which has been found to affect the lasing efficiency and thus the Raman scattered light intensity, is the gas pressure within the portion of the cavity containing the buffer and/or sample gases. Typically, the optical elements are aligned to maximize the circulating laser light intensity within the sample chamber. However, it has been discovered that as the pressure of the gas along the path of the laser beam changes, the intensity of the laser beam fluctuates. While some previous analysis systems monitor the gas pressure, none has recognized the relationship between the pressure and the light beam intensity. One prior system, U.S. Pat. No. 4,784,486 to Van Wagenen, monitors the gas pressure in the sample chamber and signals if the pressure drops below a threshold value, usually an indication of a plugged filter or other obstruction in the flow path of the sample gas from the patient to the chamber. The present invention improves the overall performance of the instrument by maintaining a constant pressure in the gas chamber, thus maintaining optimum signal intensity.
SUMMARY OF THE INVENTION
The present invention compensates for pressure fluctuations in the gas cell by maintaining a constant pressure in the cell. A pressure control circuit eliminates pressure variations that affect laser alignment by maintaining a constant pressure in the gas cell. The pressure transducer monitors the pressure at the outlet of the gas cell and provides an electrical signal that is a function of pressure to an amplifier circuit. A computer supplies a reference voltage to the amplifier that establishes a pressure set point. The amplifier compares the reference voltage with the transducer output to control a pulse width modulator. The pulse width modulator output is amplified by a pump drive circuit which controls a pump. If the pressure in the gas cell starts to rise, the pump works harder and increases the flow which results in a larger pressure drop between the patient and the gas cell thereby lowering the pressure in the gas cell. If the pressure in the gas cell decreases, the pump rate is reduced causing the pressure in the gas cell to increase.
In one embodiment, the present invention provides a gas analysis system comprising a cavity for containing a gas sample and propagating a beam of optical radiation through said gas sample; a pressure transducer for sensing gas pressure in the cavity; a gas pressure controller for controlling the pressure of the gas sample in the cavity; and a processor for receiving a signal from the pressure transducer indicative of the gas pressure in the cavity, interpreting the signal, and transmitting a signal to the gas pressure controller to maintain a predetermined gas pressure within the cavity. In some embodiments, the cavity is a resonant cavity which is a lasing cavity adapted for the amplification of light. Additionally, the gas pressure controller may comprise a gas flow controller for controlling the flow of the gas sample through the cavity. The gas flow controller may comprise a pump. In an alternate embodiment, the processor may further comprise a feedback loop wherein an error signal, which is proportional to the difference between the predetermined gas pressure and the measured pressure in the cavity, is used to control the flow of the gas sample through the cavity in a manner which minimizes the error signal. In yet another configuration, the gas pressure controller may comprise a variable restrictor for controlling the pressure of the gas sample in the cavity.
In another embodiment, the invention provides an apparatus for the analysis of a gas sample comprising: a laser for producing a laser beam, the laser comprising: a resonant cavity, and a lasing medium located within the resonant cavity; a gas cell positioned within the resonant cavity, the gas cell comprising: a housing, an analysis chamber within the housing, the analysis chamber having a sample interaction region containing a gas sample wherein the laser beam interacts with the gas sample; and a laser beam stabilizer comprising: a pressure transducer for sensing gas pressure in the sample interaction region, a gas pressure controller for controlling the pressure of the gas sample in the sample interaction region, and a processor for receiving a signal from the pressure transducer indicative of the gas pressure in the sample interaction region, interpreting the signal, and transmitting a signal to the gas pressure controller to maintain a predetermined gas pressure within the sample interaction region.
Another configuration of the invention provides a gas analysis system which comprises: a cavity for propagating a beam of optical radiation, the cavity having a first region containing a first gas adjacent to a second region containing a second gas, the first and second regions separated by a gaseous interface layer comprising a mixture of the first and second gases; a pressure transducer for sensing gas pressure in the cavity; a gas pressure controller for controlling the pressure of the gases in the cavity; and a processor for receiving a signal from the pressure transducer indicative of the gas pressure in the cavity, interpreting the signal, and transmitting a signal to the gas pressure controller to maintain a predetermined gas pressure within the cavity.
The invention further provides a method for analyzing a gas sample within a sample interaction region located in an optical resonant cavity, the method comprising the steps of: introducing the gas sample into the sample interaction region; illuminating the gas sample with a beam of electromagnetic radiation which is resonant in the resonant cavity; and stabilizing the optical characteristics of the beam of electromagnetic radiation within the sample interaction region, the step of stabilizing further comprising the steps of: monitoring the pressure of the gas sample within the sample interaction region; and maintaining a predetermined pressure within the sample interaction region.
In accordance with one embodiment of the present invention, a gas analysis cell is located within the resonant cavity of a laser in a gas analysis system. The ends of the resonant cavity are defined by two reflectors, preferably in the form of high reflectivity mirrors, gratings, or other known reflective elements. A sample of the gas to be analyzed is admitted to an analysis chamber within the analysis cell and a laser beam is directed through the analysis chamber such that the beam intercepts the gas sample therein. Raman scattered light is collected in detector channels adjacent the analysis chamber and analyzed with signal processing means in order to determine the type and quantity of the various gases comprising the sample.
The gas analysis cell of the present invention includes in addition to a sample input port, two input ports through which a flow of buffer gas is introduced. The flow of buffer gas is directed past optical elements on either end of the analysis cell. Two output ports are located on the ends of the analysis chamber to remove both the buffer gas and gas sample. The buffer gas flow acts to effectively confine the sample gas within the analysis region of the chamber and prevents the gas sample from contacting and contaminating the mirrors and any other optical elements in the cavity. Since no exposure of the optical elements to the gas sample occurs, the detrimental effects of the sampled gas upon the system optics are prevented. In addition, the constant, nonturbulent flow of buffer gas reduces the variation in density gradients of the gas flow within the gas cell, thereby reducing adverse effects such as beam steering and Schlieren effects which result from abrupt changes in refractive index caused by varying density gradients in the gas flow along the optical path of the light beam.
The present invention provides a gas analysis system comprising a cavity having an optical element wherein the cavity is capable of propagating a beam of optical radiation. A gas cell is positioned within the cavity and adapted to receive a gas sample. The gas cell is further configured to permit the beam to pass through the gas sample. A buffer gas inlet port is coupled to the cavity for introducing a flow of buffer gas to the cavity wherein the flow of buffer gas substantially prevents the gas sample from contacting the optical element. The cavity may be a resonant cavity. In addition, the resonant cavity may be a lasing cavity adapted for the amplification of light. The gas cell may further comprise at least one light output channel for transporting light which is scattered out of the beam of optical radiation by the gas sample. The analysis system may also include an outlet port coupled to the resonant cavity for removing gases from the gas cell and the cavity. The buffer gas inlet port may be constructed and arranged so that buffer gas floods a region adjacent the optical element. Also, the buffer gas inlet port may be constructed and arranged so that the flow of buffer gas into the cavity is non-turbulent.
An apparatus for the analysis of a gas sample is disclosed comprising a laser light source for producing a laser beam. The laser source comprises a resonant cavity and a lasing medium located within the resonant cavity. A gas cell is positioned within the resonant cavity. The gas cell comprises a housing and an analysis chamber enclosed within the housing. A sample gas inlet port is formed in the housing for introducing a gas sample into the analysis chamber and a buffer gas inlet port is formed in the housing for receiving a flow of buffer gas. A gas outlet port is formed in the housing wherein the outlet port provides an outlet for the buffer gas and the gas sample in a manner which substantially confines the sample gas to a region of the analysis chamber located intermediate the sample gas inlet port and the gas outlet port. The analysis chamber may further comprise at least one light output channel for transporting light which is scattered out of the laser beam by the gas sample.
In accordance with the present invention, a gas analysis system is disclosed comprising a laser having a longitudinal resonant cavity wherein the ends of the cavity are defined by first and second high reflectivity mirrors. A gas analysis cell is positioned within the resonant cavity intermediate the mirrors and comprises an analysis chamber having a first end and a second end. A sample gas inlet port is located intermediate the analysis chamber first and second ends for introducing a gas sample into the analysis chamber. First and second buffer gas inlet ports are located at the first and second ends of the analysis chamber for introducing a flow of buffer gas into the analysis cell. First and second outlet ports are located near the first and second ends of the analysis chamber for removing the gases from the analysis cell such that the flow of buffer gas between the buffer gas inlet ports and the outlet ports confines the gas sample to the analysis chamber.
A method for constraining a gas sample within a gas analysis cell located within a cavity is disclosed comprising the steps of introducing the gas sample into the analysis cell and introducing a flow of buffer gas into the analysis cell such that the flow of buffer gas through the cell substantially confines the gas sample within the analysis cell.
The present invention provides a device for the analysis of gases in a gas sample utilizing Raman light scattering comprising an optical cavity and a gas analysis chamber for receiving a gas sample. The chamber is positioned within the optical cavity and in fluid communication with at least a portion of the cavity located outside the analysis chamber. The device may further comprise an air dam for substantially constraining the gas sample to the analysis chamber.
In one embodiment, the present invention comprises a resonant cavity for propagating a beam of optical radiation; and a gas cell positioned within the resonant cavity which is adapted to receive a gas sample in an analysis chamber having an optical axis. The gas cell further comprises a first buffer gas chamber adjacent a first end of the analysis chamber and a second buffer gas chamber adjacent a second end of the analysis chamber. The cell is configured to permit the beam of optical radiation to enter and exit the analysis chamber through the first and second buffer gas chambers. A first mixed gas outlet port is located intermediate the gas analysis chamber and the first buffer gas chamber, wherein sample gases from the analysis chamber mix with buffer gases from the first buffer gas chamber to form a first air dam having a first set of optical characteristics. A second mixed gas outlet port is located intermediate the gas analysis chamber and the second buffer gas chamber, wherein sample gases from the analysis chamber mix with buffer gases from the second buffer gas chamber to form a second air dam having a second set of optical characteristics. The second set of optical characteristics are substantially the reciprocal of the first set of optical characteristics so that any steering effects on the beam of optical radiation caused by propagating the beam through the first air dam are substantially reversed so as to counteract the steering effects upon propagation of the beam through the second air dam.
The invention may further comprise a detector channel having an optical axis, wherein the detector channel optical axis and the analysis chamber optical axis define a first plane through the analysis chamber. Additionally, the first plane may intersect a portion of the first and/or second mixed gas outlet ports. The invention may also have the first mixed gas outlet port and the second mixed gas outlet port located on opposite sides of the analysis chamber optical axis.
In certain embodiments, the air dam of the present invention further comprises an interfacial region formed by the sample gases in the analysis chamber and the buffer gases in the first buffer gas chamber. The interfacial region may be planar and form an angle with respect to the analysis chamber optical axis. In some embodiments, the interfacial region is substantially perpendicular to the analysis chamber optical axis.
In another embodiment, the first air dam further comprises a region intermediate the sample gases in the analysis chamber and the buffer gases in the first buffer gas chamber, wherein the region has an index of refraction profile which is a function of the indices of refraction of the gas sample and the buffer gas.
In another embodiment, the gas analysis system of the present invention comprises a resonant cavity for propagating a beam of optical radiation; and a gas cell positioned within the resonant cavity. The gas cell comprises an analysis chamber having an optical axis; an inlet port for introducing a gas sample into the analysis chamber; and a first air dam adjacent a first end of the analysis chamber and a second air dam adjacent a second end of the analysis chamber for confining the sample gas within the analysis chamber. The beam of optical radiation can enter and exit the analysis chamber through the first and second air dams and the first and second air dams have optical characteristics which are substantially the reciprocal of each other so that any steering of the beam of optical radiation caused by propagating through the first air dam is substantially counteracted upon propagation of the beam through the second air dam.
In some embodiments of the invention, the first air dam further comprises a region intermediate the sample gases in the analysis chamber and a buffer gas in a first buffer gas chamber. The region has an index of refraction profile which is a function of the indices of refraction of the gas sample and the buffer gas.
One embodiment of the invention comprises a gas cell having an analysis chamber with a sample gas inlet port and an optical axis; a detector channel having an optical axis, wherein the detector channel optical axis and the analysis chamber optical axis define a first plane through the analysis chamber; a first buffer chamber in fluid communication with a first end region of the analysis chamber; a second buffer chamber in fluid communication with a second end region of the analysis chamber; a first gas outlet port located intermediate the sample gas inlet port and the first buffer chamber for removing gases from the analysis chamber and the first buffer chamber thereby forming a first mixed gas interfacial region between the analysis chamber and the first buffer chamber, wherein the first plane intersects a portion of the first gas outlet port; and a second gas outlet port located intermediate the sample gas inlet port and the second buffer chamber for removing gases from the analysis chamber and the second buffer chamber thereby forming a second mixed gas interfacial region between the analysis chamber and the second buffer chamber, wherein the first plane intersects a portion of the second gas outlet port and the first and second gas outlet ports are located on opposite sides of the analysis chamber optical axis.
In this embodiment, the first and second mixed gas interfacial regions may further have optical properties which are substantially the reciprocal of each other so that any steering of a beam of optical radiation propagating from the first buffer chamber through the first mixed gas interfacial region into the analysis chamber is substantially counteracted upon propagation of the beam of optical radiation propagating from the analysis chamber through the second mixed gas interfacial region into the second buffer chamber.
In yet another embodiment, the gas analysis system of the present invention comprises a laser, where the laser has a longitudinal resonant cavity with an optical axis wherein the ends of the cavity are defined by first and second high reflectivity mirrors; a detector channel having an optical axis, the detector channel optical axis and the laser optical axis defining a first plane; and a gas analysis cell having an optical axis substantially aligned with the laser optical axis, the gas analysis cell positioned within the resonant cavity intermediate the mirrors. The gas analysis cell further comprises an analysis chamber having a first end and a second end; a sample gas inlet port located intermediate the analysis chamber first and second ends for introducing a gas sample into the analysis chamber; first and second buffer gas inlet ports located at the first and second ends of the analysis chamber for introducing a flow of buffer gas into the analysis cell; and first and second outlet ports located at the first and second ends of the analysis chamber, intersecting the first plane and on opposite sides of the optical axis for removing the gases from the analysis cell such that the flow of buffer gas between the buffer gas inlet ports and the outlet ports confines the gas sample to the analysis chamber.
The present invention also provides a method for constraining a gas sample within a gas analysis cell located within a cavity. This method comprises the steps of introducing the gas sample into the analysis cell; forming a first air dam adjacent a first end of the analysis chamber and a second air dam adjacent a second end of the analysis chamber for substantially confining the gas sample within the analysis cell; and forming the first and second air dams so that each has optical characteristics which are substantially the reciprocal of the other so that any steering of a beam of optical radiation propagating through the first air dam is substantially counteracted upon propagation of the beam through the second air dam.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates a side cross-sectional view of a gas analysis cell within a laser resonant cavity in a gas analysis system in a first embodiment of the present invention.
FIG. 2 is an enlarged side cross-sectional view of the gas analysis cell shown in FIG. 1.
FIG. 2A is an enlarged side cross-sectional view of the gas cell shown in FIG. 2 illustrating the gas flows within the cell.
FIG. 3 is a top cross-sectional view of a second embodiment of a gas cell of the present invention illustrating the gas flows within the cell.
FIG. 4 shows detailed air flow and mixing patterns at the entrance to the outlet ports of the gas cell shown in FIG. 3.
FIG. 5 is a block diagram of a preferred embodiment of the invention for maintaining constant pressure within the gas cell.
DETAILED DESCRIPTION OF THE INVENTION
As shown in FIG. 1, a gas analysis cell 10 in accordance with the present invention is positioned within a resonant cavity of a laser in a gas analysis system. The resonant cavity includes a plasma discharge tube 16 and has a volume which is defined by a first reflector 18 and a second reflector 20. The first reflector 18 preferably comprises a high reflectivity mirror, i.e., a mirror with a reflectivity greater than 99.99%. The reflector 20 preferably comprises a second high reflectivity mirror. Alternatively, the second high reflectivity mirror could be coated on the back side of a Littrow prism. A Brewster prism 21 may be inserted in the cavity to select a particular wavelength of light for circulation through the resonant cavity. A lasing gas mixture is confined within the discharge tube 16 and a Brewster window 22 is positioned at the end of the discharge tube 16 adjacent the output such that the light beam propagating within the cavity enters and exits the discharge tube 16 through the Brewster window 22.
Referring to FIG. 1 and FIG. 2, the gas analysis cell 10 is positioned intermediate the Brewster window 22 and second reflector 20 within the laser resonant cavity. The analysis cell 10 comprises a housing 24 enclosing an analysis chamber 26. The analysis cell 10 includes two buffer regions 28, 30 on either end of the analysis chamber 26. The analysis chamber 26 is connected to the source of gas to be analyzed by a gas sample inlet port 34. The gas analysis cell 10 further comprises a plurality of output channels 36 which form optical passageways between the analysis chamber 26 and the outside of the gas cell 10. A first buffer gas input port 40 is connected to the buffer region 30 adjacent the Brewster window 22 and a second buffer gas input port 42 is connected to the buffer region 28 adjacent the second reflector 20. In addition, the cell comprises a first output port 44 connected to the buffer region 30 at the end of the analysis chamber 26 nearest the Brewster window 22. Output port 44 is positioned intermediate the gas sample inlet port 34 and first buffer gas inlet port 40. A second output port 46 is connected to the buffer region 28 at the end of the analysis chamber nearest the second reflector 20. Output port 46 is positioned intermediate the gas sample inlet port 34 and the second buffer gas inlet port 42.
A gas sample which is to be analyzed enters the sampling cell 10 through the input port 34 and is contained within the analysis chamber 26. The laser discharge tube 16 emits a collimated beam of polarized light with a characteristic wavelength dependent upon the type of gas within the discharge tube 16 the orientation of the Brewster prism 21, and the nature of the mirror coating on high reflector mirrors 18,20. The light beam travels an optical path through the Brewster window 22 and through the length of the analysis chamber 26 of the gas analysis cell 10 and is incident upon the second reflector 20. The length of the resonant cavity is such that the light beam resonates between the first and second reflectors 18, 20 which define the volume of the resonant cavity. Thus, the emitted light propagates within the resonant cavity, entering and exiting the discharge tube 16 through the Brewster window 22, thereby stimulating further emission of additional excited atoms within the discharge tube and achieving optimum light amplification. The Brewster prism 21 optimizes the power of a preferred wavelength and polarization state of the laser beam circulating in the resonant cavity. Thus, the Brewster window 22 serves to seal the gas within the discharge tube 16 while also providing polarization control of the light beam by completely transmitting light of a preferred polarization state.
Inside the analysis chamber 26 of the sampling cell 10, the light beam circulating in the resonant cavity intercepts the sample of the gas to be analyzed. The Raman scattered radiation from the gas sample is collected over as large a solid angle as possible by the detector channels 36, which are located approximately perpendicular to and on either side of the axis of the laser light beam propagating inside the analysis chamber 26. The Raman signals can then by analyzed with a microprocessor (not shown) associated with the detector channels 36 and, based on this analysis, the identity and concentration of each specific gas comprising the gas sample contained within the analysis chamber 26 can be determined and reported. A more detailed description of this analysis process can be found in U.S. Pat. No. 4,784,486 entitled "Multi-Channel Molecular Gas Analysis by Laser-Activated Raman Light Scattering", assigned to the assignee of the present invention and incorporated herein by reference.
Referring to FIG. 2A, a flow of buffer gas 50 is introduced into the two buffer gas inlet ports 40, 42 formed in the buffer regions 28, 30 of the cell 10. A portion 50A of the flow 50, input through the first buffer gas inlet port 40, is directed past the Brewster window 22 and toward one end of the analysis chamber 26. A second portion 50B of the flow 50, input through the second buffer gas inlet port 42, is directed past the end reflector 20 and toward the opposing end of the analysis chamber 26. Near the openings in the ends of the analysis chamber 26, the buffer gas flows 50A and 50B mix with the gas sample 52 contained within the analysis chamber 26 and forms gas mixtures 54A and 54B. The gas mixtures 54A and 54B then exit the gas analysis cell 10 through the output ports 44 and 46, respectively, formed in the housing 24 at either end of the analysis chamber 26. Thus, the buffer gas flow 50 through the analysis cell 10 forms a "dam" which constrains the gas sample 52 to the portion of the analysis chamber 26 located intermediate the analysis chamber outlet ports 44, 46. In this manner, the buffer gas flows 50A and 50B serve to protect the optical elements, i.e., the Brewster window 22, the second reflector 20, and the Brewster prism 21, of the gas analysis system from contaminants which may be present in the gas sample 52. This is a significant improvement over typical prior art gas analysis systems in which additional Brewster windows are mounted at each end of the chamber 26 to contain the gas sample 52 within the analysis chamber 26 and protect the remaining optical elements in the cavity from the detrimental effects of the gas sample. Such windows are themselves subject to contamination from the gas sample 52, resulting in laser power losses. Such windows also have intrinsic loss mechanisms which detract from the maximum attainable circulating optical power in the laser resonator. The flow of buffer gas 50A and 50B through the analysis cell 10 eliminates the need for any windows at the ends of the analysis chamber 26, thus maximizing the circulating optical power in the resonant cavity.
In addition to protecting the optics 20, 21, 22 from contaminants in the gas sample 52, the gas analysis cell 10 illustrated in FIG. 1 and FIG. 2 further serves to reduce problems caused by variations in index of refraction and beam steering which often occur as the laser beam propagates through the Brewster window 22. When the laser beam passes through the Brewster window 22 adjacent the discharge tube 16, it is "steered", i.e., deflected, and exits the Brewster window 22 at an angle which is different from the angle at which it entered if the index of refraction of the gases on the two sides of the window are not equal. The angle in reference to the axis of the resonant cavity at which the laser beam emitted from the discharge tube 16 exits the Brewster window 22 is dependent upon 1) The indices of refraction of the window material and the gases on either side of the window; and 2) The angle of the plane in which index of refraction changes occur relative to the axis of the laser beam passing through the analysis cell 10. Note, that if this plane is perpendicular to the beam axis, no change in beam direction will occur regardless of differences in indices of refraction. Obviously, the index of refraction of the window material comprising the Brewster window 22 is fixed. However, the index of refraction of the sample gas on the gas cell side of the window will change as the individual components comprising the gases vary in type and concentration.
With the gas cell lo of the present invention, the buffer gas flow 50A shown in FIG. 2A immediately in front of the Brewster window 22 along the optical path of the light beam remains constant regardless of what type and concentration of gases comprising the gas sample 52 are introduced into the analysis chamber 26. Since the index of refraction does not change next to the side of the Brewster window 22 adjacent the analysis chamber 26, the angle at which the beam exits the Brewster window is constant and beam steering effects due to the buffer gas are predictable and can be accounted for in the design. One skilled in the art will recognize that the index of refraction of the gas sample 52 contained in the analysis chamber 26 of the gas cell still varies as the concentration of the individual gases comprising the sample varies, and thus, the index of refraction changes where the sample gas mixes with the buffer gas 50 creating the gas mixture 54. If this change in index of refraction occurs in a plane which is nominally perpendicular to the optical path of the laser beam, it will not cause the beam steering problems which occur when the change in refractive index occurs at Brewster window 22, i.e., in a plane which is not perpendicular to the optical path. Furthermore, the buffer gas flow 50 can be utilized not only to prevent beam steering, but also to move unavoidable beam steering effects to a location where the effects are no longer deleterious.
Although the analysis chamber inlet port 34 need not be positioned in the center of the analysis cell as illustrated in FIG. 1 and FIG. 2, there are several advantages associated with this location. When the gas sample 52 is introduced in the center of the gas analysis cell 10, the flow is introduced immediately into the analysis chamber 26 without having to displace the volumes around the optics 20, 22 at either end of the cell. In addition, in analysis systems wherein the gas sample is introduced into one end of the analysis chamber 26, the gas sample flows past each pair of detector channels 36 sequentially. In the analysis cell 10 of the present invention, the gas sample 52 flows into the center of the analysis chamber 26 and then flows away from the inlet 34 in two directions, toward each end of the chamber 26. When input in this manner, two pairs of detector channels 36 are located immediately adjacent to the gas sample input 34, thereby advantageously decreasing response time by as much as one half compared with the response time of prior art systems wherein the gas sample 52 is introduced at one end of the analysis chamber 26.
When the buffer gas flow 50 is input at relatively low flow rates, the flow generally is laminar rather than turbulent in nature. Thus, the point inside the analysis cell 10 at which the gas sample 52 mixes with the buffer gas 50 to form the gas mixture 54 occurs in the laminar flow region, thereby eliminating turbulent mixing and changes in refractive index, i.e., Schlieren effects, which can cause power losses in the transmission of the laser beam.
FIG. 3 shows a top cross-sectional view of a second embodiment of a gas cell 110 according to the present invention. The analysis cell 110 comprises a housing 124 enclosing an analysis chamber 126. The gas analysis cell 110 is positioned intermediate a Brewster window 122 and second reflector 120 within the laser resonant cavity. The gas cell 110 includes two buffer regions 128, 130 on either end of the analysis chamber 126. The analysis chamber 126 is connected to the source of gas to be analyzed by a gas sample inlet port 134. The gas analysis cell 110 further comprises a plurality of output channels 136 which form optical passageways between the analysis chamber 126 and the outside of the gas cell 110. As shown in FIG. 3, the output channels 136 define an output channel plane which, in the top view shown in FIG. 3, coincides with the plane of the drawing. In FIG. 1, the output channel plane is perpendicular to the plane of the drawing. Referring again to FIG. 3, a first buffer gas input port 140 is connected to the buffer region 130 adjacent the Brewster window 122 and a second buffer gas input port 142 is connected to the buffer region 128 adjacent the second reflector 120. In addition, the cell 110 comprises a first output port 144 connected to the buffer region 130 at the end of the analysis chamber 126 nearest the Brewster window 122. Output port 144 is positioned intermediate the gas sample inlet port 134 and first buffer gas inlet port 140. Additionally, the outlet port 144 has a longitudinal axis which lies in the output channel plane. A second output port 146 is connected to the buffer region 128 at the end of the analysis chamber 126 nearest the second reflector 120. Output port 146 is positioned intermediate the gas sample inlet port 134 and the second buffer gas inlet port 142. Additionally, the outlet port 146 has a longitudinal axis which lies in the output channel plane. Thus, the outlet ports 144 and 146 lie in the same plane. Additionally, in the embodiment shown in FIG. 3, the outlet ports 144 and 146 lie in the output channel plane and on opposite sides of the analysis chamber 126. However, other relative orientations between the plane of the outlet ports 144 and 146 and the plane of the output channels 136 may also be employed.
Referring to FIG. 3, a flow of buffer gas 150 is introduced into the two buffer gas inlet ports 140, 142 formed in the buffer regions 128, 130 of the cell 110. A flow of agent/gas, i.e., analyte gas, 152 is introduced into the analysis chamber 126 via the gas sample inlet port 134. A portion 150A of the flow 150, input through the first buffer gas inlet port 140, is directed past the Brewster window 122 and toward one end of the analysis chamber 126. A second portion 150B of the flow 150, input through the second buffer gas inlet port 142, is directed past the end reflector 120 and toward the opposing end of the analysis chamber 126. Near the openings of outlets 144 and 146 in the ends of the analysis chamber 126, the buffer gas flows 150A and 150B mix with the gas sample 152 contained within the analysis chamber 126 and form gas mixtures 154A and 154B. The gas mixtures 154A and 154B then exit the gas analysis cell 110 through the output ports 144, 146 formed in the housing 124 at either end of the analysis chamber 126. Thus, the buffer gas flow 150 through the analysis cell 110 forms a "dam" which constrains the gas sample 152 to the portion of the analysis chamber 126 located intermediate the analysis chamber outlet ports 144, 146. In this manner, the buffer gas flows 150A and 150B serve to protect the optical elements, i.e., the Brewster window 122, the second reflector 120, and the Brewster prism 121, of the gas analysis system from contaminants which may be present in the gas sample 152. The flow of buffer gas 150A and 150B through the analysis cell 110 eliminates the need for any windows at the ends of the analysis chamber 126, thus maximizing the circulating optical power in the resonant cavity.
In addition to protecting the optics 120, 121 and 122 from contaminants in the gas sample 152, the gas analysis cell 110 illustrated in FIG. 3 further serves to reduce problems caused by variations in index of refraction and beam steering which often occur as the laser beam propagates through the system. Each time the laser beam passes through an optical interface, for example, the Brewster window 122 adjacent the discharge tube 16, it is "steered", i.e., deflected, and exits the Brewster window 122 at an angle which is different from the angle at which it entered if the index of refraction of the gases on the two sides of the window are not equal. The angle in reference to the axis of the resonant cavity at which the laser beam emitted from the discharge tube 16 exits the Brewster window 122 is dependent upon 1) The indices of refraction of the window material and the gases on either side of the window; and 2) The angle of the interface or interfacial region in which index of refraction changes occur relative to the axis of the laser beam passing through the analysis cell 110. If this interface or interfacial region, or any other interface representing a change in index of refraction, is perpendicular to the beam axis, no change in beam direction will occur regardless of differences in indices of refraction. Obviously, the index of refraction of the window material comprising the Brewster window 122 is fixed. However, the index of refraction of the sample gas on the gas cell side of the window will change as the individual components comprising the gases vary in type and concentration.
With the gas cell 110 of the present invention, the buffer gas flow 150A shown in FIGS. 3 and 4 immediately in front of the Brewster window 122 along the optical path of the light beam remains constant regardless of what type and concentration of gases comprising the gas sample 152 are introduced into the analysis chamber 126. Since the index of refraction does not change next to the side of the Brewster window 122 adjacent the analysis chamber 126, the angle at which the beam exits the Brewster window is constant and beam steering effects due to the buffer gas are predictable and can be accounted for in the design. One skilled in the art will recognize that the index of refraction of the gas sample 152 contained in the analysis chamber 126 of the gas cell still varies as the concentration of the individual gases comprising the sample varies. Thus, the index of refraction varies in a region surrounding an interfacial region or interface P' (see FIG. 4) formed when sample gas flow 152A and buffer gas flow 150A mix to form the outgoing gas mixture flow 154A. Likewise, the index of refraction varies in a region surrounding an interfacial region or interface P formed when sample gas flow 152B and buffer gas flow 150B mix to form the outgoing gas mixture flow 154B. Thus, due to the mixing of the gases 150 and 152 in the regions proximate to the interfacial regions P and P', there exists an index of refraction profile. For example, if the indices of refraction of the sample gas 152 and buffer gas 150 are not equal, the index of refraction along a path from inside the analysis chamber 126 through interfacial region P to buffer region 128 will define a specific index of refraction profile. Initially, the index of refraction of the profile will be equal to the index of refraction of the sample gas 152. As the path approaches the interfacial region P, crosses the interfacial region P and recedes away from the interfacial region P into the buffer region 128, the index of refraction will vary depending upon the relative concentrations of the sample gas 152 and buffer gas 150 comprising the mixture 154 as well as the magnitude of the difference of the indices of refraction of the sample gas and buffer gas. Once the path is well inside the buffer region 128 the profile will equal the index of refraction of the buffer gas 150. If interfacial regions P and P' are perpendicular to the optical path of the laser beam through the interfacial regions, beam steering does not occur. However, if the interfacial regions P and P' are not perpendicular to the optical path and the indices of refraction of the sample gas 152 and buffer gas 150 are not equal, the previously discussed beam steering may occur.
The embodiment of the invention illustrated in FIGS. 3 and 4 compensates for such beam steering effects by locating the outlet ports 144 and 146 on opposite sides of the gas analysis chamber 126. The effect of locating the outlet ports on opposite sides of the gas analysis chamber is to produce beam steering effects at the interfacial regions P and P' which are substantially equal and opposite (and thus self compensating) when they do occur.
FIG. 4 shows the beam steering that might occur when the air dam buffer gas 150 is air and the analyte gas 152 has a high concentration of nitrous oxide (N 2 O). In this case, the index of refraction of the analyte gas, n A , is less than the index of refraction of the buffer gas, n B . When a laser beam 160A, traveling from right to left as shown in FIG. 4, passes through the gas interfacial region P', it is bent, i.e., refracted, along a path 160B. The angle between incoming beam 160A and 160B and the offset of beam 160B as it passes through the gas analysis chamber 126 have been exaggerated for clarity. When the beam 160B passes through the second gas interfacial region or interface P, the laser beam is bent, i.e., refracted along a path 160C. If the indices of refraction of buffer gases 150A and 150B are substantially equal and the interfacial regions P and P' are substantially parallel, then the bending of the laser beam at interfacial region P is in a direction which is substantially equal and opposite to the bending of the laser beam at interfacial region P'. Note that if n A were greater than n B (instead of less than), then the laser beam 160 would bend in opposite directions. The self compensation would still occur, only in the opposite direction. If n A and n B are equal, then no beam bending occurs and the laser beam 160 would follow a straight path through the interfacial regions P and P'.
The amount of beam bending which occurs at each location of mixing defined by interfacial regions P and P' is determined by the angle at which the interfacial regions P and P' make relative to the axis of the laser beam as well as by the magnitude of the difference between the indices of refraction, n A and n B , of the analyte gas and the buffer gas, respectively. For one bend to be compensated by the other bend, the interfacial regions interface angles at P and P' should be substantially the same.
The interface angles of the interfacial regions P and P' are determined in part by the relative gas flow rates coming from each direction and the geometries of the flow patterns from each direction. In one embodiment, the flow rates of the analyte gas flows 152A and 152B are much greater than the flow rates of the air dam buffer gases 150A and 150B. For example, the flow rate for the analyte gases is in the range of approximately 60 to 120 Ml/min (milli-liters per minute) while the flow rate for the buffer gases is in the range of approximately 4 to 8 Ml/min. The exact flow rates are not as important as the ratio between the two rates. With the above described flow rates, the higher flow rate analyte gas overshoots the outlet ports 144 and 146 somewhat and then turns back towards the outlet ports as shown in FIG. 4. This causes the interface angle between the two gases to tilt in the directions shown by the interfacial regions P and P'.
In order for the laser beam bending which might occur at interfacial region P to be equally compensated for by that which might occur at interfacial region P', the two angles should be substantially equal. This can be achieved if the relative flow rates at each location are substantially the same (assuming the shapes of the flow paths are substantially the same). For the flow rates to be the same, the restrictions in the flow path leading to each location should be substantially equal. This can be accomplished by making the geometries of the gas flow passages leading to the interfacial regions P and P' substantially the same, including, e.g., equal lengths and diameters throughout the system. Alternatively, the air dam buffer gas flows 150A and 150B on each side of the analysis chamber 126 may be independently adjusted.
Adjustment of the angles which interfacial regions P and P' make relative to the laser axis can be individually "tuned" by adjusting the relative analyte flow rates 152A, 152B versus buffer gas flow rates 150A, 150B. In one embodiment, this is accomplished by a needle valve (not shown) located in each of the buffer gas inlet lines 140, 142. Such adjustments of the buffer gas flow rates controls the amount of beam steering which occurs at the interfacial regions P and P' at each end of the gas analysis chamber 126. Control of the flow rates makes it possible to optimize the overall system performance.
Placement of the outlet ports 144 and 146 on opposite sides of the analysis chamber 126 and control of the angles of the interfacial regions P and P' as described above, greatly reduces the heretofore deleterious effects of index of refraction beam steering in a gas analysis system. Thus, the effect of varying index of refraction gases being introduced into the gas cell, such as seen in breath by breath analysis of respiratory gases, have a minimal effect on laser power and hence, overall system performance.
As previously described, in some embodiments of the gas cell 110 the outlet ports 144 and 146, in addition to being located on opposite sides of the cell, are located in the same plane as the detector channels 136 and their associated optics. Due to changes in the index of refraction n A of the analyte gas, the path of the laser beam through the analysis chamber 126 may change direction somewhat as the analyte gas index of refraction, n A changes. It will bend one direction or the other as illustrated in FIG. 4, or go straight through without changing if the index of refraction of the analyte gas is the same as that of the buffer gas, depending on the relative indices of refraction of the analyte gases and the buffer gases. This beam movement can have the deleterious effect of causing variations in the amount or intensity of Raman scattered light which reaches the detectors.
Placement of the outlet ports 144 and 146 in substantially the same plane as the detector channels 136 minimizes the effects on detection efficiency caused by laser beam movement within the gas analysis chamber 126. This is because the detector optics which collect the light being scattered from the laser beam by the gas sample are generally focused on a location within the analysis chamber 126 which coincides with the laser beam's nominal location within the chamber 126. When the axis of the laser beam moves in a direction which is perpendicular to the plane of the detector optics, the effect on the intensity of Raman scattered light reaching the detectors is much greater than if the beam movement is in a direction which is parallel to the plane of the detector optics. The effect is similar to looking through a small window. Moving closer to or farther from the window (along the line of sight) does not greatly alter the scene observed. This is to the effect observed by the detectors when the laser beam moves parallel to the detector plane. If, however, one moves past the window in a direction which is perpendicular to the line of sight through the window, the scene can change dramatically depending on the change in the line of sight. This "changing scene" to the eye is analogous to having the intensity of the scattered light signal change at the detector and is what is observed by the detectors when the laser beam moves in a direction which is perpendicular to the plane of the detectors. In most gas analyzer systems, the accuracy of the system depends on the stability and consistency of the intensity of the scattered light signal.
Another embodiment of the present invention combines the features of diametrically opposed outlet ports with placement of the outlet ports in the same plane as the detector channels to optimize both laser performance and detection efficiency.
A constant pressure gas cell embodiment of the invention is illustrated in FIG. 5. A gas cell 210 has an inlet port 212 which is connected via a conduit 220 to a source of patient sample gas 224. A pump 226 is connected to an outlet port 228 of the gas cell 210 via a conduit 230. The pump 226 draws a gas sample from the source of patient sample gas 224 through the gas cell 212 by means of conduits 220 and 230. The gas sample is analyzed while in the gas cell by passing a light beam through the gas sample and monitoring the light scattered by the gas sample. Preferably, the gas lines connecting gas cell 210 to the source of sample gas 224 and the pump 226 also dampen pressure variations which may be caused by the pump 226 or by pressure fluctuations at the source of the patient sample. Gas cell 210 may be any type of gas cell which contains a sample while a light beam passes therethrough. For example, the gas cell 210 may be a buffer gas cell 10 or 110 as disclosed in FIGS. 1, 2, 2A and 3 herein. However, the gas cell 210 need not be a buffer gas cell and could be a closed type cell as disclosed in U.S. Pat. Nos. 4,784,486 and 4,676,639, the disclosures of which are hereby incorporated herein by reference.
Referring again to FIG. 5, a pressure transducer 242 is connected to the gas cell 212 via a conduit 244. As shown in FIG. 5, the pressure transducer is connected to the cell 212 near the outlet port 228, however, the pressure transducer may be connected to the gas cell 212 in any manner which is suitable for monitoring the gas pressure within the gas cell 212.
A pressure control circuit 250 comprises an amplifier 252, a reference voltage source 254, a processor 256, a pulse width modulator 258 and a pump drive circuit 260. In operation, the pressure transducer 242 monitors the pressure at the outlet port 228 of the gas cell 212 and provides an electrical signal which is a function of the gas pressure within the cell 212 to the amplifier circuit 252. The processor 256 supplies a reference signal to the amplifier that establishes a pressure set point. The amplifier compares the reference voltage or pressure set point with the pressure transducer pressure electrical signal to control the pulse width modulator 258. The output of the pulse width modulator 258 is amplified by the pump drive circuit 260 which provides a signal that controls the pump 226. If the pressure in the gas cell starts to rise, the pump is driven harder to increase the flow through the cell which results in a larger pressure drop between the source of patient sample gas 224 and the gas cell 212 thereby lowering the pressure in the gas cell. Conversely, if the pressure in the gas cell starts to drop, the pump rate is reduced thereby raising the pressure in the gas cell. The pressure set point is variable and determined by the user, then communicated through the processor to the controlling electronics. Alternatively, a variable restrictor 270 may be inserted into conduit 230 to regulate the flow of gas into the gas cell 210, thus controlling the pressure in the cell. Typically, the pressure in the cell is regulated at approximately 100 mm of Hg less than the prevailing atmospheric pressure, which varies with altitude and weather conditions. The gas cell pressure is controlled within approximately plus or minus 0.5 Torr of this reduced atmospheric level. If the measured pressure in the gas cell varies from the control level by more than approximately plus or minus 0.3 Torr, an error message is generated to warn of the pressure fluctuation.
Although the invention has been described in terms of preferred embodiments, it will be apparent to those skilled in the art that numerous modifications can be made without departing from the spirit and scope of the claims appended hereto. Such modifications are intended to be included within the scope of the claims. | A gas analysis cell having a pressure control system eliminates pressure variations in the gas cell regardless of changes in restriction, gas viscosity and barometric pressure. Since optical alignment through the gas cell is sensitive to gas pressure, maintaining a constant pressure in the gas cell makes the system more stable. | 6 |
BACKGROUND OF THE INVENTION
[0001] (1) Field of the invention
[0002] The present invention relates to ash formation during the burning of coal and more particularly to methods and compositions for treatment of coal to reduce the amount of ash deposition onto surfaces during the burning of coal.
[0003] (2) Description of the Related Art
[0004] Sub-bituminous coal of the Powder River Basin of the United States typically includes a significant amount of calcium bound within the coal structure. In fact, the typical calcium level of this type of coal burned in industrial boilers in the United States today is substantially higher than it had been in the past and that level is expected to increase in the future as industries continue to turn to lower sulfur level coal.
[0005] When the coal is burned, the calcium in the coal is converted to calcium oxide. The formation of calcium oxide results in an ash that is reflective and whiter than the fly ash produced upon combustion of bituminous coal. This reflective ash accumulates on surfaces situated in the structure in which the burning takes place. Such structures will be referred to herein as “furnaces,” as such term is considered in its broad sense to refer to any enclosed structure in which heat is produced. A particular situation in which such ash formation is encountered is in furnaces employed in boiler systems, but the furnaces contemplated herein are not limited to such systems and may be incorporated into any number of uses.
[0006] Prominent among the surfaces on which reflective ash tends to accumulate are the furnace tube walls through which heat is to be transferred from the combustion taking place in the furnace. Such ash accumulation is undesirable because the layer it forms over the surfaces is an insulative barrier that reduces the heat transfer through the surfaces, thereby reducing the efficiency of heat transfer from the furnace. Such ash accumulation is also undesirable because the reflective ash layer reflects the heat back into the burner area, increasing the gas and flame temperatures beyond that for which the furnace was designed, which in turn causes the increased heat to radiate back to the fly ash, eventually creating a slagging environment. Moreover, because of the inadequate heat transfer to the water flowing through the furnace wall tubes, the furnace exit gas temperature (FEGT) rises above the design level, increasing the fouling propensity in the convective zone and, in the case of the boiler, finally increasing the boiler exit gas temperature. The increased FEGT also raises the temperature of steam in downstream heat absorption sections above design conditions, requiring use of cooling spray water to reduce the steam temperature. The formation of this type of ash has become more pronounced in recent years. Many boiler furnaces were designed for burning high sulfur bituminous coal. However, as alluded to above, beginning in the late 1970's and early 1980's, environmental concerns led to conversion from burning high sulfur bituminous coal to burning low sulfur coals, such as that from the Powder River Basin in Wyoming (PRB coal), began. Even though the ash content of PRB coals is lower than that of the high sulfur coals they replace, PRB coals tend to be high in calcium. Thus, burning the lower sulfur coals in the furnaces designed for relatively high sulfur coal has resulted in increased slagging, and particularly increased white ash formation. See, for example, “PRB Coal Switch Not a Complete Panacea,” by Buecker, B. and Meinders, J., Power Engineering, November 2000, pp. 76-80.
[0007] Conventionally, equipment such as soot blowers and water lances have been employed to reduce slagging and lower the FEGT, but with limited success and the additional costs, efforts and interference associated with such equipment. Moreover, use of a water lance is undesirable because it introduces cold water into the furnace, inducing thermal stress to the tubes, decreasing the furnace wall tube life and increasing the maintenance and replacement costs of the boiler.
[0008] Other prior art methods have addressed the problem of ash accumulation on furnace walls with chemical techniques for darkening the ash on the walls. For example, U.S. Pat. No. 5,819,672, incorporated herein by reference, describes the addition of a darkening agent such as iron oxide and, preferably, also a fluxing agent to produce a dark ash coating or an additional dark ash coat over the existing ash on the furnace walls. Because the ash is darkened, not only is the tendency of the ash to reflect heat back into the furnace reduced, but the heat absorption by the ash is increased, thereby reportedly aiding transfer of heat from the furnace through the walls thereof. Although the additives may be applied to the coal, the preferred method contemplates applying the dark coat directly to the ash. In any event, such techniques do not eliminate—or even reduce—ash accumulation and suffer from various other disadvantages as well. For example, pursuant to such techniques, ash still is allowed to build up on the surfaces at previous rates with the attendant problems, such as the need for routine cleaning or replacement.
[0009] In the above-noted article in Power Engineering, it is reported that ADA Environmental Solutions has experimented with the application of a proprietary mixture of iron oxides and stabilizing chemicals to coal prior to combustion to enhance the viscosity characteristics of the slag formed from burning PRB coal and that the preliminary results from this experimentation “have been very promising.” However, no further information is provided in the article as to the composition of the additive and, although the article later discusses ash control, the article nowhere discusses the additive with respect to the ash control. Indeed, the article indicates that ash accumulation and high FEGT are still significant problems, requiring the use of water lances.
[0010] Thus, the industry is still searching for an effective and efficient means for darkening the ash and reducing the FEGT, slagging and ash accumulation on surfaces in coal-burning furnaces. Techniques that accomplish such objectives, while avoiding the need for purchasing and operating equipment such as soot blowers and water lances would be particularly desirable. And, of course, it is also especially desirable that the technique avoid raising adverse environmental implications.
SUMMARY OF THE INVENTION
[0011] Briefly, therefore, the present invention is directed to a novel method for inhibiting accumulation of reflective ash on surfaces in a furnace in which high calcium-containing coal is burned. According to the method, an effective amount of an iron compound is added to the coal to produce treated coal, free of added fluxing agent, and the treated coal is then burned.
[0012] The present invention also is directed to a novel method for increasing the melting point of ash produced during the burning of calcium-containing coal. According to the method, an effective amount of an iron compound is added to the coal to produce treated coal, and the treated coal is burned, producing ash of increased melting point.
[0013] Among the several advantages found to be achieved by the present invention, therefore, may be noted the provision of a method for darkening ash formed in the combustion of coal; the provision of such method that also reduces the tendency of the ash to accumulate on surfaces in the furnace; the provision of such method that also reduces the FEGT in the furnace; the provision of such method that improves the overall boiler efficiency and reduces generation cost; the provision of such method that eliminates the need for soot blowers and water lances; the provision of such method that reduces slagging in the furnace; and the provision of such method that avoids introduction of adverse environmental consequences.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0014] In accordance with the present invention, it has been discovered that, surprisingly, a darker ash may be produced and accumulation of reflective ash on surfaces in a furnace may be reduced simply by adding iron oxide to calcium-containing coal prior to combustion of the coal in the furnace. Thus, rather than lowering the melting point of the ash or calcium components thereof by addition of a fluxing agent to encourage adhesion to the furnace surfaces as described in U.S. Pat. No. 5,819,672, the process of the present invention involves raising the melting point to inhibit such adhesion. Moreover, it has been found that the addition of the iron oxide not only darkens the ash and inhibits the tendency of the ash to adhere to the furnace surfaces but, accordingly, also reduces the FEGT and consequently slag and fouling deposit formation. In fact, the improvements in furnace performance resulting from the method of this invention have been discovered to be even greater than those achieved with the conventional treatments by soot blowers and water lances, thus eliminating the need for such equipment. And all of this has been found to be accomplished without any detected adverse environmental consequence.
[0015] While not wishing to be bound by any particular theory of operation, applicant believes that the present invention operates by conversion of the calcium oxide formed upon combustion of the coal to calcium ferrite, thereby converting calcium oxide in the ash to relatively higher melting point and darker calcium ferrite. This conversion may be illustrated by the following idealized formula wherein ferric oxide is the additive:
CaO+Fe 2 O 3 →Ca(FeO 2 ) 2
[0016] In any event, according to the present invention, a composition comprising an iron compound is added to the calcium-containing coal prior to combustion of the coal, preferably prior to delivery of the coal to the furnace and most desirably prior even to grinding the coal. The iron compound in the most desirable embodiment contemplated by the invention is iron oxide, especially ferric oxide. It is also desirable that the additive composition contain no other component that interferes with the ability of the iron compound to raise the melting (or fusion) point of the resulting ash. The additive composition particularly should not contain a fluxing compound or an adhesive or other substance that increases the tendency of the ash to adhere to the furnace surfaces.
[0017] In one preferred embodiment, the additive is a composition of iron oxide (especially in the form of ferric oxide) and clay, which is primarily silica with traces of alumina and other calcium and magnesium compounds. One such preferred formulation comprises 93% by weight ferric oxide, 5% by weight silica, with the remainder made up of alumina and other calcium and magnesium compounds. Hematite ore has been found to be a particularly appropriate additive composition. However, in another preferred embodiment, the additive composition may be the iron compound, with no other ingredients other than at most minor impurities.
[0018] The preferred form of the additive composition is a powder. However, other forms, such as a suspension of that powder in a liquid such as a liquid hydrocarbon (e.g., kerosene), may be employed if so desired. Although the liquid may be water, such is not desirable for the obvious thermodynamic and other disadvantages of introducing water into the combustion process.
[0019] The additive composition is applied to the coal, such as by spraying or spreading, in an amount sufficient to provide an effective amount of the iron compound to combine with the calcium content of the coal. In the context of inhibition of ash on the furnace walls, by “an effective amount” of the iron compound what is meant is an amount that is sufficient to result in less ash deposition on the furnace walls when the coal treated with the iron compound is burned than forms on the walls when equivalent coal without the iron compound treatment is burned under equivalent conditions. In the context of increasing the melting point of the ash produced when the coal is burned, by “an effective amount” of the iron compound what is meant is an amount that is sufficient to increase the melting point of the ash produced when the coal is burned over the melting point of the ash produced when equivalent coal without the iron compound treatment is burned under equivalent conditions. Such ash having a melting point higher than that of the ash produced when equivalent coal without the iron compound treatment is burned under equivalent conditions is referred to herein as “ash of increased melting point.”
[0020] The optimal amount of iron compound to be added to the coal depends on the calcium content of the coal. Generally, however, when the iron compound is ferric oxide and the coal is of sub-bituminous type from the Western United States and particularly PRB coal, the optimal amount of iron compound has been found to be from about 0.1% to about 1.0%, more preferably about 0.25% to about 1.0%, especially about 0.5%, based on the weight of the coal. Based on the theorized formula set forth above, this represents, surprisingly, only about one-sixth the amount of ferric oxide required by the stoichiometry. Although greater amounts of iron compound may be used, it is believed that there is currently no economic advantage to doing so.
[0021] After application of the additive composition to the coal, the treated coal then is ground, if not already ground, and conveyed to the furnace, wherein it is exposed directly to the flame envelope of the furnace combustion process. As described above, the resulting ash is darker and has a higher melting point compared to the ash formed from coal not treated in accordance with this invention. In fact, rather than tenaciously adhering to the exposed surfaces, the darkened ash is gas-borne fly ash, most of which escapes from the furnace with the exhaust gases, reducing or even eliminating the need for cleaning out the ash from the furnace wall. And because the product comprises calcium, iron and oxygen, which pose no environmental concern. Moreover, because the FEGT is lower when the coal is treated with the iron compound according to this invention, use of the water lance may be eliminated.
[0022] The following examples describe preferred embodiments of the invention. Other embodiments with the scope of the claims herein will be apparent to one skilled in the art from consideration of the specification or practice of the invention as disclosed herein. It is intended that the specification, together with the examples, be considered exemplary only, with the scope and spirit of the invention being indicated by the claims which follow the examples.
EXAMPLE 1
[0023] Efficacy of ferric oxide in reducing furnace slagging caused by white reflective ash was tested in a 35 MW boiler furnace manufactured in 1967 and designed for high sulfur bituminous coal. The coal fed to the furnace was switched to calcium-rich PRB coal in the 1980's, causing white ash slagging, which increased the furnace exit gas temperature (FEGT) and the boiler exit gas temperature, limiting operation of the unit to reduced load despite removal of furnace slag by soot blowers and with a water lance, and requiring flue gas conditioning to meet opacity compliance. The use of the water lance was discontinued as ferric oxide was added to PRB coal in dosage rates varying from 0.25% to 1.0%, based on the weight of the coal. The FEGT was measured continuously with an optical pyrometer located at the furnace exit level and the plant operating parameters were monitored routinely. Upon such treatment, slagging was reduced significantly and the FEGT showed a reduction of 50 to 115° F. (28 to 64° C. reduction) during operation at about 30 MW. The color of the fulrnace bottom ash and fly ash darkened as the dosage rate increased. The bottom ash was of fine size and contained no lumpy slag particles. The load fluctuated from 31 MW to 15 MW due to demand constraint, but during operation at 30 MW the furnace wall remained visibly clean and the fireball was tinted orange. De-superheater spray, which prior to the addition of the ferric oxide operated constantly at 30 MW load, dropped to zero at a ferric oxide dosage rate of 0.5% and higher, based on the weight of the coal, and remained at zero for the remainder of the test period. Moreover, opacity, SO 2 and NO x were found to be well under compliance level, with the NO x level actually decreasing by 15% from the pre-test level. It is believed that the NO x reduction was due to the use of less (7.5%) excess air compared to the normal operating level of 10-11%.
EXAMPLE 2
[0024] A furnace was operating at an average heat rate of 11,892 Btu/kwh. Upon installation of a water lance and operation of the water lance twice a day, the heat rate dropped to 11,615 Btu/kwh. The coal fed to the furnace then was treated with 0.5% ferric oxide, based on the weight of the coal, and the use of the water lance was discontinued. After treatment, and without use of a soot blower or water lance, the heat rate was measured at 11,231 Btu/kwh, representing a reduction of 5.5% in coal usage, which at 7,800 tons of coal a year and US$24/ton, translates into a savings of US$187,000 a year. During the treatment period, the furnace remained clean and slag did not build up on the walls. There was a thin film of ash on the surfaces of the tubes. At 30 MW load on the generator, the steam temperatures remained reasonably constant at 870-890° F. (465-477° C.), compared to the design temperature of 900° F. (482° C.).
[0025] All references, including without limitation all papers, publications, presentations, texts, reports, manuscripts, brochures, internet postings, journal articles, periodicals, and the like, cited in this specification are hereby incorporated by reference. The discussion of the references herein is intended merely to summarize the assertions made by their authors and no admission is made that any reference constitutes prior art. The inventors reserve the right to challenge the accuracy and pertinence of the cited references.
[0026] In view of the above, it will be seen that the several advantages of the invention are achieved and other advantageous results obtained.
[0027] As various changes could be made in the above methods and compositions without departing from the scope of the invention, it is intended that all matter contained in the above description as shown in the accompanying drawings shall be interpreted as illustrative and not in a limiting sense. | A method, for inhibiting accumulation of light-colored ash on the walls of a furnace in which coal containing high levels of (coal-bound) calcium is burned, comprises adding an iron compound to the coal prior to burning the coal, burning the coal, and producing calcium ferrite, thereby improving heat transfer in furnaces and resultant plant efficiency without adverse environmental consequences. | 2 |
BACKGROUND OF THE INVENTION
The present invention relates to a pressing board and, more particularly, to a pressing board having a rounded surface.
FIG. 13 is a side sectional view of a conventional pressing board 100. Referring to FIG. 13, the pressing board 100 is constructed as follows. A rectangular flat board is employed as a base material 2, a cushion material 4 with proper shock absorbing property and a uniform thickness is stuffed between the base material 2 and a covering cloth 3 covering the base material 2, and ends of the covering cloth 3 are stapled to the base material 2 by a plurality of rivets 5.
When an iron I is pressed on a clothing C using the pressing board 100, heat generated from the flat back surface of the heated iron I is applied to the clothing, and the clothing is flattened by the back surface. Thus, wrinkles of the clothing C are ironed out.
The base material 2 of the conventional pressing board 100 employs a solid particle board or plywood in consideration of mechanical strength, cost, and the like.
As is known, a metal gauze or the like can be used as the base material 2 of the pressing board in order to facilitate release of steam when a steam iron is used.
Normally, in the pressing board, a rectangular flat board is employed as the base material 2, the cushion material 4 with proper shock absorbing property and a uniform thickness is stuffed between the base material 2 and the covering cloth 3 covering the base material 2, and ends of the covering cloth 3 are stapled to the base material 2 by the plurality of rivets 5.
When a steam iron is used, steam generated by the steam iron temporarily passes through the clothing, and is then filled between the covering cloth 3 and the base material 2. The base material 2 sometimes employs a metal gauze or the like in order to facilitate release of steam, thereby preventing steam from being filled as described above. In this case, since the metal gauze releases too much steam, the steam cannot be effectively utilized.
The solid particle board or plywood has a sufficient mechanical strength but has a large weight and is not easy to handle. For this reason, the base material 2 serving as the base portion of the pressing board is preferably formed by resin molding such as blow molding capable of forming a hollow member, thus reducing weight and cost.
However, since the conventional pressing board 100 is constructed as described above, when the iron I is moved in a direction indicated by arrow z, in particular, when the clothing C is thin like a white shirt, the clothing C is excessively squeezed and stretched by the back surface and the corner of the back surface of the iron I, and a crease A may be created. If the iron is moved in such situation, more wrinkles are left on the clothing C.
When a sliding frictional resistance between the iron I and the clothing C is large, undesirable luster may be left on the clothing C.
Therefore, the ironing operation using the conventional flat pressing board 100 requires skill and time.
Since the conventional pressing board is constructed as described above, steam is easily released, and cannot be sufficiently applied to the clothing.
A low cost resin material used for blow molding can't withstand high temperatures, and has poor mechanical strength. Such a resin material cannot be used for the pressing board.
SUMMARY OF THE INVENTION
The present invention has been made in consideration of the above problems, and has as its first object to provide a pressing board in which its iron working surface is rounded so as to achieve an almost line or point contact state between the back surface of an iron and the working surface, thereby preventing creation of a crease, and which has a low iron sliding frictional resistance so as not to require skill in ironing, and so as to shorten an ironing time.
It is a second object of the present invention to provide a pressing board in which a cushion material is appropriately deformed to prevent the clothing to be ironed from being damaged.
It is a third object of the present invention to provide a pressing board in which a large number of projections are formed on a working surface on which an iron is pressed so as to increase a heat resistance and to fill steam between adjacent projections, so that steam can be effectively applied to the clothing to be ironed, and which can have a sufficient mechanical strength even if it is formed of a resin material by relatively inexpensive blow molding or the like.
It is a fourth object of the present invention to provide a pressing board with excellent workability on which a clothing can be easily spread.
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
FIG. 1A is a plan view of a first embodiment of a pressing board 1;
FIG. 1B is a cross-sectional side view of FIG. 1A;
FIG. 2A is a plan view showing a state wherein a white shirt W is put on the pressing board 1;
FIG. 2B is a side view showing a state wherein after the white shirt W is put on the pressing board 1, the pressing board 1 is placed on a working base G;
FIG. 3 is a side view of a pressing board 10 of a second embodiment;
FIG. 4A is a perspective view showing an outer appearance of a state wherein a pressing board 1 of a third embodiment is in use;
FIG. 4B is a partially cutaway perspective view of FIG. 4A;
FIG. 5 is a plan view showing a part of a corner portion of a base material 2 of the pressing board 1 shown in FIG. 4B;
FIG. 6 is a sectional view taken along a line X--X in FIG. 5;
FIG. 7 is a plan view showing a part of the base material 2 of the pressing board 1 shown in FIG. 4A;
FIG. 8 is a sectional view taken along a line Y--Y in FIG. 7;
FIG. 9 is a partially cutaway perspective view showing a pressing board 10 of a fourth embodiment, and a steam iron 200;
FIG. 10 is a sectional view cut along a plane parallel to a longitudinal groove 18 of the pressing board 1 of the fourth embodiment;
FIGS. 11A, 11B, and 11C are plan views of a base material 2 of a pressing board 1 of other embodiments;
FIGS. 12A, 12B, and 12C are side views showing states wherein legs 6 are provided to the base material 2; and
FIG. 13 is a side sectional view of a conventional pressing board 100.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Various embodiments of a pressing board according to the present invention will now be described with reference to the accompanying drawings.
Referring to FIG. 1A, the pressing board 1 has substantially the shape of a body with a pair of longitudinal sides 17 which are sufficiently longer than lateral sides. On one lateral side, a head 12 and a pair of shoulders 13 are formed, and on the other lateral side, a border 15 is formed.
The pair of shoulders 13 are formed by parts of circles having a radius R1, whereas the border 15 is formed by part of a circle having a radius R2.
Although it is ideal to prepare various sizes of pressing boards 1 for use as clothings of adults and children, it is enough to prepare a pressing board for adults use only in consideration of the frequency of use.
Referring to FIG. 1B, the pressing board 1 is constructed as follows. The substantially body-shaped board rounded to form a convexly shaped outer surface with a radius R3 and to serve as a base material 2. A cushion material 4 having proper shock absorbing property and uniform thickness is stuffed between the base material 2 and a covering cloth 3 covering the base material 2. Ends of the cloth 3 are stapled to the base material 2 by a plurality of rivets 5.
Referring to FIG. 2A, the back portion of the white shirt W is located on the back side of the pressing board 1, so that the head 12 of the pressing board 1 extends from the neck portion of the white shirt W.
When the white shirt W is put on the pressing board 1, the shoulders 13, formed as parts of circles, cause proper tension force in the inner portion of the shoulder part of the white shirt W. Thus, the ironing operation can be performed without pressing the white shirt W by a second hand.
Referring to FIG. 2B, the back of the white shirt W is supported between both ends 1a of the pressing board 1 and the working base G. Thus, during ironing, the white shirt W need only be lightly pressed by hand.
As can be seen from FIG. 3, the pressing board 10 has a flat back surface in order to achieve stability in use.
Referring again to FIG. 2A, the state of use of the pressing board 1 will be described below. When the iron I is pressed on a white shirt W put on the pressing board 1 and is placed parallel to the longitudinal direction of the pressing board 1, as indicated by I1 in FIG. 2A, a contact state between the iron I and the white shirt W is approximate to a line contact state indicated by a dotted line x in FIG. 2A. Meanwhile, when the iron I is placed to be perpendicular to the longitudinal direction of the pressing board 1, the contact state is approximate to a point contact state as indicated by a dotted line y.
Since the cushion material 4 is appropriately deformed to serve as a shock absorbing material, the clothing C of the white shirt W can be prevented from being damaged.
Therefore, the iron I contacts the white shirt in this manner, so that creation of crease as the conventional problem can be prevented, and a sliding frictional resistance can be reduced. As a result, an ironing operation can be performed while turning the iron I, thus preventing damage to the clothing C.
Sleeves of clothings, trousers, skirt, and the like can be ironed on the rounded iron working surface.
In the above description, the base material 2 has a rounded surface as a part of circle with the radius R3 but may have a more complicated rounded surface.
Referring to FIGS. 4A and 4B, the iron working surface of the pressing board 1 is rounded upward, so that a contact state between an iron and the iron working surface is not a surface contact state but is approximate to the above-mentioned line or point contact state.
The pressing board 1 is constructed as follows. A cushion material 4 with proper shock absorbing property and uniform thickness is arranged under a covering cloth 3 covering the entire iron working surface of the pressing board 1. Ends of the cloth 3 are fixed to the base material 2 by a plurality of rivets (not shown) or laces 14.
Foldable legs 6 on the distal ends of which rubber shoes 7 are fitted under pressure are provided to the back surface portion of the base material 2.
In FIGS. 5 and 6, a large number of circular projections 20 extending upwardly and substantially normal to the working surface are formed on the top surface, i.e. the iron working surface of the base material 2, and projecting members 20A are formed on its edge portion. The base material 2 has a hollow structure as shown in FIG. 5 since it is formed by blow molding.
In FIGS. 7 and 8, a large number of projections 40 each having an illustrated shape are formed on the top surface, i.e., the iron working surface of the base material 2. A large number of projections 40 each having a shape other than the illustrated shape may be formed.
In FIG. 9, the pressing board 10 is constructed as follows. That is, as shown in FIG. 9, a large number of longitudinal and lateral grooves 18 and 19 are formed in the working surface, on which the steam iron 200 is pressed, of the base material 2 of the pressing board 10. A cushion material 4 having proper shock absorbing property and uniform thickness is arranged between the working surface and a covering cloth 3 covering the entire surface of the working surface on which the steam iron 200 is pressed. Ends of the cloth 3 are fixed to the base material 2 by a plurality of rivets (not shown) or rubber laces. In consideration of easy removal from molds upon blow molding, appropriate removal slopes are formed on the side walls of the longitudinal and lateral grooves 18 and 19.
The function of the pressing boards 1 and 10 shown in FIGS. 4A and 9, respectively, i.e., a case wherein the steam iron 200 is used, will be described with reference to FIG. 10.
The same function can be obtained by the pressing board 1 on which the large number of projections 20 are formed shown as in FIG. 5. Therefore, a description will now be made with reference to only FIG. 10.
In FIG. 10, steam S is generated by the steam iron 200, and is applied to the clothing C. Of the steam S passing through the clothing C, a steam S component reaching a top surface 2A is applied to the clothing C in the same manner as in the conventional pressing board. A steam S component reaching the lateral or longitudinal groove 19 or 18 is stored in the groove. As a result, the clothing C is vertically sandwiched by the steam S components. That is, since the steam S is caught in the grooves, the clothing C is steamed, and hence, the steam can be effectively applied to the clothing C.
On the other hand, some components of the steam S generated by the steam iron 200 are appropriately released inside the base material 2 through steam holes 8. Excessive steam S components are released to air through steam holes 8 formed in the back surface of the base material 2.
Furthermore, since the longitudinal and lateral grooves 18 and 19 and the projections 20 serve as heat radiation members, heat generated from the iron can be appropriately radiated. Therefore, the base material 2 can be formed of a blow-molded material having a low heat-resistant temperature.
Note that in the above embodiment, the longitudinal and lateral grooves are formed in the base material 2. However, grooves may be formed obliquely in a diamond shape, or recesses may be locally formed. With this structure, the same result can be obtained as a matter of course.
Referring to FIG. 11A, in order to obtain a ship-like shape shown in the drawing a head 12 and a border 15 are formed.
Referring to FIG. 11C, in this embodiment, a border 15 and a linear side are formed.
Referring to FIG. 11C, in this embodiment, two linear sides are formed.
When the pressing board 1 is constructed using the base material 2 having the shape illustrated in FIG. 11A, 11B, or 11C, the iron working surface of the pressing board 1 is rounded upward, and a contact state between the iron and the working surface almost becomes the line or point contact state, as described above, thus facilitating ironing.
Referring to FIG. 12A, the legs 6 of the pressing board are retractably arranged on the base material 2. Legs 6A and 6B cross at the central portion. When the end portion of the leg 6A is engaged with an engaging hole of a hook 16, the illustrated height can be held. The portion of clothing which is not subjected to ironing is housed in a gap portion defined according to the height of the legs 6, and the portion of the clothing C, which is to be ironed is spread on the pressing board, so that the it can be ironed.
A chain 21 is bridged between the crossing portion of the legs 6A and 6B and the base material 2, so that the legs 6 are not excessively separated from the base material 2.
FIGS. 12B and 12C are side views which show modifications of the legs 6. A portion the clothing is housed under the pressing board, and a portion to be ironed of the clothing C is spread on the pressing board, so that the clothing can be ironed.
As many apparently widely different embodiments of the present invention can be made without departing from the spirit and scope thereof, it is to be understood that the invention is not limited to the specific embodiments thereof except as defined in the appended claims. | A rounded pressing board substantially providing a line or point contact surface between the iron working surface and the bottom surface of a flat iron, thus reducing the force required to operate an iron and shortening the ironing time. The pressing board body is molded into a hollow shape by blow molding and the iron working surface of the pressing board body has a large number of projections to facilitate the application of steam to the cloth which is to be ironed and to provide the line or point contact surface. | 3 |
BACKGROUND OF THE INVENTION
The present invention relates to digital electronic circuits and, more particularly, to a voltage level shifter circuit that receives an input signal and generates an output signal that is a level-shifted version of the input signal.
Generally speaking, components and nodes in digital logic circuits transition from one logic level to another during the operation of the circuit. These transitions typically are between a logical high state at some voltage above ground level, and a logical low state at ground level. Occasionally, different circuits operating at different logical high voltage levels are required to interface with one another thereby requiring the voltage level of one circuit to be shifted with respect to the voltage level of the other circuit. For example, the voltage in one circuit may have a logic high voltage level of 0.75V and the voltage in the other circuit may have a logic high voltage level of 1.32V. The first circuit has a voltage swing of zero to 0.75V and the second circuit has a voltage swing of zero to 1.32V. Level shifters provide the connection between two such circuits, shifting the level of the signals from the first voltage swing to the second voltage swing.
One conventional voltage level shifter is illustrated in FIG. 1 . This circuit attempts to eliminate static current, i.e. leakage current, consumption using a feedback circuit and a pull-device. The circuit comprises a first CMOS inverter 100 having complementary MOSFETs P 1 and N 1 , a second CMOS inverter 110 having complementary MOSFETs P 2 and N 2 , a third CMOS inverter 120 with complementary MOSFETs P 3 and N 3 , and a feedback unit 130 comprising P-type MOSFET P fb , N-type MOSFET N fb and pull up device P pu 140 .
Each of the first and second inverters 100 , 110 receives an input signal at a voltage V in at a first, lower voltage level V DDL . The first inverter 100 outputs the inverse of the input signal at a node 150 , which is input to the third inverter 120 . The third inverter 120 inverts the signal at node 150 and provides an output signal V out at voltage level V DDH , where the logical state of V out reflects that of V in . Thus, V out is a level-shifted version of V in .
The output of the second inverter 110 also is the inverse of the input voltage V in , at the lower voltage level V DDL . This is fed to the gate of device N fb of feedback unit 130 . Similarly, the voltage at node 150 is fed to the gate of the device P fb of the feedback unit 130 . The feedback unit 130 provides an output signal at node 170 that is used to drive the gate of pull-up device P pu 140 .
Typically, the digital voltage level shifter of FIG. 1 operates as the input voltage at V in transitions between a logical high at the first voltage V DDL and a logical low at ground voltage where it is desired that the output voltage V out reflects the logical state of V in , but at the level shifted voltage, V DDH . In this circuit, the input voltage V in is at a first, lower voltage V DDL and the output voltage is at a second, higher voltage V DDH . It is believed that improvements may be realized in reduction of leakage current when V IN rises to a logic high of V DDL . For instance, and analyzing the case when V IN rises to a logic high of V DRL , N 1 turns on, but P 1 initially does not completely turn off since the source of P 1 is at a voltage level of V DDH . Thus, static current temporarily flows through P PU , P 1 , and N 1 . Given the nature of normal CMOS processes, N-channel FETs have approximately twice the current sinking and sourcing capability of identically-sized P-channel FETs. Additionally, the circuit of FIG. 1 has two P-channel FETs, P 1 and P PU , connected in series, thereby further reducing the strength of P 1 and P PO in comparison to N 1 . Therefore, N 1 succeeds in pulling node 150 to ground. V IN also turns N 2 on and P 2 completely off (since the source of P 2 is attached to V DDL ), thus pulling node 160 to ground. With the gates of both P FB and N FB pulled low, node 170 is pulled up to V DDH volts, thereby shutting off P PU and eliminating the static current that previously flowed through P PU , P 1 , and N 1 , and terminating the drive fight between P 1 and N 1 . Also, with node 150 being at ground, P 3 is on, N 3 is off, and V OUT is pulled up to V DDH , all in response to V IN rising to V DDL .
As V IN transitions to logical low, P 1 goes on and N 1 goes off, however, node 150 remains at logical low (ground) because in the previous cycle of operation (as described above), P pu was switched off, thereby isolating node 150 from V DDH , at least temporarily.
Additionally, P 2 goes on and N 2 goes off, thereby pulling node 160 to logical high at V DDL . In turn, N fb goes on and since node 150 is currently at ground, P fb is on, which means a leakage path exists from V DDH to ground through P fb and N fb . Node 170 is being driven by P fb to be pulled up to V DDH and by N fb to be pulled to ground. Because N fb is of a physically larger size in order to influence the voltage at node 170 as described above, the larger-sized device N fb wins the drive fight eventually pulling node 170 to ground. Only then is node 150 pulled up to V DDH through P pu and P 1 , thereby switching P fb off and cutting off the leakage from V DDH through P fb and N fb to ground.
The above-described circuit operation is less than optimal because of the leakage current from V DDH to ground through P fb and N fb , which flows for a relatively long time which, in turn, requires the physical size of device N fb to be relatively large. Additionally, the circuit of FIG. 1 takes a relatively long time for the output voltage to transition to ground in response to a corresponding transition on the input voltage. Accordingly, it would be advantageous to have a digital voltage level shifter that provides some improvement on the above problems.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention is illustrated by way of example and is not limited by the accompanying figures, in which like references indicate similar elements. Elements in the figures are illustrated for simplicity and clarity and have not necessarily been drawn to scale.
FIG. 1 illustrates a conventional digital voltage level shifter; and
FIG. 2 illustrates a digital voltage level shifter in accordance with an embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
In an embodiment of the invention there is provided a digital voltage level shifter for receiving an input signal of a first voltage swing and outputting an output signal of a second voltage swing, the output signal being a level-shifted version of the input signal, the digital voltage level shifter comprising: a first inverter comprising: a first input for receiving the input signal; and a first output; a second inverter comprising: a second input connected to the first output; and a second output for outputting the output signal; and a control stage for controlling switching of the digital voltage level shifter, the control stage comprising a feedback circuit branch having a control stage switch configured to assume a non-conducting state dependent on a logical state of the output signal.
In another embodiment of the invention there is provided a digital voltage level shifter for receiving an input signal of a first voltage swing and outputting an output signal of a second voltage swing, the output signal being a level-shifted version of the input signal, the digital voltage level shifter comprising: a first inverter comprising: a first input for receiving the input signal; and a first output; a second inverter comprising: a second input connected to the first output; and a second output for outputting the output signal; and a control stage for controlling switching of the digital voltage level shifter, the control stage comprising: a control stage inverter having a control stage inverter input for receiving the input signal; and a control stage inverter output; and wherein the second inverter comprises a second inverter switch having a switch control input controlled by the control stage inverter output.
In a further embodiment of the invention there is provided a method of operating a digital voltage level shifter configured to receive an input signal of a first voltage swing and output an output signal of a second voltage swing, the output signal being a level-shifted version of the input signal, the method comprising: providing a first inverter comprising: a first input for receiving the input signal; and a first output; providing a second inverter comprising: a second input connected to the first output; and a second output for outputting the output signal; providing a control stage for controlling switching off the digital voltage level shifter, the control stage comprising a feedback circuit branch having a control stage switch; applying an input signal to the first input; and controlling the control stage switch to assume a non-conducting state dependent on a logical state of the output signal.
Embodiments of the invention may provide significant technical benefits in comparison with conventional techniques. In the first place, the leakage current that flows for a relatively long time in the conventional circuit of FIG. 1 from V DDH to ground through P fb and N fb , is substantially reduced, as the digital voltage level shifter may be configured for the control stage switch to assume a non-conducting state dependent on a logical state of the output signal. Secondly, the physical size of the switching device that corresponds to device N fb in the conventional circuit of FIG. 1 may be of a significantly reduced size, thereby leading to a reduced footprint for the circuit. Thirdly, significant improvements may be realized in the time taken for the output voltage to fall to logical low/ground in response to the input voltage going to logical low.
The terms “a” or “an,” as used herein, are defined as one or more than one. Also, the use of introductory phrases such as “at least one” and “one or more” in the claims should not be construed to imply that the introduction of another claim element by the indefinite articles “a” or “an” limits any particular claim containing such introduced claim element to inventions containing only one such element, even when the same claim includes the introductory phrases “one or more” or “at least one” and indefinite articles such as “a” or “an.” The same holds true for the use of definite articles.
Unless stated otherwise, terms such as “first” and “second” are used to distinguish between the elements such terms describe. Thus, these terms are not necessarily intended to indicate temporal or other prioritization of such elements.
Because the apparatus implementing the present invention is, for the most part, composed of electronic components known to those skilled in the art, full details will not be explained in any greater extent than that considered necessary for the understanding and appreciation of the underlying concepts of the present invention and in order not to obfuscate or distract from the teachings of the present invention.
Referring now to FIG. 2 , a digital voltage level shifter 200 in accordance with an embodiment of the invention is illustrated. The digital voltage level shifter 200 includes a voltage translation stage 202 , a driver stage 204 and a control stage 206 . The voltage translation stage 202 receives an input voltage and translates the input voltage to the voltage to which it is to be level shifted. The driver stage 204 drives the level-shifted output voltage. The control stage 206 controls switching of the digital voltage level shifter 200 .
The voltage translation stage 202 comprises a first inverter 208 comprising a complementary CMOS pair of P-type MOSFET M 5 210 and N-type MOSFET M 6 212 . The first inverter 208 has a first input 214 for receiving the input signal which is at a first or lower voltage level V ddi . The first inverter 208 has a first output 216 that outputs a first output signal at node y, which is the logical inverse of the first input 214 , but translated to the second, higher voltage level V ddo . The drain terminals of M 5 210 and M 6 212 are tied together to provide the first output 216 of first inverter 208 .
The voltage translation stage 202 further comprises another switching device M 4 218 which, in the embodiment of FIG. 2 , is a P-type MOSFET having a drive input 220 at its gate. The source of M 4 218 is driven by the second, higher-voltage supply V ddo , while the drain of M 4 218 is connected in series to the source of M 5 210 .
The driver stage 204 comprises a second inverter 222 comprising a P-type MOSFET M 7 224 and N-type MOSFET M 8 226 . Note that in the embodiment of FIG. 2 , the second inverter 222 is not a true complementary CMOS inverter since the gates of M 7 224 and M 8 226 are not tied together. Instead, the gate of M 8 226 has a switch control input 228 driven by an output of the control stage 206 , which will be described in further detail below. On the other hand, the gate 230 of M 7 224 is driven by the output of the first inverter 208 on node y. The gate of M 7 224 is the second input of the second inverter 222 . The drains of M 7 224 and M 8 226 are tied together and provide the second output 232 , which is the output of the digital voltage level shifter 200 . Additionally, the source of M 7 224 is tied to the higher-voltage supply V ddo , and the source of M 8 226 is tied to ground.
The control stage 206 comprises a feedback circuit branch 234 including three switches PMOSFET M 1 236 , NMOSFET M 2 (control stage switch) 238 , and NMOSFET M 3 240 . The first switch M 1 236 has a source connected to the higher-voltage V ddo and a drain tied to a drain of the second switch M 2 238 . The second or control stage switch M 2 238 has a source connected to a drain of the third switch M 3 240 , and a source of the third switch M 3 240 is tied to ground. Thus, the control stage switch M 2 238 is connected in series between PMOS and NMOS transistors 236 , 240 . In the embodiment of FIG. 2 , the control stage switch M 2 238 is a low-voltage threshold device.
The first switch M 1 236 has a switch control input 242 , in which a gate of the first switch M 1 236 is connected to the output of the first inverter 208 at node y. The control stage switch M 2 238 has a switch control input 244 , in which a gate of the control stage switch M 2 238 is connected to the output of the second inverter 222 . The third switch M 3 240 has a switch control input 246 , in which a gate of the third switch M 3 240 is connected to an output of a third inverter 248 , as will be described below.
The control stage 206 further comprises a control stage inverter 248 comprising a complementary CMOS pair of PMOSFET M 9 250 having a source connected to a lower-voltage supply V ddi , and NMOSFET M 10 252 having a source terminal tied to ground. The drains of M 9 250 and M 10 252 are connected together and provide the control stage inverter output 256 at node Ab, which drives device M 3 240 at its gate 246 , as noted above. Also the gates of M 9 250 and M 10 252 are tied together and form the control stage input 254 of the control stage inverter 248 . For the avoidance of leakage between V ddi and ground through M 9 250 and M 10 252 , the gates M 9 250 and M 10 252 are driven by a signal A which has a range from ground to V ddi . Thus, the feedback circuit branch 234 has the third switch M 3 240 , which has its gate 246 controlled by the output 256 of the control stage inverter 248 .
In operation, when input A goes to logical high/V ddi , MOSFET device M 5 210 of the first inverter 208 is switched partially on, and transitions to being switched fully off after node net 131 is pulled up to logical high. This is driven by M 1 236 and M 2 238 , the gates y 242 and Z 244 of which are, respectively, at logical low and logical high/V ddo and MOSFET device M 6 212 being switched on. This pulls the first output 216 of the first inverter 208 at node y to logical low/ground. In turn, this switches M 7 224 on and the second output 232 at node Z is pulled to high/V ddo . So, the logical state of the second output at node Z reflects the logical state of input A, but at the higher voltage level, V ddo .
Because the first input A on 214 is at logical high/V ddi , and because the control stage inverter input A 254 is tied to the first input 214 , PMOSFET M 9 250 of the control stage inverter 248 is switched off, corresponding NMOSFET M 10 252 is switched on and the control stage inverter output 256 at node Ab is pulled to logical low/ground. This drives second inverter switch M 8 226 to off, as the switch control input 228 of M 8 226 is tied to the control stage inverter output 256 at node Ab. This ensures that the second output 232 at node Z remains at logical high/V ddo .
As node y is at logical low/ground, switch M 1 236 is turned on because its gate is tied to node y 216 . Additionally, and because the second output Z 232 is tied to the switch control input 244 of control stage switch M 2 244 , this device switches on. Further, the third switch NMOSFET M 3 240 of the feedback circuit branch 234 is also switched off because it is driven by the control stage inverter 248 output Ab 256 . As a consequence, the node net 131 220 at the gate of M 4 218 is pulled up approximately to logical high/V ddo . Actually, the gate of M 4 218 is at the level of V ddo less the threshold voltage V t1 of the control stage switch M 2 238 which is, in this embodiment, a low voltage threshold device. Therefore, this means that M 4 218 is eventually switched off, as the difference between the gate voltage of M 4 218 and the source voltage should be greater than the threshold voltage V t of M 4 218 , in this embodiment a standard threshold voltage device. That is, (Vddo−Vt 1 ) gate voltage of m 4 −(Vdd 0 ) source voltage of m 4 |=|Vt 1 |<|Vt| of M 4 218 as the standard MOSFET threshold voltage is greater than the threshold voltage of a LVT MOSFET. As a consequence of M 4 218 being switched off, there is no leakage current from V ddo to ground through M 4 218 , M 5 210 and M 6 212 .
Now, considering the case where input A 214 goes to logical low/ground, M 6 212 is switched off and M 5 210 is switched on. However, because M 4 218 remains in the off state from the previous cycle of operation when the input voltage switched to a logical level high, as noted above, the first output 216 of the first inverter 208 at node y is floating.
Additionally, M 9 250 is switched on and M 10 252 is switched off, thereby pulling up the control stage inverter output 256 at node Ab to logical high/V ddi . In turn, this switches on M 8 226 , pulling the second output 232 at node Z to ground. (M 7 224 is in the conducting state at this time, but only for a very short period. M 3 240 and M 8 226 are switched on simultaneously, so net 131 220 is pulled to ground, in turn switching on M 4 218 and pulling node y 216 to logical high/V ddo very quickly through M 4 218 and M 5 210 and, therefore, M 7 224 is switched off.) Therefore, the logical state of the second output 232 at node Z reflects the logical state of the signal on input 214 , on node A. The control stage inverter 248 has a control stage inverter input 254 for receiving the input signal A and a control stage inverter output 256 . The second inverter switch 226 of the second inverter 222 has a switch control input 228 controlled by the output Ab 256 of the control stage inverter 248 .
It will also be appreciated that FIG. 2 illustrates a digital voltage level shifter 200 for receiving an input signal of a first voltage swing and outputting an output signal of a second voltage swing, the output signal being a level-shifted version of the input signal. In the embodiment of FIG. 2 , the switch control input 228 of the second inverter 222 is connected to the control stage inverter output 256 on node Ab.
Immediately following the switching on of M 8 226 , which pulls the second output 232 at node Z to ground, the control stage switch M 2 238 assumes a non-conducting state because its gate 244 is tied to and driven by output 232 at node Z, and the feedback circuit branch 234 is put into an open-circuit condition, regardless of the state of the first switch M 1 236 (still on at this point from the previous cycle of operation when the input on 214 went to logical high) and the third switch M 3 240 .
Further, because the control stage inverter output 256 has been pulled to logical high/V ddi , then M 3 240 is also switched on, thereby pulling the voltage at node net 131 220 to ground, switching on M 4 218 and driving the voltage of the first output 216 of the first inverter 208 at node y to logical high/V ddo , thereby switching off M 7 224 . Switching on of M 8 226 as mentioned above pulls the second output 232 at node Z to ground. So, the second inverter switch M 8 226 (an NMOSFET) is configured to assume a conducting state when the input signal A is at a logical low state. The second inverter 222 further comprises a PMOSFET M 7 224 , which has a gate terminal that receives the second input 230 of the second inverter 222 at node y.
After the first output 216 at node y has been pulled up to logical high, the first switch M 1 236 switches off because its gate 242 is tied to, and driven by, node y. However, and as mentioned above, the feedback circuit branch 234 is already in open circuit due to the fact that the control stage switch M 2 238 is off because the output 232 at node Z has been driven low.
Thus, this provides a significant improvement from the conventional circuit of FIG. 1 , because the gate 244 of the control stage switch M 2 238 is tied to node Z, as soon as the second output 232 at node Z goes to logical low, then, the control stage switch M 2 238 is immediately switched off, thereby cutting off any leakage current that might otherwise flow from V ddo to ground through the first and third switches M 1 236 and M 3 240 , as was the case with the conventional circuit of FIG. 1 . As discussed above, in the absence of the control stage switch M 2 238 and it being driven by the output Z, leakage current flow in the feedback circuit branch 234 is not cut out until the first output 216 at node y is driven high, thereby switching of the first switch M 1 236 . Consequently, the current rating and/or physical size of the third switch M 3 240 can be significantly reduced in comparison with device N fb of FIG. 1 . Therefore, the overall footprint of the digital voltage level shifter 200 may be significantly smaller than that of the conventional digital voltage level shifter of FIG. 1 .
In the embodiment of FIG. 2 , the concept implemented is that of using a single path from the higher-voltage supply Vddo to charge or discharge the intermediate nodes. This single path is cut off when the input assumes a low voltage domain high logic. The same circuit path and then re-made when the input voltage is at logical low, also reducing the fall delay, and assisted by an inverted input signal.
In the embodiment of FIG. 2 , the control stage switch M 2 238 assumes a non-conducting state when the output signal of the second output 232 is in a logical low state. The control stage switch M 2 238 has a switch control input 244 connected to the second output 232 of the second inverter. As described above, in this embodiment, the control stage switch M 2 238 is an NMOSFET having its gate at the switch control input 244 , which is connected to the output of the second inverter at node Z so when the second output (node Z) goes low, the control stage switch M 2 238 goes to the non-conducting or off state.
The first switch M 1 236 also assists in helping to curtail leakage power in instances where the control stage switch M 2 238 is a LVT device; that is, in this embodiment, the control stage switch M 2 238 comprises a low voltage threshold (LVT) NMOSFET. Such devices have a higher sub-threshold leakage even when the voltage on the input (gate) of this transistor is sitting very close to, but not quite at, V ddo . Thus, when the first switch M 1 236 is in a non-conducting state, this helps prevent the possibility of breakdown of the control stage switch M 2 238 when it is a LVT device. Additionally, the combination of voltages at the inputs of the switches M 1 236 , M 2 238 , and M 3 240 that takes the voltage at node net 131 220 quickly to ground.
As noted above, the embodiment of FIG. 2 may provide significant technical benefits when compared to, for example, the conventional circuit of FIG. 1 . In this regard, circuit simulations were performed for the purposes of comparison between the conventional circuit FIG. 1 and the level shifter 200 of FIG. 2 . The simulations were conducted with the 55 nm technology mode, in the voltage range of 0.9V to 1.32V, with the models of best, worst, typ, bpwn and wnwp. Rise delay, fall delay and leakage were measured, yielding the results shown in Tables 1-4.
TABLE 1
Transition times for low to high (0.9 V to 1.32 V)
Circuit
Corner
Temp C.
Cell Rise (ns)
Cell Fall (ns)
FIG. 2
wcs
−40
0.111
0.383
FIG. 1
wcs
−40
0.119
6.700
FIG. 2
typ
25
0.093
0.264
FIG. 1
typ
25
0.100
0.364
TABLE 2
Leakage current for low to high (1.32 V to 0.9 V)
Circuit
Corner
Temp C.
Leakage (W)
FIG. 2
wcs
150
8.59E−08
FIG. 1
wcs
150
1.36E−07
TABLE 3
Input transition for high to low (1.32 V to 0.9 V)
Circuit
Corner
Temp C.
Cell Rise (ns)
Cell Fall (ns)
FIG. 2
wcs
−40
0.113
0.106
FIG. 1
wcs
−40
0.115
0.509
FIG. 2
typ
25
0.093
0.091
FIG. 1
typ
25
0.095
0.362
TABLE 4
Leakage current for high to low (1.32 V to 0.9 V)
Circuit
Corner
Temp C.
Leakage (W)
FIG. 2
wcs
150
4.05E−08
FIG. 1
wcs
150
5.92E−08
In tables 1-4, bcs refers to the best condition on which the chip is working i.e. chip is experiencing the most favorable conditions or more specifically when PMOS and NMOS are performing best means fastest (MOS behavior under these conditions). wcs refers to the worst condition on which the chip is working i.e. chip is experiencing the most unfavorable conditions or more specifically when PMOS and NMOS are performing worst means slowest. Typ refers to the typical condition on which the chip is working i.e. chip is experiencing the normal conditions or more specifically when PMOS and NMOS are performing typically means expected. bpwn refers to the best PMOS and worst NMOS condition on which the chip is working i.e. chip is experiencing the corner conditions or more specifically when PMOS are operating under the best conditions and NMOS are working under worst conditions. bnwp refers to the best NMOS and worst PMOS condition on which the chip is working i.e. chip is experiencing the corner conditions or more specifically when NMOS are working under best conditions and PMOS are working under worst conditions.
Table 1 illustrates the advantage of the level shifter 200 when compared with the level shifter of FIG. 1 in the cell fall time, when the input signal is at 0.9V and being shifted to 1.32V at the output. Table 2 illustrates that the level shifter 200 has lower leakage power than the circuit of FIG. 1 , when the input signal is at 0.9V and being shifted to 1.32V at the output. Table 3 illustrates that the level shifter 200 has faster cell fall time than the circuit of FIG. 1 when the input signal is at 1.32V and shifting it to 0.9V at the output. Table 4 illustrates that the level shifter 200 has improved leakage power consumption over the circuit of FIG. 1 when the input signal is at 1.32V and being shifted to 0.9V at the output.
Therefore, it can be seen that significant improvements are realized in the cell fall times. For instance, the simulation cell fall time when transitioning from logical low to logical high for the circuit of FIG. 1 on the wcs process corner is 6.7 ns, compared with 0.383 ns as simulated for the circuit of FIG. 2 . Further, the simulated leakage power loss is reduced from 1.36E-07 W in the circuit of FIG. 1 to 8.59E-08 W of FIG. 2 . In low to high voltage shifting, the circuit of FIG. 2 can translate signals in the range of 0.75 V to 1.32 V under the bcs, typ, wcs, wnbp, and bnwp process corners. Further, signal translation by the level shifter 200 is bidirectional. The embodiment may be implemented in applications where shifting from a lower to a higher voltage is required, and also when shifting from a higher to a lower voltage.
Table 5 illustrates the FMEA (Failure Mode Analysis) results for the level shifter 200 .
TABLE 5
FMEA RESULTS
Functional
Cell Rise
Cell Fall
Corner
Temp
Voltage V
result
(ns)
(ns)
wcs
−40
Vddi = 0.75,
FAIL
0.173
1.06
Vddo = 1.32
wcs
25
Vddi = 0.75,
PASS
0.173
0.853
Vddo = 1.32
wcs
150
Vddi = 0.75,
PASS
0.168
0.670
Vddo = 1.32
wcs
−40
Vddi = 0.76,
PASS
0.162
0.986
Vddo = 1.32
wcs
25
Vddi = 0.76,
PASS
0.166
0.792
Vddo = 1.32
wcs
150
Vddi = 0.76,
PASS
0.163
0.637
Vddo = 1.32
The results in the above tables demonstrate a significant reduction in the fall delay, approximately 20 times less when compared with the circuit of FIG. 1 . Further, leakage is less when compared to the prior art, an improvement of between 50 and 100%, as may be derived from Tables 1 to 4.
Furthermore, this allows a significant area reduction in the footprint of the digital voltage level shifter in comparison to the prior art. Yet further, the circuit of FIG. 2 is able to operate with an input voltage of down to 0.75 V.
By now it should be appreciated that there has been provided novel techniques for digital voltage level shifting which may be implemented across, for example, all low-power System on Chip (SoC) designs using multiple voltage domains, where it is required to pass signals from one voltage domain to another. This may be realized by having a switching device in a feedback circuit branch assume a non-conducting state when the output of the digital voltage level shifter falls to logical low.
Although the invention is described herein with reference to specific embodiments, various modifications and changes can be made without departing from the scope of the present invention as set forth in the claims below. Accordingly, the specification and figures are to be regarded in an illustrative rather than a restrictive sense, and all such modifications are intended to be included within the scope of the present invention. Any benefits, advantages, or solutions to problems that are described herein with regard to specific embodiments are not intended to be construed as a critical, required, or essential feature or element of any or all the claims. | A dual supply bidirectional level shifter performs voltage level shifting in two directions, low to high and high to low. A feedback control branch and a control stage inverter are provided that reduce leakage power and allow for low delay time while also allowing for a small circuit footprint. | 7 |
RELATED APPLICATION
This is a divisional application of application Ser. No. 136,900 filed Dec. 22, 1987, which, in turn, was a continuation-in-part application of Ser. No. 852,474, filed Apr. 15, 1986, abandoned.
BACKGROUND OF THE INVENTION
The present invention relates to a process for preparing bismaleimides, and more particularly, to a process for preparing aromatic ether bismaleimides. The invention also relates to an improved and more efficient process for preparing bismaleamic acids which are the precursors of the desired bismaleimides.
Currently, bismaleimide resins are being favorably considered as replacements for epoxy resins because of their greater thermal stability and lower moisture sensitivity. Current epoxy resins have a maximum useful temperature of 350° F. and are weakened by absorbed moisture, particularly when used as matrix resins in fiber reinforced composites. However, the currently available commercial bismaleimides are brittle and are not competitive with epoxies in terms of toughness.
Aromatic ether bismaleimides promise to have greater toughness and lower moisture retention than other bismaleimides because of the ether groups in the main chain and the relatively large monomer chain length. Preliminary data indicate that this type of structure is tougher than state of the art bismaleimides and moisture retention levels are around 2% compared with 4-5% for conventional commercial bismaleimides.
As a result of the aforementioned properties, a great commercial interest in aromatic ether bismaleimides exists at this time. Aromatic ether bismaleimides find application as composite matrix resins for structural composites and electric circuit boards, and as adhesives for bonding structural materials. The aromatic ether bismaleimides may be used alone or in conjunction with other co-monomers.
U.S. Pat. No. 3,839,287 discloses typical polyarylimides which are prepared from aromatic diamines and maleic anhydride. The diamines are reacted with maleic anhydride and then the product is chemically converted to the imidized form by addition of acetic anhydride and triethylamine, or sodium acetate. These polyarylimides are taught to be useful in the preparation of glass cloth prepregs, molding materials, and adhesives.
U.S. Pat. No. 4,288,583 discloses a curable mixture which contains maleimides and phenols. The maleimides may be aliphatic or aromatic, and are prepared by reacting the appropriate amines or polyamines with the maleic anhydride in a polar solvent and in the presence of a catalyst.
U.S. Pat. No. 4,464,520 discloses aromatic bismaleimides which are prepared by using the usual imidization reaction where the imidization is carried out in an inert aprotic solvent using a slight excess of maleic anhydride. Useful inert aprotic solvents include dimethylformamide, dimethylsulfoxide, and dimethylacetamide. Typical reaction temperatures are 40°-60° C. with a preferred range of 50°-60° C. Typical reaction times are 1-1.5 hours. The resulting polybismaleimides are useful as binders in composite molded components, and for circuit board manufacture.
U.S. Pat. No. 4,460,783 is similar to U.S. Pat. No. 3,839,287 in disclosing first reacting aromatic ether diamines with maleic anhydride to form bismaleamic acids which then are reacted with acetic anhydride in the presence of a catalyst such as potassium acetate to convert the amic acid groups to imide groups.
Among aromatic ether bismaleimides, particular commercial interest exists in a bismaleimide of the Formula (I) ##STR2## which is derived from Bisphenol A. This bismaleimide is disclosed in U.S. Pat. No. 4,460,783 to Niahikawa et al and U.S. Pat. No. 3,839,287 to Kwiatkowski et al. This compound reportedly can be prepared by reacting Bisphenol A with 4-chloro-1-nitrobenzene to yield the compound 2,2-bis4(4-nitrophenoxy)phenyl)propane which is reduced to the corresponding diamine 2,2-bis[4-(4-aminophenoxy)phenyl]propane and reacted with maleic anhydride to produce the bismaleimide. The latter reaction proceeds in two stages, first, with formation of the maleamic acid derivative, and then with imidization. For the reasons discussed infra, it is believed that neither the Niahikawa nor the Kwiatkowski process produces the bismaleimide of Formula (I) in significant yield and free of large concentrations of co-products.
Several problems are encountered when the Niahikawa reaction sequence is used on an industrial scale. On an industrial scale, the aromatic diamine reactant is employed at a high concentration in the reaction solvent. As the conversion of the aromatic diamine to the maleamic acid increases, the maleamic acid precipitates from the reaction mixture and the reaction mixture becomes too thick to stir even at low concentrations. The mixture has the appearance of an aerosol foam. On a large scale, the temperature cannot be controlled and the mixture does not react uniformly. As a result, a product is obtained which contains high concentrations of by-products. This product is disadvantageous because these by-products interfere with the normal overall curing mechanism of the bismaleimide, and in addition, generate excessive volatiles during cure which results in voids in the cured products.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a process for producing in high yields aromatic ether bismaleimides of the Formula (II) ##STR3## wherein A is a divalent mononuclear or polynuclear aromatic linking group which proceeds with good yields, can be scaled up readily, and provides fewer by-products.
In a preferred embodiment, A in Formula (II) is a divalent mononuclear or polynuclear aromatic linking group selected from but not limited to the group consisting of ##STR4## where in the above divalent mononuclear or polynuclear aromatic linking group, one or more of the aromatic nuclei may be substituted by a halogen atom (e.g., fluorine, chlorine, bromine, or iodine), an alkyl group (e.g., having 1 to 4 carbon atoms , an aryl group, or an arylalkyl group.
More specifically in a preferred embodiment, A is a divalent mononuclear or polynuclear aromatic linking group selected from the group consisting of ##STR5## where in the above divalent mononuclear or dinuclear aromatic linking group, one of the aromatic nuclei may be substituted by a halogen atom (e.g., fluorine, chlorine, bromine, or iodine), an alkyl group (e.g., having 1 to 4 carbon atoms), an aryl group, or an arylalkyl group.
In accordance with the present invention, aromatic ether bismaleimides of Formula (II) above are produced by the process which comprises first preparing a bismaleamic acid of Formula (III) ##STR6## where A is defined as above in Formula (II). This reaction is carried out by adding maleic anhydride to a solution of an aromatic diamine of the Formula (IV) ##STR7## wherein A is defined as above in Formula (II) in a solvent under conditions such that the temperature of said maleic anhydride and said diamine does not exceed about 15° C., but preferably such that the temperature does not exceed about 0° C. At a critical point in the reaction, preferably before more than 1.4 mol of maleic anhydride has reacted with 1.0 mol of the aromatic diamine, a trialkylamine is added to the reaction mixture in an amount not in stoichiometric excess of the maleamic acid and in an amount sufficient to materially reduce the viscosity of the reaction medium so that it can be stirred more easily. The trialkylamine reacts to ionize the maleamic acid moiety and form an amine salt. The maleic anhydride addition is continued until the stoichiometrically required amount is added to the reaction mixture. In the second step of the process, an additional quantity of the trialkylamine is added to convert substantially all of the acid groups of the bismaleamic acid to amine salt groups. An imidization catalyst such as nickel (II) acetate and a dehydrating agent such as acetic anhydride are then added and the reaction is continued to convert the maleamic acid groups to imide groups.
By infrared spectra and liquid chromatography data, it has been established that the products prepared by the above process contain at least about 80 weight % of the desired bismaleimide product. Such products have properties which differ significantly from products produced by the prior art processes and are superior in performance properties when employed as resins, and particularly, as impregnating resins in the manufacture of composites and circuit boards.
Other objects and advantages of the invention will be apparent from the following description, the accompanying drawings, and the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an infrared spectrum of a bismaleimide of Formula (I);
FIG. 2 is the infrared spectrum of the bismaleamic acid precursor of the bismaleimide of Formula (I);
FIG. 3 is an infrared spectrum of a product prepared by a process corresponding to Example I of U.S. Pat. No. 4,460,763;
FIG. 4 is an infrared spectrum of a product prepared by a process corresponding to U.S. Pat. No. 3,839,287;
FIG. 5 is an infrared spectrum of a product offered for experimental use by a U.S. manufacturer and which is reported to be the bismaleimide of Formula (I); and
FIG. 6 is a liquid chromatographic plot of the product of Formula (I).
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The aromatic diamines employed as starting materials in the manufacture of the bismaleimides of Formulae (I) and (II) may be prepared by following a technique which involves the reaction of the corresponding diphenol with 4-nitrochlorobenzene to produce an intermediate bis-nitro compound The nitro groups on this compound are subsequently reduced to amine groups in a well-known manner.
In the first step of the process, an aromatic diamine of Formula (IV) is reacted with maleic anhydride to form a maleamic acid intermediate of Formula (III). To provide an efficient economical process, the aromatic diamine is dissolved in a good solvent to prepare a high solids solution containing a minimum concentration of about 0.3 g/ml of solvent, and preferably, about 0.3 to 0.5 g/ml of solvent. Representative examples of solvents useful in the present invention are acetone, dimethylacetamide (DMAC), N-methyl pyrrolidone (NMP), and tetrahydrofuran (THF). These solvents are selected on the basis of the solubility of the diamine therein, their inertness with respect to the starting and intermediate materials, and the ease of removal of the solvent from the final product. Tetrahydrofuran is the preferred solvent because of ease of its removal from the final product. DMAC and NMP can be used but they are more difficult to remove from the final product.
The maleic anhydride is added to the diamine under a combination of conditions of reactant temperature and addition rate which is designed to maintain the reaction temperature at a temperature below 15° C., preferably at a temperature below 0° C., and more preferably at -5° C. or less. The reaction between the diamine and the maleic anhydride proceeds very quickly. If the temperature becomes too high, the reaction proceeds too quickly and undesirable by-products are formed.
Before reaction, the diamine solution is cooled to 15° C. or less, preferably to a temperature below 0° C., and more preferably to -5° C. or less. The maleic anhydride is preferably added to the diamine as a solution (preferably in the same solvent used to dissolve the aromatic amine) having a concentration of about 0.2 to 0.4 g of maleic anhydride per 1 ml of solvent. This solution can be added to the diamine solution through an addition funnel. The rate of addition of the maleic anhydride solution is adjusted such that the reaction proceeds at a controlled rate. The maleic anhydride solution is typically added slowly to the diamine solution with stirring at the rate of approximately 1 to 3 g/mol aromatic diamine/min., with a preferred rate of 1.50 to 1.70 g/mol aromatic diamine/min.
As the reaction proceeds, the concentration of the maleamic acid product increases and the solubility relationships in the reaction medium change. Eventually, typically when about 1.25 to about 1.40 mol of maleic anhydride has been reacted with 1.0 mol of aromatic diamine, the maleamic acid product precipitates. The reaction mixture becomes too thick to stir and has the appearance of an aerosol foam.
The discovery has been made that the addition of a trialkylamine to the reaction mixture prevents precipitation of the maleamic acid products and the rapid build-up of viscosity. The trialkylamine ionizes the maleamic acid intermediate to form an amine salt such that the reaction product remains soluble and does not precipitate from the reaction solution. A preferred trialkylamine useful in the present process is triethylamine, but other liquid trialkylamines such as tripropylamine and tributylamine may also be used.
The trialkylamine can be added in periodic increments or in a single charge subject to the consideration that the concentration of unreacted maleic anhydride is minimal (to avoid possible rearrangements of maleic anhydride) and that the trialkylamine is not added in stoichiometric excess of the maleamic acid content. The trialkylamine is added in at least the minimum amount sufficient to materially reduce the viscosity of the reaction medium so that it can be stirred more easily. Since the trialkylamine is employed for another purpose in the second step of the overall process, it is convenient to add the trialkylamine in an approximate stoichiometric quantity. The trialkylamine is usually added to the reaction mixture at a rate of approximately 2 to 8 g/mol aromatic diamine/min. The rate is controlled so that the temperature is maintained within the limits earlier noted, viz. below about 15° C., preferably below 0° C., and more preferably -5° C. or less.
After the trialkylamine addition is completed, the addition of maleic anhydride is continued. The total amount of maleic anhydride added is less than, equal to, or greater than 2 mols maleic anhydride/mol aromatic diamine (i.e., a stoichiometric excess), and typically, about 2.0 to 2.5 mols per mol diamine.
After the addition of the maleic anhydride is completed, the reaction solution is allowed to increase in temperature gradually to insure that all of the diamine has reacted. For example, the reaction solution can be allowed to heat to 20° C. for about 1 hour and then to 60° C. for 30 minutes which forces the reaction to completion so that any unreacted diamine will react to form maleamic acid products.
The products formed as described above consist predominantly of bismaleamic acids conforming to Formula (III). Where these products are desired for purposes other than conversion to bismaleimides of Formula (II), they can be recovered, isolated, and purified by techniques readily apparent to those skilled in the art.
To convert the bismaleamic acid products prepared above to desired bismaleimides of Formula (II), the following procedures are employed. A further quantity of trialkylamine is added to the previous reaction mixture to convert substantially all of the maleamic acid groups to the corresponding amine salt. The further alkylamine so added serves as a co-catalyst for the ring closure reaction. The reaction mixture is cooled to a temperature of 15° C. or less before the trialkylamine is added, and the addition is made at a rate such that the temperature does not exceed this limit. This temperature reduction is necessary because at higher temperatures, the maleamic acids can isomerize to fumaric acids, undesired by-products.
With formation of the maleamic acid completed, the process moves to the second stage, namely, formation of the maleimide rings. The ring closure reaction is customarily accomplished through use of a ring closure catalyst and a dehydration agent added directly to the maleamic acid product. In this process, the ring closure catalyst and dehydration agent are added to the amine salt of the maleamic acid. In this invention, it has been found that the preferred ring closure catalyst is nickel (II) acetate and the preferred dehydration agent is acetic anhydride. The nickel (II) acetate is used with the trialkylamine salt as a co-catalyst for maximum effectiveness. Nickel acetate, sodium acetate, or excess triethylamine, for example, can be used alone in catalytic amounts, but result in a slower reaction rate and a product with higher concentrations of by-products.
After liquid acetic anhydride and dry nickel (II) acetate tetrahydrate are added to the reaction mixture, the reaction mixture is held at an elevated temperature for 1 to 3 hours but preferably for 1.5 hours. A preferred temperature range is 55° to 65° C. The acetic anhydride is added to the reaction mixture in an amount of approximately 222 to 246 ml/mol maleamic acid. The nickel (II) acetate tetrahydrate is added to the reaction mixture in an amount of approximately 11 to 13 g/mol maleamic acid.
Various methods can be used to recover the aromatic ether bismaleimide product. One example of a recovery method is as follows.
The solvent is removed under a vacuum. After the solvent has been removed from the reaction mixture, the resultant syrup is poured into ice water while stirring very rapidly The mixture must be stirred with good shear in order to promptly quench the mixture so that the resulting powder is very fine. Otherwise, an agglomeration will result.
The resulting slurry is allowed to stand for 18 hours. The solid is collected by filtration and washed twice with cold water. The solid is air dried for 18 hours.
The process of the invention provides compositions which contain at least 80 weight % of the desired bismaleimide product of either Formula (I) or Formula (II). Such compositions differ significantly from prior art products which reportedly are bismaleimides of Formula (I) or Formula (II), but which in fact contain very large concentrations of by-products resulting from isomerization reactions and an evident failure to obtain significant yields in the dehydration/ring closing reaction of the maleamic moieties to form the desired imide moieties. The factual data supporting the above conclusions are discussed infra.
A composition which contains at least 80 weight % of the bismaleimide of Formula (I) will be characterized in:
(a) being curable to a thermoset resin by the application of heat,
(b) having a glass transition (T g ) endotherm of about 65° C. and a reaction exotherm peak of about 240° C. as measured by differential scanning calorimetry at a heating rate of 10° C./min.,
(c) having a viscosity of less than about 300 poises at 120° C.,
(d) having the following solubilities, in weight %, at 25° in the following solvents:
(i) Dioxane - ca 16%
(ii) Methylene Chloride - ca 44%
(iii) Tetrahydrofuran - ca 39%
(iv) Toluene - ca 4%
(v) Acetone - ca 55%
(e) having an infrared spectrum corresponding substantially to FIG. 1 of the drawings,
(f) having a strong infrared absorption peak at about 690cm-l,
(g) having, in a fully cured state, a glass transition temperature of at least about 300° C.,
(h) having, as a fully cured compression molded, neat resin, a moisture uptake of only about 2 weight % when exposed to boiling water for 96 hours, said moisture containing specimens retaining at least about 70% of the dynamic modulus values of the bone dry specimens when measured at temperatures up to 300°, and
(i) releasing only about 2 weight % of volatiles when heated to 300° at a heating rate of about 10° C./min.
The concentration of the desired bismaleimide component in a composition can be determined by a number of analytical techniques. The method used in obtaining the data reported herein was a Reverse Phase High Pressure Liquid Chromatography separation. This method is well known in the art. Briefly, in the work reported herein, a sample of the composition is dissolved in dioxane (0.1 weight % solids). This sample is passed through a packed column and the sample is sorbed on the packing. The sorbed sample is eluted with a dioxane-water mixture of constantly changing proportions. The dioxane-water proportions are controlled and changed by the instrument. The eluting solvent is passed through an ultraviolet light detector which continuously measures solute concentration. The detector output signal is plotted v. time to produce linear plots in which the vertical peaks represent a single component present in the sample. The area under each peak represents the concentration of that eluted component. By comparing the areas under each peak, the concentration of any component in the sample can be expressed quantitatively.
The present invention is more fully illustrated by the following non-limiting Examples.
EXAMPLE I
Part A-Preparation of Bismaleamic Acid
To a 5-liter flask equipped with two addition funnels, mechanical stirrer, reflux condenser, thermometer, and N 2 inlet tube, were added 500 g (1.218 moles) of 2,2-bis4-(4-aminophenoxy)phenyl]propane and 1300 ml of tetrahydrofuran. The reaction solution was cooled to -5° C. by means of an external acetone/dry ice bath. To the addition funnel was added a solution of 239 g (2.437 mol) of maleic anhydride dissolved in 810 ml of tetrahydrofuran. This solution was added slowly to the reaction flask with stirring while maintaining the temperature of the reaction at -5° C. When 66.6% of the maleic anhydride solution (approximately 80 minutes) had been added, this addition was stopped. Into the second addition funnel was placed 150 ml (108.9 g; 1.076 mol) of triethylamine and added slowly to the reaction mixture,
still maintaining the temperature at -5° C. When the triethylamine addition was completed, the addition of the maleic anhydride solution was continued. The total time for the two maleic anhydride additions was two hours. The reaction mixture was stirred an additional hour at -5° C. The cooling bath was removed and the mixture stirred one hour at 20° C. A heating mantle was added and the reaction mixture was heated to 60° C. for 30 minutes.
Part B-Preparation of Bismaleimide
The reaction mixture of Part A containing the bismaleamic acid intermediate product was cooled to -5° C. At this temperature, 530 ml (384.8 g; 3.802 mol) of triethylamine was slowly added, keeping the temperature at -5° C. Then 285 ml (308.4 g; 3.021 mol) of acetic anhydride and 15 g (0.060 mol) of nickel (II) acetate tetrahydrate were added and the reaction mixture was heated to 60° C. and held at that temperature for 1.5 hours. At this time, the heating mantle was turned off and vacuum applied to the system to remove the tetrahydrofuran. Once the tetrahydrofuran had been removed from the reaction mixture, the resultant syrup approximately 400 m portions) was poured into 2400 ml of ice water while stirring very rapidly. The slurry which resulted was allowed to stand for 18 hours. The solid was collected by vacuum filtration and washed two times with 2 liters of cold water each time. The solid was air dried for 18 hours. The yield was 690 g(1.209 mol; 99% yield).
EXAMPLE II
Part A-Preparation of Bismaleamic Acid
To a one-liter flask equipped with two addition funnels, mechanical stirrer, reflux condenser, thermometer, and N 2 inlet tube, were added 100 g (0.342 mol) of 1,3-bis(4-aminophenoxy)benzene and 300 ml of tetrahydrofuran. The reaction solution was cooled to -5° C. by means of an external acetone/dry ice bath. To one of the addition funnels was added a solution of 67.8 g (0.691 mol) of maleic anhydride dissolved in 160 ml of tetrahydrofuran. This solution was added slowly to the reaction flask with stirring while maintaining the temperature of the reaction at -5° C. When 66.6% of the maleic anhydride solution (approximately 80 minutes) had been added, this addition was stopped. Into the second addition funnel was placed 42 ml (30.5 g; 0.301 mol) of triethylamine and added slowly to the reaction mixture, still maintaining the temperature at -5°. When the triethylamine addition was completed, the addition of the maleic anhydride solution was continued. The total time for the two maleic anhydride additions was two hours. The reaction mixture was stirred an additional hour at -5° C. The cooling bath was removed and the mixture stirred one hour at 20°. A heating mantle was added and the reaction mixture was heated to 60° C. for 30 minutes.
Part B-Preparation of Bismaleimide
The reaction mixture of Part A containing the bismaleamic acid intermediate product was cooled at -5° C. At this temperature, 147.5 ml (107.1g; 1.058 mol) of triethylamine was slowly added, keeping the temperature at -5° C. Then 80 ml (86.6 grams; 0.848 mol) of acetic anhydride and 2 g (0.008 mol) of nickel (II) acetate tetrahydrate were added and the reaction mixture was heated to 60° C. and held for 1.5 hours. At this time, the heating mantle was turned off and vacuum applied to the system to remove tetrahydrofuran. Once the tetrahydrofuran had been removed from the reaction mixture, the resultant partially crystalline syrup was poured into 2500 ml of ice water while stirring very rapidly. The solid was collected by vacuum filtration and washed two times with 500 ml of cold water each time. The solid was air dried overnight. A yield of 155 g (0.342 mol; 100% yield) was obtained.
EXAMPLE III
Using the same reaction procedures of Examples I and II and the proper molar ratio of reactants, a bismaleimide was prepared from 2,2-bis4-(4-aminophenoxy)phenyl] hexafluoropropane. Starting with 100 g (0.193 mol) of the diamine, 130 g (0.192 mol; 99% yield) of the bismaleimide was obtained.
EXAMPLE IV
Another bismaleimide product was prepared in essentially quantitative yield following the general employed was prepared by first reacting 4-nitrochlorobenzene with a commercial mixed isomer sample of bishydroxyphenyl methanes and subsequently reducing the intro groups to amine groups.
The properties of a bismaleimide of Formula (I) - sometimes identified as 2,2-bis[4-(4-maleimidophenoxy)phenyl) propane or BPA-BMI for convenience of expression - prepared in general in accordance with the process of Example I was evaluated for certain performance properties as a thermosetting resin. The results of this evaluation were reported at the Spring 1986, Conference of the Society of Plastics Engineers. This paper was published in Volume 32 (1986), pages 1311-1315 of the Society of Plastics Engineers Technical Papers. The entire disclosure of this paper is incorporated herein by reference. Relevant portions of this paper are reproduced below.
NEAT RESIN CHARACTERIZATION
A differential scanning calorimetry scan (FIG. 1)* (This Figure is not reproduced) of 2,2-bis[4-(4-maleimidophenoxy) maleimidophenoxy)phenyl) propane, BPA-BMI, showed a T g for the uncured resin around 70° C. with a maximum peak exotherm in the vicinity of 210° C.
The heat of reaction was on the order of 30 cal/g. The observation that the uncured material had a T g around 70° C. gave the BPA-BMI the potential for being hot melt prepreggable. An iso-conversion kinetic plot (FIG. 2)* based on the rate equation dα/dt=k(1-α) n was obtained for the BPA-BMI. Using a degree of conversion of 25% to reach the gel point, the plot indicated that gelation occurred in 60 minutes at 180° C. This observation was consistent with other gel time determinations. Using the glass cloth impregnated sample and a typical cure cycle for commercially available BMIs (2 hour cure at 200° C., followed by a 5 hour post-cure at 250° C.), the resultant BPA-BMI was analyzed by dynamic mechanical analysis (DMA). The initial DMA scan (FIG. 3)* (this figure is not reproduced) showed a T g of 240° C. (464° F.). However, additional curing was observed to occur in the material while being heated to 350° C. under a nitrogen atmosphere within the DMA heating compartment. A DMA rescan (FIG. 4)* of the same sample indicated at the T g was now in the vicinity of 360° C. (680° F.).
Cast samples of the BPA-BMI cured by compression molding techniques showed similar results That is, the first DMA scan indicated a relatively low Tg material, while the DMA rescan for the same sample (after being heated through the first scan) showed a higher value of Tg. It is clear that after the initial two hour cure of 200° C. and five hour post-cure at 250° C., the BPA-BMI has not fully cured because the Tg advances during the DMA scan. The fully cured T g of the BPA-BMI is in the vicinity of 360° C. (680° F.). The density of the cast specimen was 1.26 g/cc. and its moisture retention was 1.6% maximum when exposed to 100% R.H.
A cast specimen of the BPA-BMI has been exposed to boiling water for 96 hours and tested by DMA. The total moisture uptake of this specimen was 2.1%. (this figure is not reproduced) The DMA data (FIG. 5)* compared modulus and loss tangent values for the wet sample to a comparable dry specimen. The data show relatively little influence of moisture on the properties. This observation is even more evident at high temperatures as illustrated in Table I.
Neat resin dogbone microtensile specimens were compression molded from the BPA-BMI. The specimens were cured using the following cycle: 180° C. hold for 14 min; apply 600 PSI pressure and an additional 46 min hold at 180° C.; heat to 200° C. and hold for one hour. After the cure cycle, the specimens underwent a free-standing post-cure at 250° C. for five hours. The mechanical testing results indicated a neat resin potential for tensile modulus in the range of 500 ksi (3.4×10 9 pa) and ultimate tensile strength of the order of 7 ksi (4.8×10 7 pa) with elongation values of approximately 1.5%. A second set of microtensile specimens post-cured at 250° C. for 16 hours gave similar results.
It should also be pointed out that the microtensile specimens prepared were not brittle in comparison to similar samples of commercially available BMIs.
PREPREG FABRICATION
As mentioned earlier, since the uncured BPA-BMI showed a Tg in the vicinity of 70° C., it was believed that this material was amenable to hot melt prepregging. Initial studies indicate that the BPA-BMI can indeed be hot melt prepregged. The material heated above its uncured glass transition temperature and applied to fiber reinforcement flows and wets fibers readily.
The disadvantage of this material in a hot melt prepregging application occurs once the resin cools down below its uncured T g . The resultant prepreg is boardy and lacks tack and drape. Experiments are underway to improve on this fabrication drawback. The BPA-BMI is being formulated with additives known to improve on the tack and drape of commercially available BMIs. Initial results indicate that the BPA-BMI can be formulated to a lesser extent than known commercial BMI formulations. Thus, the overall thermal stability and mechanical properties of the BPA-BMI formulations are affected less in comparison to BMI formulations which contain high levels of non-BMI type additives.
Solution prepregging of the BPA-BMI appears to cause no significant problems. The material is very soluble in a host of common organic solvents. Acceptable tack and drape can be maintained with residual solvent.
CONCLUSIONS
The series of aromatic ether bismaleimides discussed in this work meets the new requirements needed for matrix resins.
The ones studied to date, in particular the BPA-BMI, have high thermal stability. In fact, the Tg of the fully cured BPA-BMI surpasses the Tg's of some of the polyimides which are used in very high temperature applications [288° C. (550° F.)]. These flexible-type aromatic ether BMIs exhibit low moisture sensitivity, and the BPA-BMI has been fabricated into non-brittle specimens.
TABLE 1______________________________________COMPARISON BETWEEN WET AND DRY MODULUSVALUES FOR BPA--BMI AT SELECTED TEMPERATURES______________________________________Temperature Modulus, GPa % Modulus°C. (°F.) dry wet Retention______________________________________240 (464) 0.981 0.837 85280 (536) 0.895 0.720 80320 (608) 0.830 0.597 72The neat resin mechanical properties of this resin were:MODULUS 500 ksiULTIMATE STRENGTH 8 ksiELONGATION 1.5-2%COMPARES FAVORABLY TO OTHERS E.G., FOR NEATRESIN MDA-BMIELONGATION 1.0% OR MDA--BMIThe neat resin dielectric properties of this resin were: DIELECTRIC DISSIPATIONFREQUENCY CONSTANT FACTOR______________________________________1 kh.sub.z 3.24 --8 kh.sub.z 3.23 0.0012128 kh.sub.z 3.21 0.00581 mh.sub.z 3.18 0.00894 mh.sub.z 3.19 0.0151______________________________________
The resin was analyzed by the Reverse Phase High Pressure Chromatographic method discussed supra to establish the purity of the resin. The chromatogram plot is shown as FIG. 6 of the drawings. The sample contained well in excess of 80 weight % of the BPA-BMI component.
FIG. 1 of the drawings is an infrared spectrum of a BPA-BMI product corresponding to Formula (I) and which was prepared by a procedure corresponding to Example I. It will be noted that the spectrum has a strong absorption peak at about 690cm -1 . This peak is indicated by the arrow in the drawing.
The solubility of a product prepared by a procedure corresponding to Example I in several solvents was measured. The solubilities in weight % at 25° C. were:
______________________________________Solvent Wt. % Dissolved at 25° C.______________________________________Dioxane Ca 16%Methylene Chloride Ca 44%Tetrahydrofuran Ca 39%Toluene Ca 4%Acetone Ca 55%______________________________________
Example I of U.S. Pat. No. 4,460,783 reports that the BPA-BMI product of Formula (I) was prepared by reacting maleic anhydride with 2,2-bis[4-(4-aminophenoxy)phenyl]propane in acetone to prepare an intermediate bismaleamic acid product which then was reacted with acetic anhydride in the presence of potassium acetate at a temperature of 80°-100° C. The patentees reported that the product ostensibly having structure of Formula (I) was recovered from the acetone reaction medium by filtration. In effect, the patentees have indicated that his product has a very low solubility in acetone.
Since the product produced by the applicants' method and reportedly having the structure of Formula (I) is highly soluble in acetone whereas the reportedly identical product produced in Example I of U.S. Pat. No. 4,460,783 is insoluble in acetone, it necessarily follows that the two products do not have the same compositions. The applicants therefore have carried out certain experiments to establish the differences existing between products of supposedly identical composition.
Comparative Example I
In considering the experimental conditions used to duplicate the work of Example I of U.S. Pat. No. 4,460,783, it was noted that an ambiguity was present or one of more reaction parameters were not set forth. Specifically, at column 7, lines 5 and 6, it is stated that the reaction, in an acetone solvent, was carried out at 80°-100° C. Since acetone has an atmospheric bp of 56° C., this statement cannot be correct, unless the reaction was carried out in a pressurized reactor. It is most likely that the patentee intended to state that the reaction vessel was heated to 80°-100° C., possibly in an oil bath, with the reaction mixture attaining the temperature of the refluxing solvent, i.e., the acetone. Based on this assumption, the following work was carried out.
An apparatus was assembled and consisted of a 500 ml, 3-necked, round bottom flask equipped with a condenser, an overhead stirrer, an addition funnel, and an inlet for nitrogen gas. An initial charge of 200 grams of reagent grade acetone and 20 grams (0.05 mol) of 2,2-bis[4(4-aminophenoxy)phenyl]propane was made to the apparatus. The mixture was cooled using a dry ice/acetone bath to 0°-5° C. Then, 10.0 grams (.10 mol) of freshly ground maleic anhydride was added to the reaction mixture. The mixture was stirred for three hours. The initial mixture was a light brown, clear solution. Ten minutes of mixing at 0°-5° C. produced a cloudy yellow mixture. The flask and its contents were removed from the dry ice/acetone bath after three hours. Ten (10.0) grams of acetic anhydride and 0.05 gram of potassium acetate were added to the mixture. No apparent physical changes occurred. The reaction mixture was heated to 60° C. over a period of about 45 minutes and maintained at this temperature for 30 minutes. The flask was then transferred to a 90° C. oil bath. After 50 minutes, the reaction flask and its contents were removed from the oil bath. No apparent loss of acetone occurred. The reaction mixture maintained the cloudy yellow color throughout the reaction up to completion of the experiment.
After cooling, the solid was filtered off and the reaction flask was rinsed out with reagent grade acetone to remove all the solid. The solid was then washed with water and air dried overnight. The weight of the solid was 26.5 grams. The solid was insoluble in water and dioxane.
FIG. 3 is an infrared spectrum of a product prepared by the foregoing procedure. The spectrum has no absorption peak at 690 cm -1 as shown in the infrared spectrum of FIG. 1. Accordingly, the product is not the bismaleimide product of Formula (I).
The product was characterized in a Differential Scanning Calorimeter (DSC) run at a heating rate of 10° C./min. An endotherm occurred at 160° C. Thermogravimetric analysis (TGA) indicated a release of about 14 weight % volatiles when heated to 300° C. and decomposition at 375° C. The product could not be analyzed by the Reverse Phase High Pressure Chromatographic method discussed supra as the product was insoluble in dioxane. Because of its high volatiles, the product has poor resin processability. The product was found to be insoluble in dioxane, methylene chloride, THF, toluene, and acetone.
A small quantity of a by-product was recovered from the filtrate of this run. The by-product, after drying, weighed less than 5.0 grams and had a gooey consistency. In view of the sample size and consistency, no evaluation was made of it.
Comparative Example II
An attempt was made to prepare a bismaleimide of Formula (I) by following general procedures shown in U.S. Pat. No. 3,839,287.
The apparatus employed consisted of a 2 liter, 3-necked, round bottom flask equipped with an overhead mechanical stirrer, an inlet for nitrogen gas, and a thermometer. An initial charge of 82.1 grams (0.2 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane and 400 ml of N,N-dimethylacetamide was made to the apparatus. After all the solid dissolved, the reaction mixture was cooled to 0° C. A charge of 39.22 grams (0.4 mol) of dry maleic anhydride was made in increments at a rate such that the solution temperature did not exceed 10° C. The reaction mixture was then allowed to stir at 10° C. for another hour. A charge of 40.8 grams (0.4 mol) of acetic anhydride and 4 grams (0.04 mol) of triethylamine was made to the reactor and the reaction mixture was stirred for 4 hours at ambient temperature. The reaction mixture was added dropwise with efficient stirring to a large volume of water. A yellow solid kicked out of the solution. The solid was separated by filtration and washed repeatedly on a filter until the washings had the pH of tap water. The dry solids weighed 91.7 grams for a 80.4% yield.
FIG. 4 is an infrared spectrum of a product prepared by the foregoing procedure. The spectrum does not
contain a strong absorption peak at 690 cm -1 as did the infrared spectrum of FIG. 1.
The product was characterized in a Differential Scanning Calorimeter (DSC) run at 10° C./min. A Tg endotherm occurred at 60° C. and an endotherm occurred at 193° C. followed by an exotherm at about 210° C. A thermogravimetric analysis (TGA) showed a release of 12.5 weight % volatiles when heated to 30° C. and decomposition at 400° C. The resin could not be analyzed by the Reverse Phase High Pressure Chromatographic method discussed supra as the product was insoluble in dioxane. Because of its high volatiles, the product has poor resin processability. The product was found to be insoluble in dioxane, methylene chloride, THF, toluene, and acetone.
Comparative Example III
To provide a control, an authentic sample of the bismaleamic acid of Formula (III) was prepared. A charge of 102.8 grams (0.25 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane was dissolved in 1400 ml of THF. The solution was cooled to about -11° C. in a dry ice/acetone bath. A solution of 49.6 grams (0.50 mol) of high purity maleic anhydride in 225 ml of THF was added to the stirred diamine solution over 20 minutes. After this addition was completed, a yellow precipitate began forming. Stirring was continued at -10° C. for 1 hour, then raised to 25° C. and maintained at 25° C. for 1 hour, and then slowly increased to 65° C. The reaction mixture continued to thicken throughout this heating cycle. The reaction mixture was cooled to 20° C., filtered, pressed free of solvent, and air dried overnight. The recovered solids weighed 132 grams (76% of theory). An infrared spectrum of the product is shown in FIG. 2.
When subjected to analysis in a Differential Scanning Calorimeter with the temperature increase being 10° C./min., the product showed two endotherms at 135° and 175° C. and an exotherm at about 200° C. Thermogravimetric analysis (TGA) showed a loss of 13.5 weight % when heated to 300° C. followed by decomposition at 400° C. The product was insoluble in dioxane, methylene chloride, THF, toluene, and acetone. By reason of its insolubility in dioxane, the product could not be analyzed by the Reverse Phase High Pressure Liquid Chromatographic Method discussed supra. By reason of its volatiles loss on heating, the product has poor resin processing characteristics.
Comparative Example IV
A major U.S. chemical company has recently offered a bismaleimide product reported to have the structure of Formula (I) for evaluation. In view of several prior art workers misidentifying the product of Formula (I), a study of the newly offered product was made to confirm its structure. As infrared spectrum of the product is set forth as FIG. 5. The presence of a band at 690 cm -1 (shown by the arrow)confirms that the product does indeed contain a fraction having the structure of Formula (I).
The solubility of the product in representative solvents was measured at 25° C. The data are set forth in the Table below:
______________________________________Solvent Weight % Dissolved at 25° C.______________________________________Dioxane Ca 1%Methylene Chloride Ca 26.8%THF Ca 15.5%Toluene Ca 9%Acetone Ca 29.2%______________________________________
An attempt was made to estimate the product's content of the desired bismaleimide of Formula (I) by the Reverse Phase High Pressure Liquid Chromatographic procedure discussed supra. A valid analysis could not be made as only about 1% of the sample dissolved in dioxane. A chromatographic tracing of the soluble fraction was similar to the curve shown in FIG. 6.
The product had an endotherm at 107° C. when analyzed in a Differential Scanning Calorimeter (DSC) using a heating rate of 10° C./min. In a thermogravimetric analysis (TGA), a volatiles loss of 12.4% was suffered when the sample was heated to 300° C. The sample decomposed at 450° C. By reason of its high volatiles content, the product has no viability as a commercial thermosetting resin.
Having described the invention in detail and by reference to preferred embodiments thereof, it will be apparent that modifications and variations are possible without departing from the scope of the invention defined in the appended claims. | The present invention provides a process for producing aromatic ether bismaleimides of the Formula (II) ##STR1## wherein A is a divalent mononuclear or polynuclear aromatic linking group. The process provides good yields and can be scaled up readily to commerical size runs.
The present invention also provides compositions containing at least about 80 weight % of the bismaleimide of Formula (II) above. | 7 |
BACKGROUND OF THE INVENTION
[0001] a. Field of the Invention
[0002] The invention generally relates to catheters for guided introduction into a body cavity. More specifically, the invention relates to a catheter that includes a distal deflectable segment having an anisotropic deflecting (or bending) stiffness that reduces or eliminates unintended out-of-plane movement of a distal end of the catheter.
[0003] b. Background Art
[0004] Catheters can be used for medical procedures to examine, diagnose, and treat while positioned at a specific location within the body that is otherwise inaccessible without more invasive procedures. During these procedures a catheter is typically inserted into a vessel near the surface of the body and is guided to a specific location within the body for examination, diagnosis, and treatment. For example, catheters can be used to convey an electrical stimulus to a selected location within the human body, e.g., for tissue ablation, as well as to monitor various forms of electrical activity in the human body, e.g., for electrical mapping. Catheters are also being used increasingly for medical procedures involving the human heart. In such cases, the catheter is typically inserted in an artery or vein in the leg, neck, or arm of the patient and guided, sometimes with the aid of a guide wire or introducer, through the vessels until a distal end of the catheter reaches a desired location in the heart.
[0005] In a normal heart, contraction and relaxation of the heart muscle (myocardium) takes place in an organized fashion as electro-chemical signals pass sequentially through the myocardium. Sometimes abnormal rhythms occur in the heart, which are referred to generally as cardiac arrhythmia. The cause of such arrhythmia is generally believed to be the existence of an anomalous conduction pathway or pathways that bypass the normal conduction system. An increasingly common medical procedure for the treatment of certain types of cardiac arrhythmia is catheter ablation. During conventional catheter ablation procedures, an energy source is placed in contact with cardiac tissue (e.g., associated with an anomalous conduction pathway) to create a permanent scar or lesion that is electrically inactive or noncontractile. The lesion partially or completely blocks the stray electrical signals to lessen or eliminate arrhythmia. As will be appreciated, ablation of a specific location within the heart requires the precise placement of the ablation catheter within the heart.
[0006] Guidance of a catheter to a specific location in the body can be performed using feel, electrophysiological guidance, computer generated maps/models and/or a combination of the above. In any case, it may be necessary to deflect the distal end of the catheter to facilitate movement of the catheter through a body cavity (e.g., vessel) and/or to position the distal end of the catheter relative to an internal structure of interest. In this regard, guidable catheters and/or introducers typically include a selectively deflectable segment near their distal tip. For instance, an ablation catheter may include a distal end portion (e.g., insertion portion) having an ablation electrode and a soft and flexible distal deflectable segment that is disposed between the electrode and the relatively rigid (e.g., metallic wire-braided) catheter shaft that extends to a proximal actuator. Pull wires extend through the deflectable segment and attach to a pull ring (e.g., positioned between the deflectable segment and the electrode). The pull wires extend through the catheter and are axially connected to a pull mechanism of the proximal actuator. Upon the deflection by manipulating the actuator, the pull wires generate a pull force that imposes a bending moment on the flexible deflectable segment. This leads to the deflection of the distal end of the catheter, which allows the distal end to be routed to and/or positioned relative to desired internal locations.
[0007] Several difficulties may be encountered, however, when attempting to precisely locate the distal end of a catheter at an internal location of interest for guidance purposes and/or for performing an internal procedure, such as, for example, ablating tissue.
BRIEF SUMMARY OF THE INVENTION
[0008] In order to facilitate deflecting movement of the distal tip of a catheter, it may be desirable to constrain the movement of the catheter tip to a consistent and repeatable plane when actuated by a pull wire. That is, upon pulling a pull wire (e.g., actuation) to deflect the distal tip of the catheter, it may be desirable that the catheter tip deflect within a sweeping plane that is repeatable from actuation to actuation. However, due to the previous construction of distal deflectable segments, the tip of the catheter is often able to move out of the desired sweeping plane. That is, it has been determined that deflecting movement of the distal tip may not be consistent between actuations. Therefore, it is desirable to provide a distal deflectable segment that constrains the movement of the distal tip of the catheter in a predictable and consistent manner. Accordingly, the present invention is directed to a distal deflectable segment that permits its deflecting movement within one plane (i.e. “in-plane” or “sweeping plane”), while resisting unintended movements in other plane (i.e. “out-of-plane”).
[0009] According to a first aspect, a guidable catheter is provided. The catheter includes a catheter body that has a proximal portion and a distal portion where the distal portion is adapted for insertion into a body cavity (e.g., internal tissue lumen, blood vessel, etc.). A selectively deflectable segment is incorporated into the distal portion of the catheter body. The selectively deflectable segment may be interconnected (e.g., axially) to the proximal portion of the catheter body by one or more pull wires. Upon actuation of such pull wires the distal deflectable segment may be deflected to move/sweep the distal catheter tip within a virtual plane called a sweeping plane. To maintain tip movement in a desired sweeping plane, the deflectable segment has a first bending stiffness for deflection in a first plane and a second bending stiffness for deflection in a second plane where the first bending stiffness and the second bending stiffness are different.
[0010] Generally, a bending stiffness for deflection in one plane is significantly larger than a bending stiffness for deflection in other plane. That is, one of the planes may be significantly stiffer than other plane under a deflecting, or flexing or bending deformation mode. Accordingly, the tip movement of the deflectable segment may be substantially isolated to a single, virtual plane, i.e. sweeping plane. In one arrangement, the bending stiffness for deflection in one of the planes can be enhanced to form a reinforced plane. The bending stiffness for deflection in the reinforced plane is at least 5% greater than the bending stiffness for deflection in the other plane. In a further arrangement, the stiffness may be at least twice the stiffness for deflection in the other plane. In a yet further arrangement, the stiffness may be at least 10 times greater than the stiffness for deflection in the other plane.
[0011] Generally, the plane, for deflection in which a deflectable segment has the greater bending stiffness, may define a reinforced plane of the segment, while the plane, for deflection in which the segment has the lower bending stiffness may define a virtual, sweeping plane. The sweeping plane is typically perpendicular to the reinforced plane, and both planes pass through a reference, longitudinal axis (e.g., central axis) of the deflectable segment along its length. In one arrangement, the guidable catheter may also include a first pull wire that extends through at least a portion of the length of the deflectable segment. In a particular arrangement, the pull wire and/or its endpoints or end-lines anchoring onto the deflectable segment, may be substantially disposed within the sweeping plane. However, it will be appreciated that due to the high bending stiffness for deflection in the reinforced plane, minor misplacement of the pull wire(s) away from the sweeping plane may not result in out-of-plane movement of the distal end of the catheter body upon deflection of the deflectable segment.
[0012] In one reinforced plane arrangement, the selectively deflectable segment further includes a stiffening element that is disposed along at least a portion of the length of the deflectable segment. The stiffening element may extend over the entirety of the length of the deflectable segment and/or multiple stiffening elements may be disposed in, for example, series and/or parallel. In one arrangement, stiffening elements have a Young's modulus that is greater than the Young's modulus of the flexible material (e.g., polymeric material) forming the deflectable segment. In such an arrangement, stiffening elements may be formed of, for example, relatively rigid polymeric material and/or metallic material. In any arrangement, the cross section of a stiffening element may have an area moment of inertia about a first centroidal axis that is greater than an area moment of inertia about a second centroidal axis. In this regard, the stiffening element may permit bending or deflection in a plane in parallel with the first centroidal axis, while significantly restricting bending in another plane. Accordingly, such a stiffening element may be disposed in the vicinity of a reinforced plane of a distal deflectable segment to prevent out-of-plane movement while permitting in-plane movement (e.g., sweeping plane movement).
[0013] In one arrangement, in a non-deflected state, the deflectable segment has a substantially circular cross-section and an internal lumen. In a further arrangement, the internal lumen shares a cross-sectional shape with the outside surface of the deflectable segment. In such an arrangement, the deflectable segment may be a tubular segment having a substantially constant sidewall thickness. One or more stiffening elements may be disposed within the sidewall. In a further arrangement, an electrode may be connected to the distal end of the catheter body (e.g., distally to the selectively deflectable segment). Such an electrode may be utilized for mapping purposes and/or tissue ablation.
[0014] In another aspect, a guidable catheter is provided having a distal deflectable segment. In a non-deflected state, a length of the deflecting statement defines a reference longitudinal axis between its proximal and distal ends. At least one stiffening element extends over at least a portion of the length of the deflectable segment between its proximal and distal ends. The catheter further includes at least one pull wire that extends through the deflectable segment for selectively moving the deflectable segment from a non-deflected state to a deflected state.
[0015] In one arrangement, the distal deflectable segment is formed of a first material (i.e., body material), and the stiffening element is formed of a second material. In such an arrangement, the second material may have a Young's modulus that is greater than the Young's modulus of the first material for the distal deflectable segment. In one arrangement, the first and second materials may be formed of polymeric materials. For instance, the first material may be a flexible thermoplastic elastomer (TPE) material, and the second material may be a relatively rigid polymeric material having a Young's modulus that is greater than the TPE material. Where two polymeric materials are utilized, the first and second materials may be co-extruded to form the distal deflectable segment. In a further arrangement, the stiffening element may be a preformed polymeric component and/or metallic component made of the second material. Accordingly, the first material of the distal deflectable segment may be melt extruded over and/or laminated to the performed stiffening element.
[0016] In another aspect, a guidable catheter is provided having a distal deflectable segment formed of a first material and at least one stiffening material formed of a second material. In a non-deflected state, the deflectable segment is substantially tubular, and the length of the deflectable segment defines a reference longitudinal axis. The stiffening element is incorporated into a sidewall of the deflectable segment and extends over at least a portion of the length of the deflectable segment. In such an arrangement, the distal deflectable segment may define an internal lumen that may be substantially free of intrusion by the stiffening element. That is, in one arrangement, the stiffening element may be fully encapsulated within the sidewall. This may enhance or maximize the size of the lumen for fluid passage and/or passage of devices through the lumen.
[0017] According to another aspect, a guidable catheter is provided having a distal deflectable segment that, in a non-deflected state, is substantially tubular and defines a reference longitudinal axis along its length. At least one stiffening element extends over at least a portion of the length of the deflectable segment. The stiffening element has a cross section with an area moment of inertia I 1c about its first centroidal axis being at least two to fifty times an area moment of inertia I 2c about a second centroidal axis. The stiffening element may be disposed in the vicinity of and/or in alignment with a desired reinforcing plane of the distal deflectable segment, or preferably, the second centroidal axis is in alignment and/or parallel with that plane. What is important is that the stiffening element resists bending or deflecting in the reinforced plane, while permitting bending or deflection in other plane.
[0018] According to another aspect, a guidable catheter is provided having a distal deflectable segment that, in a non-deflected state, is substantially tubular and defines a reference longitudinal axis along its length. At least one stiffening element extends over at least a portion of the length of the deflectable segment. The stiffening element has a cross section with an identical area moment of inertia about its two centroidal axes. The stiffening element may be disposed in the vicinity of and/or in alignment with a desired reinforced plane of the distal deflectable segment. What is important is that the stiffening element resists bending or deflecting in the reinforced plane, while permitting bending or deflection in another plane.
[0019] The foregoing and other aspects, features, details, utilities, and advantages of the present invention will be apparent from reading the following description and claims, and from reviewing the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] FIG. 1 is an exemplary catheter system including an introducer and an ablation catheter.
[0021] FIG. 2A illustrates an electrode catheter disposed in a heart with a distal deflectable segment in a non-deflected state.
[0022] FIG. 2B illustrates an electrode catheter disposed in a heart with a distal deflectable segment in a deflected state
[0023] FIG. 3A illustrates a distal deflectable segment in a non-deflected state.
[0024] FIG. 3B illustrates internal components of the distal deflectable segment of FIG. 3 a.
[0025] FIG. 3C illustrates the distal deflectable segment of FIG. 3 a in a deflected state.
[0026] FIG. 4 illustrates local deflection of a distal deflectable segment in the sweeping plane (i.e. xz plane).
[0027] FIG. 5 illustrates in-plane and out-of-plane bending stiffness in the cross-sectional area of a distal deflectable segment.
[0028] FIGS. 6A-6J illustrates various embodiments of distal deflectable segments incorporating one or more stiffening elements aligning with a reinforced plane.
[0029] FIG. 7A-7D illustrates a further embodiment of an anisotropic stiffening element and a distal deflectable segment incorporating one or more of that element.
[0030] FIGS. 8A and 8B illustrate embodiments of a distal deflectable segment with integral stiffeners.
DETAILED DESCRIPTION OF THE INVENTION
[0031] Exemplary embodiments of a catheter system and methods of using the system to access internal areas of interest are depicted in the figures. As described further below, use of a catheter having a distal deflectable segment having anisotropic bending properties allows for improved catheter guidance and/or improved control for tissue access/contact.
[0032] FIG. 1 illustrates an exemplary electrode catheter system that may be utilized to access, map and/or perform medical procedures on internal tissue of interest. The catheter system 10 may include a guiding introducer having a sheath 12 , which may be inserted into a patient. The sheath 12 may provide a lumen for the introduction of a catheter 18 which may be disposed beyond the distal insertion end of the sheath 12 . In the particular configuration of FIG. 1 , the sheath 12 is configured to receive and guide the catheter 18 to an internal location in the heart once the sheath is pre-positioned in an appropriate location. During an exemplary cardiac procedure, a user (e.g., the patient's physician or a technician) inserts the sheath 12 of the introducer into one of the patient's blood vessels (e.g., through the leg or neck). The user, typically guided by an imaging device (e.g., fluoroscopy, ICE, electro-anatomical mapping, etc.) moves the sheath 12 into the patient's heart 50 . See FIG. 2A . When the sheath 12 of the guiding introducer is positioned in a desired location within the heart 50 of the patient, the electrode catheter 18 may be extended through a lumen of the sheath 12 such that the electrode catheter 18 may be guided to a desired location within the heart to perform, for example tissue mapping and/or tissue ablation. However, the catheter 18 may be used alone or with other guiding and introducing type devices depending on the particular procedure being performed.
[0033] As shown in FIG. 1 , the catheter includes a tubular body or shaft 16 extending from a proximal handle 14 , through the sheath 12 and extending out of the distal end of the sheath 12 . As used herein and commonly used in the art, the term “distal” is used generally to refer to components of the system, such as a tip electrode 20 , located toward the insertion end of the of the catheter 18 (i.e., toward the heart or other target tissue when the catheter is in use). In contrast, the term “proximal” is used generally to refer to components or portions of the system that are located or generally orientated toward the non-insertion end of the catheter (i.e., away from or opposite the heart or other target tissue when the catheter is in use).
[0034] The proximal handle 14 includes a sliding actuator 8 that is interconnected via one or more pull wires to a distal deflectable segment 24 that is incorporated into the distal portion of the catheter 18 . As shown in FIG. 1 , the distal tip of the exemplary catheter includes an ablation tip/electrode 20 . Located proximally behind the electrode 20 is a pull ring 22 and the distal deflectable segment 24 . The proximal end of the distal deflectable segment 24 is connected to the distal end of the catheter shaft 16 . Generally, the catheter shaft 16 is more rigid that the generally soft and flexible distal deflectable segment 24 . For instance, the catheter shaft 16 may be formed of a flexible resilient material covered by a wire-braiding that may extend to the proximal handle 14 .
[0035] In one exemplary embodiment, the sheath 12 and shaft 16 are fabricated with a flexible resilient material. The sheath and the components of the catheter are preferably fabricated of materials suitable for use in humans, such as biocompatible polymers. Suitable polymers include those well known in the art, such as numerous thermoplastics including, but not limited to, Fluoropolymers, polyolefins, polyesters, polyamides, polycarbonate, polyurethanes, polyimides, polysulfones, polyketons, liquid crystal polymers and the like. Various thermoplastic elastomer (TPE) materials can be also selected, including, but not limited to thermoplastic polyurethanes, polyamide-based TPE's, polyester-based TPE's, thermoplastic polyolefins, styrenic TPE's and the like.
[0036] FIGS. 3A-3C variously illustrate the distal deflectable segment. As shown in FIG. 3A , in a non-deflected state, the distal deflectable segment 24 extends, as a substantially tubular structure, between the distal end of the catheter shaft 16 and the tip electrode 20 . In order to deflect the deflectable segment 24 , pull wires 26 A, 26 B (generally 26 unless individually referenced) extend from the sliding actuator 8 , through the shaft 16 and deflectable segment 24 and attach to a pull ring 22 . This is illustrated in FIG. 3B , where the deflectable segment, shaft and electrode are removed for purposes of illustration. Upon the deflection by manipulating the actuator 8 , the pull wires 26 generate eccentric pull force on the pull ring 22 , which imposes the bending moment M on the flexible distal deflectable segment 24 . As illustrated in FIG. 3C , this deflects of the distal end of the catheter and thereby allows for disposing the distal tip of the catheter relative to internal areas of interest. See also e.g., FIG. 2B .
[0037] More specifically, as illustrated in FIG. 3C the distal tip (e.g., tip electrode 20 ) of the catheter 18 is caused to move within a bending or sweeping plane 100. As may be appreciated, for precise placement and guidance of the distal tip of the catheter to an internal location of interest, it may be desirable that the deflection of the distal tip be constrained only within the sweeping plane 100. Such constraint to the desired sweeping plane may provide consistent and predictable displacement between deflections of the catheter. However, the flexible distal deflectable segments currently used for most deflectable catheters are simply hollow tubes typically made of a single polymer material that is typically soft and flexible. Such deflectable segments have not resulted in constrained (i.e., in-plane) deflection or consistency between deflections. That is, previous deflectable segments have permitted some out-of-plane movement.
[0038] In this regard, the sweeping planes of previous distal deflectable segments have depended on the direction of the bending moment (M) imposed on the distal deflectable segment and the isotropic bending stiffness of a generally hollow polymeric tube. As illustrated in FIG. 3B , pull wires 26 A, 26 B may be disposed in a common plane with the sweeping plane. By pulling axially on one of the wires 26 (e.g., using the actuator 8 ), a bending moment M may be applied to the distal deflectable segment 24 which causes the distal tip (e.g., electrode 20 ) of the catheter to move in plane (i.e., the sweeping plane 100) that includes the pull wires 26 .
[0039] To ensure the sweeping planarity and consistency of deflectable segment 24 , the pull wire-generated pull force or bending moment M must be in near perfect alignment with the designated sweeping plane 100 as shown in FIG. 3B . This is a challenge for part assembly during manufacturing as misalignment between the pull wires 26 , pull ring 22 and the desired sweeping plane 100 is almost unavoidable. Such misalignment typically results in the distal tip of the catheter 18 moving at least partially outside of the sweeping plane 100. That is, misalignment results in non-planarity issues for deflectable catheters. Further, during use, small disturbance in the directions of the pull force or bending moment and/or minor internal inconsistencies of the hollow polymeric tube will allow the distal deflectable segment to deflect outside of the sweeping plane. This leads to twisting or torsion of the distal deflectable segment and the movement of the distal end in an unpredictable way. The result is that it may be difficult to guide the distal tip of the catheter or an introducer to a desired internal location of interest in a highly controlled manner.
[0040] To overcome these problems, the distal deflectable segment 24 of the present invention utilizes an anisotropic bending stiffness such that deflection of the segment 24 may be more effectively isolated to a desired plane (e.g., the sweeping plane). As will be discussed herein, embodiments of such an anisotropic deflectable segment may be produced by altering the physical cross-sectional dimensions of the segment and/or by incorporating one or more stiffening elements into the segment. In the latter regard, it will be appreciated that based on the combinations of at least two different materials (e.g., forming the stiffening element and deflectable segment) having significantly different material stiffness (e.g., Young's moduli), a resulting distal deflectable segment 24 may possess anisotropic bending stiffness for deflection in different planes. Stated otherwise, the incorporation of a stiffening element into the deflectable segment may only allow deflection or catheter tip sweeping within a designated plane and structurally prevent any deflection out of the designated plane (i.e., out-of-plane movement).
[0041] Referring again to FIG. 3A , coordinate system is set forth for purposes of discussion and not by way of limitation. Specifically, in a non-deflected state, the distal deflectable segment 24 is a generally tubular structure and its long axis defines a reference longitudinal axis (e.g., z axis) between its distal end 32 and its proximal end 34 . In this embodiment, while the segment is non-deflected, the sweeping plane 100 defines the x axis as illustrated in subsequent Figures. The plane 110 that is perpendicular to the sweeping plane 100, and which extends through the reference longitudinal axis, defines the y axis in the subsequent Figures. In a non-deflected state, the plane 110 that incorporates the reference longitudinal axis and is perpendicular to the sweeping plane defines a reinforced plane 110. In the following Figures, it will be appreciated that the cross sections of the distal deflectable segment 24 reside in the plane (i.e., xy plane) that is perpendicular to the sweeping plane 100 and the reinforced plane 110 as well as the longitudinal axis of the deflectable segment (i.e. z axis).
[0042] FIG. 4 shows the deflection of the distal deflectable segment 24 under a pure bending moment imposed by the pull ring 22 and the localized infinitesimal portion of the distal deflectable segment 24 , dz, at the axial position of z (i.e. located along the reference longitudinal z-axis). From beam theory, the bending stiffness, S, for deflection in a plane is related to the localized deflection curvature radius, ρ, via the following equation:
[0000]
1
ρ
=
M
S
;
S
=
∫
E
I
Eq
.
(
1
)
[0000] where M is the bending moment in or along the plane; E is the material stiffness (or Young's modulus) and I is the area moment of inertia (i.e. second moment of area) relative to the neutral bending axis of the cross section of the deflectable segment, which is perpendicular to the plane. It will be appreciated that for a given bending moment, low bending stiffness for deflection in the plane will introduce large deflection (i.e. smaller curvature radius). Thus, bending stiffness for deflection in a plane may be considered a direct measure for the deflection occurring in the plane. In this sense, low bending stiffness for deflection in the sweeping plane 100 is preferred to promote in-plane deflection, while high bending stiffness for deflection in reinforced plane 110 (at non-deflecting state) is required to prevent out-of-plane movement of the distal deflectable segment. For in-plane deflection of the deflectable segment 24 in sweeping plane 100, local interception line of the reinforced plane 110 with the cross section of the segment 24 , namely y-axis, is the local neutral bending axis of the cross section of the segment 24 . For out-of-plane deflection of the deflectable segment 24 , local intercept line of sweeping plane 100 with the cross section of the segment 24 , namely x-axis, is the local neutral bending axis of the cross section of the segment 24 .
[0043] To minimize or prevent the deflection deviations in planes other than the designated sweeping plane 100, the bending stiffness in these other planes may be increased, while still maintaining low bending stiffness for in-plane deflection in the sweeping plane. This leads to the anisotropic bending stiffness for a given cross section of the distal deflectable segment 24 . For this purpose, referring to FIG. 5 , the in-plane and out-of-plane bending stiffness can be defined as:
[0000]
S
i
n
-
plane
=
∫
E
I
=
∫
E
(
x
)
·
x
2
A
Eq
.
(
2
)
S
out
-
of
-
plane
=
∫
E
I
=
∫
E
(
y
)
·
y
2
A
Eq
.
(
3
)
[0000] wherein for promoting in-plane deflection in sweeping plane 100 and preventing any deflections in other plane, it must meet that:
[0000]
S
i
n
-
plane
<<
S
out
-
of
-
plane
.
Eq
.
(
4
)
[0044] It will be appreciated that a tubular deflectable segment formed of an isotropic material will have the same bending stiffness for the in-plane deflection (i.e., the deflection about the neutral in-plane bending axis, namely y-axis) and the out-of-plane deflection (i.e., the deflection about the neutral out-of-plane bending axis, namely x-axis). Accordingly, to permit the in-plane deflection in the sweeping plane 100 (e.g. xz-plane) about a neutral in-plane bending axis (e.g. y-axis) while preventing the out-of-plane deflection in the reinforced plane 110 (e.g. yz-plane) about the neutral out-of-plane bending axis (e.g. x-axis), it is desirable to increase the out-of-plane bending stiffness. As illustrated in FIG. 5 , this entails that for designing the cross section of a distal deflectable segment 24 , the area moment of inertia about its neutral out-of-plane bending axis (i.e. x-axis) shall be increased, without significantly changing the other area of moment of inertia about the neutral in-plane bending axis (i.e. y axis).
[0045] In a first arrangement, an out-of-plane bending stiffness is increased by including a stiffening element that is incorporated into the cross-section of the deflectable segment at a location that increases the overall moment of inertia about the neutral out-of-plane bending axis ( i.e. x-axis) without significantly changing the area moment of inertia about the neutral in-plane bending axis (i.e. y-axis), about which the deflectable segment will be deflected in the sweeping plane 100 (i.e. xz-plane) as a whole entity. Broadly stated, inclusion of one or more stiffening elements having a material stiffness (i.e., Young's modulus) that is greater than the flexible material used to form the distal deflectable segment 24 , may allow an out-of-plane bending stiffness (i.e. S out-of-plane ) about the neutral out-of-plane axis (i.e. x-axis), per Eq. 3, to be significantly increased, while minimally changing the in-plane bending stiffness (i.e. S in-plane ) about the neutral in-plane bending axis (i.e. y-axis), per Eq. (2). Further, it will be appreciated that by increasing the spacing of a stiffening element from one axis (e.g., x axis) that the stiffeners may significantly increase the overall out-of-plane bending stiffness of the distal deflectable segment, per Eq. (3).
[0046] That is, by using stiffening materials having different material stiffness than the deflectable segment and proper placement of such stiffeners, various designs for the cross section of the distal deflectable segment can provide very low in-plane bending stiffness (S in-plane ) but very high out-of-plane bending stiffness (S out-of-plane ). This will allow deflection within the designated sweeping plane while largely limiting deflection out of the sweeping plane.
[0047] FIGS. 6A-6J show a series of designs where stiffening elements 80 are incorporated into sidewall of the distal deflectable segment 24 . In all theses designs, shaded areas designate the placement of the rigid materials or stiffening elements 80 having a Young's modulus that is greater than the Young's modulus of the surrounding material of the deflectable segment 24 . As shown, the cross-sectional shape of the stiffening elements 80 may be varied. Further, the stiffening elements 80 may, in various embodiments, be entirely encased within the sidewall of the deflectable segment. This may minimize or eliminate intrusion into a lumen defined by the segment 24 .
[0048] These stiffening elements 80 can be metals or metallic alloys commonly used for reinforcing catheter shafts, including steels, stainless steels, NiTi alloys, tungsten, and others. Also, those stiffening materials can be engineering polymers such as polycarbonates, nylons, polyesters, polyurethanes, nylon-based copolymers, polystyrenes, poly(methyl methacrylate), polysulfones, liquid crystalline polymers, etc. The un-shaded areas in FIGS. 6A-6J (i.e., the sidewall of the deflectable segment 24 ) have generally smooth, cylindrical outside surfaces extruded from a soft and flexible polymer material, which is commonly used to make current distal deflectable segment. These soft materials may include, without limitations, thermoplastic elastomers (TPE) of all kinds such as polyamide-based TPE (Pebax®, Vestamid® E and the like), polyester-based TPE's (Hytrel® and the like), styrenic TPE (Kraton®, Versaflex®, SIBStar®), and the like), functionalized olefinic TPE (Engage® and the like), ionic TPE's (Surlyn® and the like), thermoplastic polyurethanes (Pellethane®, Estane®, and the like), silicone-urethane TPE (Elaston®, PurSil®, CarboSil®, and the like) and etc. Elastomers or rubbers can be also used, including silicone rubbers and other synthetic rubbers such as polybutadiene, polyisoprene, and the like. When polymeric stiffening elements are used, they will typically have a Young's modulus that is significantly larger than the flexible polymeric material used to form the deflectable segment. The designs shown in FIGS. 6A-6J can be made using conventional melt co-extrusion, melt over-extrusion, extrusion-curing and heat lamination (or reflow) manufacturing processes, dependent of the rigid and flexible material pairs as well as the cross-sectional geometry used for the design of the distal deflectable segment 24 .
[0049] For the designs shown in FIGS. 6A-6J , the stiffening elements 80 are placed where x˜0 in the cross section of the distal deflectable segment 24 . That is, the stiffening elements are placed near a neutral in-plane bending axis (i.e. y-axis). Therefore, the stiffening elements 80 have minimal contribution to the in-plane bending stiffness about the neutral in-plane bending axis (i.e. y-axis), per Eq. (2). However, due to high Young's modulus of the stiffening material 80 and its placement along the reinforced plane 110 (i.e. yz-plane) and near the outside diameter of the cross section of the distal deflectable segment 24 , the stiffening element 80 significantly increases the out-of-plane bending stiffness about the neutral out-of-plane bending axis (i.e. x-axis), per Eq. (3). Therefore, this combination of a stiffening element in the cross section of the distal deflectable segment 24 leads to high anisotropic bending stiffness for the distal deflectable segment 24 with the out-of-plane bending stiffness being significantly higher than the in-plane bending stiffness. As will be appreciated, deflectable catheters with highly anisotropic bending stiffness in their distal deflectable segments will typically exhibit improved deflecting planarity and consistency and become much less influenced by disturbance of out-of-plane bending moments generated by the pull wires and pull ring. That is, even if the pull wires 26 and their anchoring points on the pull ring 22 are misaligned with the sweeping plane 100, the out-of-plane bending stiffness for deflection in the reinforced plane 110 or about the neutral out-of-plane bending axis (i.e. x-axis) will minimize or prevent the distal tip of the catheter from moving outside of the sweeping plane 100. In this regard, distal deflectable segment 24 allows for improved controllability of the distal catheter deflection and/or improved placement of the catheter relative to internal tissue areas of interest.
[0050] While the above exemplary embodiments illustrated in FIG. 6A-6J utilize one or two stiffening elements 80 disposed along, and in the vicinity of, the reinforced plane 110 as well as in symmetry with the desired sweeping plane 100, it will be appreciated that alternative placements of stiffening elements 80 in the deflectable segment 24 may be also effective for promoting in-plane deflection and preventing out-of-plane deflection. Further, stiffening elements may have different shapes and their cross sections may have the same or different area moments of inertia about their neutral centroidal axes. In addition to varying size, shape and/or location of the stiffening elements in the segment 24 , it will be appreciated that the stiffening elements may extend over the entirety or only a portion of the length of the distal deflectable segment 24 . This may allow for tailoring the deflected shape of the distal deflectable segment.
[0051] FIG. 7A illustrates a typical anisotropic stiffening segment 80 whose cross section has large difference in the area moments of inertia about its two centroidal axes, namely 1c and 2c, due to its ribbon-like rectangular shape. The first area moment of inertia about the first centroidal 1c-axis is:
[0000]
I
1
c
=
tw
3
12
Eq
.
(
5
)
[0000] while the area moment inertia about the second centroidal 2c-axis is:
[0000]
I
2
c
=
wt
3
12
Eq
.
(
6
)
[0000] wherein the ribbon width, w, is significantly larger than the ribbon thickness, t, in the cross section of the segment 80 . It is appreciated from Eq. (5) and Eq. (6) that the area moment of inertia 11 , (i.e., geometrical resistance to bending) about the first centroidal axis (i.e. 1c-axis) of the ribbon-like stiffener 80 is much greater than the area moment of inertia I 2c about the second centroidal axis (i.e. 2c-axis) because w>>t. That is, the shape of the stiffening element 80 provides an anisotropic bending stiffness, aid may be advantageously used to increase the out-of-plane bending stiffness in a more effective way. Therefore, by incorporating one or more stiffening elements 80 into the distal deflectable segment in such a way that the first centroidal axis (i.e. 1c-axis) of the stiffener 80 is in parallel with the sweeping plane 100 and that the second centroidal axis is aligned with the reinforced plane 110, the bending stiffness of the deflectable segment 24 for deflection in the reinforced plane could be maximized. This embodiment is shown in FIG. 7B , and also in FIG. 6D and 6I .
[0052] Another embodiment for disposing an anisotropic stiffening elements 80 , as shown in FIG. 7A , in the deflectable segment 24 is further illustrated in FIG. 7C , where the first centroidal axes of the stiffening element is aligned with the reinforced plane 110 of the deflectable segment while the second centroidal axis is in parallel with the sweeping plane 100. It will be appreciated that under certain conditions, such placement of the stiffening elements may still largely enhance the out-of-plane bending stiffness, namely S out-of-plane , while the in-plane bending stiffness, namely S in-plane , is kept relatively small. For instance, where the stiffening elements 80 are formed of metallic material, which has significantly higher Young's modulus (i.e. E s ) than the flexible polymeric materials forming the deflectable segment 24 (i.e. E). In general, Young's modulus of a metallic element 80 is hundreds of, even thousands of times the Young's modulus of a soft, flexible polymeric material forming the body of the segment 24 . Therefore, it can be further appreciated that the contribution of the elements 80 to the in-plane bending stiffness, ΔS in-plane , and the contribution to the out-of-plane bending stiffness, ΔS out-of-plane , are equivalent to the respective bending stiffness of the deflectable segment 24 . That is,
[0000] S in-plane ≈ΔS in-plane and S out-of-plane ≈ΔS out-of-plane Eq. (7)
[0000] Using transfer formula for area moment of inertia, it can be further appreciated that
[0000]
S
out
-
of
-
plane
≅
2
E
s
I
x
=
2
E
s
(
twr
2
+
I
2
c
)
=
2
E
s
(
tw
·
r
2
+
1
12
wt
3
)
Eq
.
(
8
)
S
i
n
-
plane
≅
2
E
s
I
y
=
2
E
s
I
1
c
=
1
6
E
s
tw
3
Eq
.
(
9
)
[0053] From Eq. (8) and (9), it will be appreciated that if the distance of the element 80 from the sweeping plane 100 is comparable to the width of the ribbon-like, rectangular stiffening element 80 , e.g. r˜w. the out-of-plane bending stiffness can be at least twelve times the in-plane bending stiffness.
[0054] Yet another embodiment for disposing an anisotropic stiffening elements 80 , shown in FIG. 7A , in the deflectable segment 24 is illustrated in FIG. 7D , where the first centroidal axes (i.e. 1c-axes) of the ribbon-like stiffening element 80 is aligned with the sweeping plane 100 at a distance (namely r) from the reinforced plane 110. Similar to the above discussion, it can be appreciated that the in-plane bending stiffness and the out-of-plane bending stiffness of a deflectable segment 24 , which is incorporated with metallic elements 80 , can be approximated as follows,
[0000]
S
out
-
of
-
plane
≅
2
E
s
I
x
=
2
E
s
I
1
c
=
1
6
E
s
tw
3
Eq
.
(
10
)
S
i
n
-
plane
≅
2
E
s
I
y
=
2
E
s
(
twr
2
+
I
2
c
)
=
2
E
s
(
twr
2
+
1
12
wt
3
)
Eq
.
(
11
)
[0000] From Eq. (10) and (11), it will be appreciated that if the element distance from the reinforced plane 110 (namely r) is significantly less than 0.28√{square root over (w 2 −y 2 )}, the out-of-plane bending stiffness of the deflectable segment can be still effectively enhanced by so-disposed reinforcing elements as illustrated in FIG. 7D .
[0055] From a series of embodiments as illustrated in FIG. 7B , 7 C and 7 D, it can be appreciated that an anisotropic stiffening element 80 can be incorporated in a deflectable segment 24 in multiple ways. Considering anisotropy of in-plane and out-of-plane bending stiffness as required by controlling planarity of deflection and manufacturability, one incorporating way may be more advantageous than other ways with the cross-sectional selections of both a stiffening element 80 and its placement in a deflectable segment 24 . However, it is appreciated from the embodiments that uses of stiffening elements 80 in alternative ways are still within the spirit and scope of this invention.
[0056] It will be further noted that despite a cross-sectional shape, inclusion of any stiffening element 80 having a Young's modulus (Es) that is greater than the Young's modulus of a material(E) forming the body of the distal deflectable segment 24 will more or less increase out-of-plane bending stiffness of the segment 24 , if the element 80 is properly disposed in the segment 24 For instance, referring to FIG. 6C , it is noted that the inclusion of the generally circular metallic or rigid polymer wire/rod-like stiffening elements 80 along the reinforced plane 110 may increases the out-of-plane bending stiffness about the neutral out-of-plane bending axis (i.e., x axis) without significantly changing the in-plane bending stiffness about the neutral in-plane bending axis (i.e., y axis). Further, as shown in FIGS. 6E , 6 F and 6 J, it will be noted that a single stiffening element may be included along the reinforced plane and may extend entirely across the distal deflectable segment and thereby divide the internal lumen of the deflectable segment into two. As discussed above, such a single stiffening element having the width that is considerably larger than its thickness, when properly disposed in the cross section of a deflectable segment, may significantly increase the out-of-plane bending stiffness of the segment.
[0057] In a further arrangement, the cross section of a distal deflectable segment 24 may be designed or properly shaped to moderately enhance the out-of-plane bending stiffness without utilizing different material and/or separate stiffening elements. FIGS. 8A and 8B illustrate two embodiments where the sidewall thickness and/or shape of the cross-section of the distal deflectable segment 24 are altered to enhance out-of-plane bending stiffness. As shown in FIG. 8A , the distal deflectable segment 24 maintains a generally circular outside surface. However, the sidewall thickness of the distal deflectable segment is non-uniform. More particularly, first and second nodules 82 are formed on the sidewall where the nodules 82 are axially along the deflectable segment 24 and distributed in the vicinity of the reinforced plane 110. As will be appreciated, this non-circular cross section of the segment 24 will increase the area moment of inertia (I x ) about the neutral out-of-plane bending axis (i.e. x axis), thereby increasing the out-of-plane bending stiffness of the deflectable segment 24 . FIG. 8B illustrates a second embodiment wherein the outside surface of the distal deflectable segment is ovular. Again, area moment of inertia (I x ) about the neutral out-of-plane bending axis (i.e. x-axis) will be larger than the area moment of inertia (I y ) about the neutral in-plane bending axis (i.e. y-axis) of the distal deflectable segment 24 . This will likewise provide anisotropic bending characteristics to the distal deflectable segment.
[0058] Although multiple embodiments of this invention have been described above with a certain degree of particularity, those skilled in the art could make numerous alterations to the disclosed embodiments without departing from the spirit or scope of this invention. For example, different cross-sectional shapes of the deflectable segment by increasing or decreasing the sidewall thickness of the deflectable segment 24 and/or various stiffening elements with different combinations of material selections and geometrical shapes as well as their placements in the cross section of, and longitudinally along, a deflectable segment 24 are possible. An important feature of this invention is that the resulting deflectable segment, regardless of the exact configuration of the segment, exhibits anisotropic bending stiffness. Further, it is noted that all directional references (e.g., upper, lower, upward, downward, left, right, leftward, rightward, top, bottom, above, below, vertical, horizontal, clockwise, and counterclockwise) and planar references (e.g. in-plane, out-of-plane, reinforced plane, sweeping plane and the like) are only used for identification purposes to aid the reader's understanding of the present invention, and do not create limitations, particularly as to the position, orientation, or use of the invention. Joinder references (e.g., attached, coupled, connected, and the like) are to be construed broadly and may include intermediate members between a connection of elements and relative movement between elements. As such, joinder references do not necessarily infer that two elements are directly connected and in fixed relation to each other. It is intended that all matter contained in the above description or shown in the accompanying drawings shall be interpreted as illustrative only and not limiting. Changes in detail or structure may be made without departing from the spirit of the invention as defined in the appended claims. | A guidable, or steerable, or deflectable catheter is provided that includes a proximal portion and a distal portion for insertion into a body cavity. A selectively deflectable segment having an anisotropic bending stiffness for deflection in individual planes is incorporated into the distal portion of the catheter shaft. Upon actuation of pull wires, the distal deflectable segment may be deflected to move/sweep the distal catheter tip through a sweeping plane. The anisotropic bending stiffness of the distal deflectable segment permits in-plane movement of the distal catheter tip in the sweeping plane while resisting any out-of-plane movements. In one arrangement, stiffening elements are selectively disposed within the distal deflectable segment such that the out-of-plane bending stiffness is largely increased and greater than the in-plane bending stiffness for deflection in the sweeping plane. In another arrangement, the cross section of a distal deflectable segment is altered to produce anisotropic area inertias of moment about its centroidal axes, and thus anisotropic bending stiffnesses. | 0 |
Field of the Invention
This invention pertains to the field of grain stirring devices, and more particularly pertains to an apparatus for automatically powering off the stirring device in the absence of forward movement of the stirring mechanism for a predetermined length of time.
BACKGROUND OF THE INVENTION
It is current practice to dry grain or other like materials by placing same in a cylindrical container and forcing heated air upwardly therethrough. Various methods, such as batch drying and layer drying have been developed to overcome problems encountered in such drying operations. Both such methods are inefficient since considerable time and labor is required. Additionally, problems such as uneven drying, incomplete drying, and crusting of the upper surface further complicate such drying operations and may result in insect infestation and/or spoilage. A more efficient method is deep-bed drying, wherein the container or bin is substantially filled with grain and a stirring device, such as that disclosed in U.S. Pat. No. 3,251,582 and U.S. Pat. No. 3,580,549, is used to constantly stir or mix the grain throughout the drying cycle. Such devices are normally constructed to travel a predetermined path circumferentially and radially within the container during the drying cycle thereby overcoming the above problems.
A new problem has arisen, however, in the case when a stirring device operates in a stationary position for a substantial length of time. Such operation results in overstirring and possible damage of grain surrounding the mechanism. With the typical two motor grain stirring mechanism in which a first motor drives the stirring unit in an orbital and radial path around the bin, and a second motor powers the stirring mechanism, the above-described problem can occur as a result of failure of the first motor, malfunctions in the drive linkage, or obstructions.
Unlike prior art systems, the present invention provides an apparatus for continually monitoring the orbital movement of the stirring mechanism support structure and automatically powering off the motors in the absence of orbital movement after a predetermined time period. In this manner the present invention avoids needless damage to the material contained within the container and conserves electrical energy for more productive uses.
SUMMARY OF THE INVENTION
The present invention comprises apparatus for controlling delivery of power to a stirring device mounted in a grain storage bin. The device has means for stirring grain and means for moving the stirring means about the interior of the bin. The stirring means and the moving means are driven by the indicated power. The apparatus comprises means for sensing movement of the moving means and means for interruptably connecting the power to said stirring means, said stirring means being controlled by the sensing means. In this fashion, when the sensing means senses absence of movement of the moving means, after a predetermined time period, the connecting means interrupts power to the stirring means thereby protecting the grain from harmful overstirring.
In a preferred embodiment, the grain stirring device has a central shaft and an auger support mechanism depending radially therefrom to the wall of a bin. A pair of motors drive an auger and drive the supporting mechanism orbitally around the central shaft. The present invention senses movement or absence of movement of the supporting mechanism. The sensing mechanism is comprised of a cam fixedly attached to the stationary central shaft and a microswitch attached to the auger support structure which rotates about the shaft. The microswitch has a cam follower which causes the switch to be periodically activated as the support mechanism rotates about the central shaft. Actuation of the switch causes a solid state timer to reset a predetermined time interval. The timer is connected to a relay. If the time interval times out without being reset, the relay opens, thereby disconnecting the power to the motors, which causes stirring to cease.
As long as the auger support mechanism continues to orbit about the bin, the switch will continually be actuated causing the timer to continually reset thereby keeping power connected to the drive motors. The present invention is particularly advantageous, therefore, since any malfunction or obstruction that stops orbital movement of the stirring mechanism structure prevents actuation of the switch thereby allowing the timer to time out and the relays to open so as to power down the drive motors. Thus, the present invention prevents damage to the drive motors and to the grain. More particularly, excessive stirring of a small portion of grain will cause cracking or grinding of the grain, which may result in heating or loss of market value and nutritional quality. Thus, the present invention not only protects the grain stirring device, but also protects the quality of the grain product which the grain stirring device is designed to otherwise enhance.
These advantages and other objects obtained by the use of the present invention may be better understood by reference to the drawings which form a further part of this disclosure and to the accompanying descriptive matter in which there is illustrated and described in more detail a preferred embodiment of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
Reference numerals designate identical or corresponding parts throughout the several views in the drawings as follows:
FIG. 1 shows a side elevational view of a grain bin having a stirring apparatus with an automatic power off device in accordance with the present invention;
FIG. 2 is a top view, taken along line 2--2 of FIG. 1, showing the trolley in relation to other mechanism near the bin wall;
FIG. 3 is a partially cut away side view of the enclosure housing apparatus in accordance with the present invention;
FIG. 4 is an enlarged view in elevation of a portion of the grain stirring device of FIG. 1 illustrating mechanism for controlling the degree of inclination of the auger relative to the vertical axis;
FIG. 5 is a view in vertical section as seen from line 5--5 of FIG. 4;
FIG. 6 is a sectional view taken along line 6--6 of FIG. 3 showing microswitch mechanism cooperating with cam mechanism; and
FIG. 7 is a schematic diagram illustrating electrical connections in accordance with the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIG. 1, reference number 10 generally indicates a cylindrical drying container or bin typically utilized in the drying of grain or other like harvested crops. Inside bin 10 there is shown grain 12 and a grain stirring device generally indicated by the numeral 20 which includes a support mechanism in the nature of a bridge frame 21 having a pair of laterally spaced rails 22 connected at opposite ends thereof by crossmembers 23. A circular track 24 is mounted near the upper end of the wall 11 of the container 10 and provides a support for the outer end of the bridge frame 21. Frame 21 extends radially of bin 10 moving about a vertical axis in an orbital path above material 12. A carriage 25 is pivotally secured to the outer end of the bridge frame 21 and supported on the circular track 24 for movement therealong by a pair of grooved wheels 27 rotatably carried by the carriage 25 at longitudinally spaced opposite ends.
The inner end of bridge frame 21 is suspended by a flexible mechanism in the nature of a plurality of chains or cables 30 engaged at one end in the opening 18 using hook elements 31. A generally horizontally disposed T-bar 32 is adjustable secured to the end portions of chains 30. A depending shaft 34, supported by the T-bar 32, in turn supports generally rectangular enclosure 35 on the inner end of a longitudinally extended frame element 36. A gooseneck portion 37 of frame 36 depends from the enclosure 35 and is rotatably mounted to the inner end of the bridge frame 21, as at 38. A yoke 39 is pivotally secured to the outer end of the frame element 36, as at 40, and fixedly secured to one of rails 22 of the bridge frame 21, as at 41.
Numeral 45 generally indicates a trolley mounted on the bridge frame 21 for movement longitudinally therealong in directions radially toward and away from the wall 11 of the container 10. The trolley 45 includes depending leg 46, positioned between the rails 22, which forms an auger support means for a stirring auger 47. A first pair of laterally spaced groove wheels 50 are rotatably mounted on the upper end of the depending leg 46 in a manner to engage an upper edge of each of the rails 22 and support the trolley 45 for movements along the bridge frame 21. A second pair of laterally spaced wheels 68 is mounted on the opposite end of the trolley arm 63 for rotation on an axis parallel to the axis of rotation of the wheels 50. Roller elements 69 are rotatably carried by the trolley arm 63 in a manner to engage an under surface of the rails 22. The above-described structure generally coincides with that disclosed in U.S. Pat. 3,580,549 and further detailed description relative thereto is eliminated in the interest of brevity.
A drive mechanism, connected to move the bridge frame 21 in its orbital path of travel, includes a gear head electrical motor 72. Geared motor 72 is mounted to one end of the carriage 25 with rotary output shaft thereof having one of the grooved wheels 27 fixedly secured thereto for driving engagement along the circular track 24.
A second drive mechanism connected to move the trolley 45 radially toward and away from the wall 11 includes a sheave 78 which is rotatably mounted on depending shaft 34. A pair of rotatable sheaves 79 are mounted on the yoke 39 for rotation on vertical axes. Sheaves 79 are spaced from each other transversely of the bridge frame 21 and from the sheave 78 longitudinally of the bridge frame 21. An endless flexible drive element 80 is entrained over sheaves 79 and sheave 78. A connection between the drive element 80 and the trolley 45 is made with a pitman arm 81. Pitman arm 81 is connected at one end thereof to a fixed point on the flexible drive element 80 by a pivotal connection 82. The other end of the pitman arm 81 includes a cross head 83 which is slidably mounted to an arcuate element 84 fixedly connected to the trolley arm 63 as at 85. Arcuate element 84 is mounted to extend transversly of the bridge frame 21.
In order to impart movement to the fixed point or pivotal connection 82 of flexible drive element 80 and consequently, movement of the pitman arm 81 and trolley 45 longitudinally of the bridge frame 21, sheave 78 is immobilized relative to the rotation of the bridge frame 21 about the vertical axis of the bin 10. To immobilize the sheave 78 an arm 90 is fixedly mounted on the depending shaft 34 to extend radially to the sheave 78 and closely underlying relationship thereto. A detachable mechanism, in the nature of a metal loop 91, is pivotally carried by the sheave 78 and is adapted to engage the outer end of the radial arm 90 to prevent rotation of the sheave 78. Immobilizing of the sheave 78 causes the drive element 80 to wrap about the pulley 78 and the fixed point or pivotal connection 82 to travel in a path between the sheaves 79 and between the sheave 78 and sheaves 79. It will be appreciated that such movement of the fixed point or connection 82 between the sheaves 78, 79 causes the trolley means 45 to move longitudinally of the bridge frame 21 and that movement of the fixed point between the sheaves 79 positions the trolley means 45 at the outer end of the bridge frame 21 with little or no movement longitudinally of the bridge frame 21 during orbital movement of the bridge frame in the container 10.
An electric motor 100 provides drive means for imparting rotation to the auger 47. Motor 100 is mounted on the trolley means 45 in cantilever fashion by means of a laterally projecting plate 98.
Referring now to FIG. 7 there is shown schematically a wiring diagram of the electrical connections for a single auger according to the present invention. A power source (not shown) comprising the ground 101 and ac voltage lines 102 and 103 are passed through switch 104 and fuses 105 of fuse switch box 99 to swivel slip ring connectors 106, 107, and 108 respectively. Swivels 106-108 are mounted within the rectangular enclosure 35. Switching mechanism 104 is normally mounted on the T-bar 32. Ground line 101 is connected via conductor 109 from swivel connector 106 to receptacle 125. Conductors 110 connect from the other side of receptacle 125 to the ground terminals 112 and 111 of the respective auger motor 100 and gear motor 72.
Conductor 115 connects swivel 107 to terminal 116 of solid state timer 117 and to terminal 118 of relay 119. Conductor 120 connects from terminal 121 of relay 119 to receptacle 125. Conductor 123 connects from the corresponding output terminal of receptacle 125 to terminal 124 of gear head motor 72. Conductor 122 depends from the same terminal of receptacle 125 and is connected to mercury switches 126 and 127. Conductor 128 connects mercury switch 127 through fuse 129 and to terminal 130 of auger motor 100.
Conductor 131 connects to swivel connector 108 and to terminal 132 of relay 133. Conductor 131 is further connected to terminal 134 of relay coil 135 and to terminal 136 of solid state timer 117. Conductor 137 connects from terminal 138 of relay 133 to receptacle 125. Conductor 139 connects from the side of receptacle 125 corresponding to conductor 137 through fuse 140 to terminal 141 of auger motor 100. Conductor 142, which is connected to the same terminal as connector 139 connects to terminal 143 of gear motor 72.
Conductor 144 connects from terminal 145 of relay coil 135 to terminal 146 of timer 117. Terminal 150 of microswitch 151 connects through conductor 152 to terminal 153 of said timer. Terminals 155 and 156 of microswitch 151 are connected through conductors 154 and 157 to the respective terminals 158 and 159 of timer 117.
Referring now to FIG. 3 there is shown an elevational fragmentary view of enclosure 35. The electrical components shown in the enclosure generally correspond to those schematically illustrated in FIG. 7. Junction box 51 connects power lines 101, 102 and 103 to the respective circular contacter plates 170, 171 and 172 which are circumferentially mounted on shaft 34. As described with regard to FIG. 1, enclosure 35 rotates about shaft 34 as frame 21 orbits grain bin 10. Washers 173 separate and maintain swivel connectors 106-108 in position with contactors 170-172. Terminal block 180 connects swivel connectors 106-108 to the respective conductors 109, 115 and 131.
The electronic components and their terminals have reference numbers corresponding directly to those of the appropriate portions of FIG. 7. It should be noted that relay coil 135, and contacts 133 and 119, are mounted within relay housing 182.
Referring now to FIG. 6, there is shown gear tooth cam 190 and microswitch 151. During the orbiting of journal box 35 about the shaft or pivot axis 34, roller bearing 191 of microswitch 151 rides the cam surface 192. As the enclosure 35 rotates about the pivot axis 34, plunger 193 is depressed when roller bearing 191 traverses the apex of a cam gear tooth. Depression of plunger 193 causes a circuit path from terminal 150 to terminal 155. When plunger 193 is fully extended, a circuit path exists between terminal 150 and terminal 156.
Although the present embodiment is described with cam 190 located on shaft 34 and switch 151 orbiting thereabout, it is to be understood that switch 151 and cam 190 could be interchanged such that cam 190 orbits about switch 151. It is further understood that an actuating mechanism other than a cam may operate a switch equally well and that switch 151 could be located other than near or on shaft 34. For example, switch 151 could be located near track 24 and actuated periodically by the brackets (not shown) which attach track 24 to bin 10.
Referring to FIG. 4, there is shown the mechanism for controlling the degree of inclination of the auger relative to a vertical axis. Mercury switches 126 and 127 correspond to those switches illustrated and identified with the same reference numbers in FIG. 7. FIG. 5 is another view of mercury switch 126. The operation of these switches is more fully explained by the above-identified prior patent.
Referring generally to FIGS. 6 and 7 the operation of the present invention will now be explained. The energization of motors 72 and 100 and consequently the turn-on of the grain stirring device for operation is accomplished by actuating ac power switch 104. Upon closing switch 104 power is delivered to the various circuits of FIG. 7 through swivel connectors 106-108. Upon initial power-up of solid state timer 117 via conductors 115 and 131 and the respective terminals 116 and 136, timer 117 applies a low level signal to terminal 145 of relay coil 135 from its output terminal 146 through conductor 144. As the other side of coil 135 is connected to an ac power source at terminal 134 through conductor 131, coil 135 energizes and causes contacts 119 and 133 to close. A path is thereby provided from conductor 131 to 137 and from conductor 115 to 120, delivering the AC power necessary to drive motors 72 and 100 via conductors 122, 123, 139 and 142. Timer 117 continues to ouput a coil energizing signal on conductor 144 for a predetermined time period, 45 minutes in the preferred embodiment, and in the absence of a reset signal from microswitch 151 the relay energizing signal is terminated at the end of said period.
During normal operation, a reset signal is applied to timer 117 before coil deenergization occurs. The reset signal required to maintain power continuity is recurringly generated by microswitch 151 and gear tooth cam 190. Normally, the time required for roller bearing 191 to travel from one gear tooth to the next and thereby generate a reset signal path between terminals 158 and 153 of timer 117 is less than the predetermined time period of timer 117. In this manner AC power is delivered to motors 72 and 100 continuously and without interruption.
In the case where microswitch 151 fails to rotate about pivot shaft 34 due to a malfunction or failure in the drive mechanism of bridge frame 21, timer 117 does not receive the necessary reset signal to maintain continuity of power to motor 72 and 100. More specifically, the relay energizing signal to coil 135 is terminated at the end of the predetermined time period thereby opening contacts 133 and 119 which in turn terminates the supply of ac power to motors 72 and 100. To restart the stirring unit main power switch 104 is opened and reclosed.
The present invention is described hereinbefore with reference to existing grain stirring apparatus as described in U.S. Pat. No. 3,580,549. An electrical embodiment of the present invention is also described. It is to be understood, however, that the present invention is equally applicable to other grain stirring devices and that the present invention is not limited to an electrical embodiment since fluid, pneumatic or mechanical devices may function in a similar fashion to accomplish similar results. Consequently, although numerous characteristics and advantages of a preferred embodiment, together with details of the structure and function, have been described in this disclosure, it is to be understood that the disclosure is illustrative. Any changes made, especially in matters of shape, size and arrangement, to the full extent extended by the general meaning of the terms in which the independent claims are expressed, are within the principle of the invention. | Apparatus for controlling delivery of power to a grain stirring apparatus is disclosed. A bridge frame (21) is supported between a shaft (34) and a circular track (24) on the wall (11) of bin (10). Frame (21) supports a trolley mechanism (45) having a rotating auger (47) operatively attached thereto. Frame (21) moves orbitally around bin (10) as trolley (45) moves radially inward and outward thereby allowing auger (47) to stir grain (12).
The apparatus for controlling power delivery has a switch (151) which senses orbital movement using roller (191) to follow cam (190) fastened to shaft (34). If orbital movement is not appropriately sensed, timer (117) causes relays (119) and (133) to open thereby powering off grain stirring apparatus (20). | 8 |
CROSS REFERENCE TO RELATED APPLICATIONS
This is a continuation-in-part of International Application PCT/GB97/02883, filed Oct. 17, 1997, which is a continuation of U.S. application Ser. No. 08/734,228, filed Oct. 21, 1996 (now abandoned).
FIELD OF THE INVENTION
This invention relates to chemical synthesis, and more particularly to an improved apparatus and method for distributing microscopic beads of the kind used as substrates in combinatorial chemistry.
BACKGROUND OF THE INVENTION
In combinatorial synthesis, it is often desirable to be able to distribute beads into a two-dimensional array, so that each variant in a combinatorial library can be identified by its position in the array. The array can consist of a set of plates, each having rows and columns of wells, with one bead, or some other predetermined number of beads, in each well. The beads are typically made of polystyrene, and serve as substrates for different compounds produced in the process of split and combine synthesis. Ultimately, the synthesized compounds are stripped from the beads and tested for activity. The identity of an active compound is determined by spectrographic analysis, in the light of the information available concerning the reaction histories of the beads being distributed.
The beads are spherical and of extremely small size, e.g. 300 mm in diameter. Consequently, they are difficult to handle, and it has been very difficult to separate a single bead from a mixture of beads.
SUMMARY OF THE INVENTION
The principle object of this invention is to provide an apparatus and method for selecting individual beads, or preselected numbers of beads from a mixture of beads, and distributing the selected beads into a two-dimensional array.
A further object of the invention is to provide a bead distribution apparatus which is both simple and highly reliable.
This apparatus utilizes a head similar to that of a "Coulter" counter, a device used to count and size particles in a liquid. For example, it is used in the petroleum industry to assess engine wear by counting particles in lubricating oil. The principle on which the Coulter counter operates is that electrical resistance of a conductive fluid, measured by electrodes on both sides of a small aperture, increases momentarily as a solid particle passes through the aperture. The passage of particles through the aperture is detected as a electrical pulses, which can be counted electronically. The Coulter counter is described in detail in U.S. Pat. No. 2,656,508, issued Oct. 20, 1953, and the disclosure of that patent is here incorporated by reference.
The preferred embodiment of this invention takes advantage of the principle of the Coulter counter, but uses the principle in a different way and for a different purpose.
In accordance with the invention, beads, from a mixture of beads of uniform size, are distributed into an array having multiple locations, so that a predetermined number of beads is deposited at each location in the array. This is carried out by forming a suspension of the mixture of beads in a carrier liquid; causing a part of the liquid to flow through an aperture of a size such that the beads can pass through the aperture only one at a time; detecting the passage of a predetermined number of the beads through the aperture; and, in response to the detection of the passage of the predetermined number of the beads through the aperture, depositing them at a predetermined location of the array.
In one embodiment of the invention, the selection of beads to be deposited is carried out by discontinuing the flow through the aperture upon detection of the passage of the predetermined number of the beads through the aperture. In an alternative embodiment, flow takes place continuously through the aperture, and is diverted in response to a detection signal to effect bead deposition.
The carrier liquid is electrically conductive, and is stirred to keep the beads in suspension. In a first embodiment, to deposit a single bead, a syringe is operated to produce a steady flow of liquid through an aperture in the side wall of a tube extending through the container for the carrier liquid. Eventually, a bead will pass through the aperture along with the liquid. When the passage of a bead is detected electrically, the operation of the syringe is discontinued and the flow of liquid through the aperture stops. This prevents other beads from passing through the aperture. After its passage through the aperture is detected, the bead is flushed out of the tube by a pumped liquid, and deposited at its location in the array, preferably into a well in a well plate. Preferably, while the syringe is causing liquid to flow into the tube through the aperture, liquid is withdrawn from the upper end of the tube by a pump at the same rate at which it flows into the tube through the aperture. This prevents liquid from passing through the lower end of the tube. Normally only one bead will be deposited at each location in the array. However, multiple beads can be deposited at each location. This is done by counting the electrical pulses corresponding to peaks in resistance. When the desired number of beads is counted, the flow of the suspension liquid is discontinued.
In a second embodiment, the aperture at which detection takes place is at the end of a tube through which liquid flows continuously. When a bead is detected at the aperture, a signal is produced causing the flow of liquid to be diverted so that the bead is carried to the location at which it is to be deposited.
In a preferred embodiment of the invention, a stack of empty well plates is initially placed in the apparatus. The lowermost well plate in the stack is automatically moved to a position underneath the head with a first row of wells positioned underneath, and parallel to a linear path of movement of the head. The head moves successively from one well to the next, depositing a bead in each well of the column. The well plates are indexed laterally to position successive rows of wells underneath the path of the head. When a plates are filled, i.e. it has one bead in each of its wells, it is moved into a new stack and the apparatus retrieves a new plate from the supply stack and begins to distribute beads to the new plate.
Further objects, details and advantages of the invention will be apparent from the following detailed description, when read in conjunction with the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagrammatic front view of a bead distribution apparatus, showing a movable bead distribution head, and mechanisms for transporting well plates from a supply stack to a location underneath the distribution head, and from the distribution head to a second stack;
FIG. 2 is a diagrammatic top plan view of the bead distribution apparatus;
FIG. 3 is a vertical section through the bead distribution head;
FIG. 4 is a fragmentary sectional view, showing details of the bead selection aperture in the bead distribution head;
FIG. 5 is a top plan view of the cover of the bead distribution head;
FIG. 6 is a section taken on plane 5--5 in FIG. 4; and
FIG. 7 is a section taken on plane 6--6 in FIG. 4;
FIG. 8 is a schematic diagram showing the fluid paths and controls of the apparatus, and illustrating the manner in which a bead is selected from a suspension of beads in a liquid;
FIG. 9 is a schematic diagram illustrating the movement of well plates from the supply stack to a location underneath the distribution head, and from the distribution head to the second stack;
FIG. 10 is a typical plot of electrical voltage versus time across the aperture of the bead distribution apparatus; and
FIG. 11 is a schematic diagram showing a distribution head assembly in accordance with an alternative embodiment of the invention.
DETAILED DESCRIPTION
Referring to FIGS. 1 and 2, the bead distribution apparatus 10 comprises a loading guide 12 in which empty well plates, of a standard, commercially available type, may be stacked. The empty well plates are unloaded from the bottom of guide 12 by an unloader 14 into a conveyor 18, and are transferred individually by the conveyor to a position underneath a distribution head 16. Each well plate, e.g. well plate 19 in FIG. 2, has a rectangular array of wells disposed in rows and columns. While a well plate is underneath the distribution head, the distribution head moves from well to well in a row (perpendicular to the plane of FIG. 1), depositing a bead in each well. When the distribution head has traversed a row of wells, the conveyor 18 indexes the well plate to position a next row underneath the path of the head. This is repeated until beads are deposited in all of the wells. Then the conveyor moves the well plate to a position underneath a stacking guide 20, and the well plate is loaded into the stacking guide by a stacker 22.
The unloader 14 and the stacker 22 are elevators with platforms which engage the lowermost well plates in the guides and move vertically to load and unload the conveyor. Catches (not shown in FIGS. 1 and 2) are provided at the lower end of the loading guide 12 for supporting the stack of well plates in the loading guide when the unloader 14 is retracted. These catches are electrically operated, and microprocessor controlled so that they cooperate with the unloader 14, allowing the unloader to receive a well plate from the loading guide 12 and deposit the well plate onto the conveyor. Ratchet-type catches (not shown in FIGS. 1 and 2) are provided at the lower end of the stacking guide 20 to support well plates in the stacking guide while allowing the stacker 22 to deposit the well plates therein.
While the well plate is underneath the distribution head 16, a bead is deposited in each well, the distribution head being indexed from well to well in each row of wells along a supporting arm 24. The distribution head can also be moved to a position just above a waste collector 25, which, as shown in FIG. 2, is located behind the path of movement of the well plates.
The distribution head supporting arm 24 is itself movable vertically so that the distribution head can be moved up and down. All of the fluid conducting lines and electrical leads to the distribution head 16 are flexible, and preferably bundled together in a single flexible sheath 15 (FIG. 1), so the that the distribution head can move freely.
The distribution head, shown in detail in FIG. 3, comprises a cup-shaped vessel 26 having a cover 28 secured to a flange 30 of the vessel by a threaded ring 32. A sleeve 34 extends through the center of the cover, and a pipette 36 is held in the sleeve by seals 38 and 40. The pipette extends through vessel 26, its upper end 42 being located above the cover 28, and its lower end 44 being below the bottom of the vessel. The pipette extends through a seal 46 at the bottom of the vessel.
The outside wall of the pipette is cylindrical throughout most of its length. However, a flat area 48 is formed on the outer wall of the pipette at a location within the interior of the vessel 26 just below the lower end of sleeve 34. As shown in FIG. 4, an opening 50 is formed in the wall of the pipette within the flat area 48, and a small watch jewel 52, having an accurately machined aperture 54 is secured to the flat area by an adhesive, with aperture 54 in register with opening 50. The aperture 54 is typically 500 mm in diameter, but can be larger or smaller, depending on the size of the beads to be distributed. In general, the diameter of the aperture should be less than twice the diameter of the beads. Alternatively, the aperture can be formed directly in the wall of the pipette, obviating the use of the jewel.
As shown in FIG. 4, a first platinum electrode 56 is located within the pipette, with its tip adjacent to opening 50. Electrode 56 extends through a seal 60 in the wall of the pipette and is connected to a flexible, multistrand lead 58, which is isolated from the suspension in vessel 26 by sleeve 34. Another platinum electrode 62 has its tip located adjacent to the outer end of aperture 54, and extends through seal 40 into the space between the pipette and the inner wall of sleeve 34, where it is connected to a flexible lead 64.
Returning to FIG. 3, the top of the pipette is provided with a fitting 66 for connection to a pump. The pump (not shown in FIG. 3) is used to withdraw liquid from the upper end of the pipette as it flows into the pipette through aperture 54. The pump is also used to deliver liquid for flushing selected beads out through the lower end of the pipette.
FIGS. 5, 6 and 7 show that the cover 28 has three additional openings besides its central opening through which sleeve 34 extends. The first opening, 68, is an opening for introducing beads into the vessel, and is closable by a removable threaded plug 70 (FIG. 3). The second opening, 72, is an inlet for connection to a syringe used to produce flow of liquid into vessel 26. The third opening, 74, is a vent opening. As shown in FIGS. 3, 6 and 7, the underside of the cover 28 has an annular groove 76 which varies in depth, with its deepest point being at the location of vent opening 74. The groove becomes continuously shallower in both directions from the vent opening toward a shallowest point 78 (FIG. 7) opposite the vent opening so that air can be exhausted completely from the vessel. A porous filter 80 is provided in the vent opening.
FIG. 8 shows vessel 26 filled with a suspension consisting of a liquid 82 and beads 84, held in suspension by an external magnetic stirring mechanism 86 cooperation with an agitator 88 inside the vessel. The density of the beads 84 is preferably greater than that of the liquid, so that they sink in the liquid. To prevent surface tension from causing the beads to float, they are pre-treated so that they are wetted by the liquid.
An example of an ideal liquid for use with polystyrene beads is a solution of ammonium acetate (2% w/w), and ammonium carbonate (2% w/w).
The liquid 82 is supplied to vessel 26 from a supply container 90 through a peristaltic pump 92, which is controlled by a control unit 94, and a check valve 93. A syringe 96 is used to control the flow of the liquid after the vessel 26 is filled. The syringe is operated by an actuator 98, controlled by the control unit. When the plunger of the syringe is withdrawn, the syringe draws liquid from supply container 90 through a check valve 100. Forward movement of the plunger causes the liquid to flow through check valve 101 into vessel 26.
A reversible peristaltic pump 104 is provided to withdraw liquid from the upper end of the pipette 36 as it flows into the pipette through aperture 54, and to pump liquid through the pipette from container 102 for the purpose of flushing beads out of the pipette either to the wells, or to the waste collector 25. Pump 104 is also under the control of unit 94.
In the operation of the system, the beads are introduced into the vessel 26 through opening 68 (FIGS. 5 and 6), which is then closed by plug 70 (FIG. 3). The control unit then operates pump 92 to fill the vessel with liquid from supply container 90. The operation of the pump 92 is discontinued when the vessel is filled with liquid. In the meanwhile, a well plate 106 is removed from the supply stack in guide 12 (FIG. 1) and moved into position underneath the vessel 26, which is a part of the distribution head.
The well plate 106, as shown in FIG. 1, comprises a two-dimensional rectangular array of wells 108 (FIG. 8), each of which is preferably closed at its bottom.
With the distribution head positioned so that the pipette is over the waste collector 25, the syringe 96 is operated to initiate a controlled flow of liquid at a constant rate into vessel 26 through check valve 101. While other kinds of pumps can be used to carry out this operation, the syringe is desirable because it is capable of producing a steady flow of liquid at a very slow rate. While the syringe 96 is causing liquid to flow into the vessel 26 and through the aperture 54 into the pipette 36, pump 104 is operated to withdraw liquid from the upper end of the pipette 36. The pump withdraws liquid at the same rate at which it is being introduced into the pipette by the operation of the syringe 96. The result is that liquid is prevented from being forced out the tip of the pipette, no matter how long it takes for a bead to pass through the aperture. This prevents unnecessary flow of liquid into the waste collector, and also prevents loss of beads through the tip of the pipette when multiple beads are being collected in the pipette for deposit into a well.
As seen in FIG. 8, a bead 110 in the suspension will eventually pass through aperture 54 into the interior of the pipette. The passage of the bead is detected by the control unit 94 as a change in the resistance measured between platinum electrodes 56 and 62. When the control unit detects the passage of a single bead, it causes actuator 98 to stop pushing the plunger of syringe 96 and simultaneously stops pump 104. As a result, the liquid flow through the aperture is discontinued, and only a single bead passes into the pipette. The control unit moves the distribution head to the next well in sequence, and after a predetermined delay, during which the bead inside the pipette settles by gravity to the tip of the pipette, the control unit activates pump 104 in the opposite direction for a short interval just sufficient to wash the bead out of the pipette 36 into the well.
The control unit then causes the distribution head to return to the waste collection point, and the bead depositing operation is repeated for each well in the row. After beads are deposited in each well in a row, the well plate is indexed to position another row of wells underneath the path of the distribution head. The bead depositing operation continues until beads are deposited in each well in the well plate, whereupon, the well plate is transferred to a position underneath the stacking guide 20, and elevated into the stacking guide. The movement of the well plates is depicted in FIG. 9.
FIG. 9 also depicts laterally-slidable catches 111, which are operated by actuators (not shown) under the control of the control unit, for supporting the stack of well plates in the loading guide. Also shown are the ratchet-type catches 113, which support well plates in the stacking guide while allowing well plates to be raised into the stacking guide 20 by stacker 22.
The passage of beads through the aperture 54 in the pipette of the distribution head is detected by measuring changes in the electrical resistance across the aperture between electrodes 56 and 62. Preferably this is achieved by applying a current to the aperture by means of a constant current source 126, as shown in FIG. 8, and monitoring the voltage across the aperture. Alternating current is preferred in order to avoid the effects of polarization. The passage of a bead through the aperture results in an increase in the resistance across the aperture manifested by an increase in the voltage measured across the aperture. The voltage variation is depicted in FIG. 10, in which the voltage level remains essentially constant except when a bead passes through the aperture, at which time a voltage peak 128 appears. The peak is detected in the control unit and used to produce a signal to stop the operation of actuator 98 and pump 104.
As will be apparent from the description, the apparatus reliably selects individual beads from the mixture and deposits them in wells in the well plates.
Although the flow of liquid through aperture 54 is stopped almost immediately when the passage of a bead through the aperture is detected, occasionally, more than one bead will pass through the aperture into the pipette. The accidental passage of multiple beads through the aperture will be detected by the control system as a series of voltage peaks, and the control system responds by causing the distribution head to remain over the waste collector 25 while the beads are flushed out of the pipette. These beads can be reintroduced into the cup-shaped vessel 26 for later distribution. Waste liquid is delivered to a closed container 122, and a vacuum is drawn continuously on the waste collector 25, through container 122, by pump 120.
In the alternative embodiment shown in FIG. 11, a suspension of beads 130 is established in a vessel 132. The vessel comprises a cylinder 134 having a top closure 136 and a bottom closure 138. The top closure has a bottom face 140 in the form of a symmetrical cone. A fluid inlet is provided at 142, and an air outlet 144 at the peak of the cone has a filter 146. The bottom closure 138 has its top face 150 in the form of an asymmetric cone with an emptying port 152 provided with a valve 154.
A metal tube 158 extends upward through the bottom closure 138 to a location within the cone defined by bottom face 140 of the top closure. The tube is coaxial with that cone and has an opening 160 at its upper end for receiving beads along with liquid from the suspension 130. The beads are maintained in suspension by a magnetic flee 162 operated by an external magnetic stirrer 164.
The cone tends to concentrate beads at the location of the end opening 160 of tube 158, and beads enter the tube 158 along with liquid.
The lower part of tube 158 extends through the bottom closure 138 of the vessel 132, and into an insert 164 of PTFE or other similar material which is not electrically conductive. The insert fits into the upper end of a passage 166 in a metal block 168, and tube 158 extends into the insert to a location near, but spaced from the lower end of the insert. The lower end of the insert has an opening 170, having a diameter equal to the internal diameter of the tube 158 so that the tube and opening 170 form a continuous, smooth passage for the flow of liquid and beads.
The exterior of the lower end of insert 164 is narrower than the portion of passage 166 surrounding it, thereby providing an annular space 172 for the flow of liquid received through a passage 174. The liquid introduced through passage 174 flows past the tip of insert 164, downwardly through a tapered part 176 of passage 166, and outwardly thorough an exit opening 178. The tip of the insert and the passage 166 are gradually tapered and shaped so that the flow past the tip of the insert is laminar.
The flow of liquid through passage 174 draws beads individually from the tip of insert 164 and delivers them into the upper part of passage 178, which serves as a collection chamber, from which they can be deposited in an array through opening 180. A solenoid-operated valve 182, located above opening 180, is movable in a direction perpendicular to the plane of the drawing to permit or block flow through opening 180. This valve is shown in its closed condition. A branch 184, communicating with passage 178, is provided with a similar solenoid-operated valve 186, which is shown in its opened condition. The valves 182 and 186 are provided with hollow internal passages through which liquid can be caused to flow for washing the passages 178 and 184.
In the apparatus of FIG. 11, the tube 158 serves as one of two electrodes, and block 168 serves as the other electrode. Passage of a bead through opening 170 effects a change in the electrical resistance measurable between tube 158 and block 168 in the same manner in which a bead passing though aperture 54 in FIG. 4 affects the resistance measured between electrodes 56 and 62. In the absence of an electrical signal produced by the passage of a bead through opening 170, valve 182 is closed and valve 186 is open, allowing liquid entering the block 168 through passage 174 to flow to waste through branch 184. The electrical signal produced in response to the passage of a bead controls the operation of valves 182 and 186 in such a way that valve 182 opens momentarily and valve 184 closes. The time delay between the detection signal and the operation of the valves is set in relation to velocity of movement of beads in the space below the tip of tube 158, so that valve 182 opens and valve 186 closes precisely at the time that the detected bead is in close proximity to the connection of the branch 184 to passage 178. The operation of the valves allows beads to be deposited individually into a suitable array, for example into wells in a microtitre plate.
In the apparatus of FIG. 11, the fluid introduced through passage 174 serves as a sheath fluid, and may be the same as the suspension fluid passing downwardly through tube 158 from vessel 132. The sheath fluid flows in the same direction in which the beads move through tube 158. Preferably, the suspension fluid and the sheath fluid flow through passage 178 in laminar flow, i.e. in substantially non-mixing layers respectively of the suspension fluid and the sheath fluid. Such laminar flow helps the beads to flow through passage 178 along a substantially straight path the sheath fluid also helps to even out the flow of beads and assists in achieving suitable serial separation of beads. The sheath flow may be controlled to optimize the flow of beads through passage 178.
Various modifications can be made to the apparatus and process described. For example, by incorporating an electronic counter in the control unit, it is possible to count electrical peaks and disable the syringe actuator only after a predetermined number of peaks is counted. In this way, if desired, a preselected number of beads can be deposited in each well. The control system can be programmed to cause the beads in the pipette to be flushed into the waste collector if the number of beads passing through the aperture into the pipette exceeds the preselected number.
The pipette (with its aperture 54) can be readily removed for cleaning, or for replacement by another pipette having a different aperture. It is possible to eliminate the jewel 52 altogether, and thereby avoid the potential problems resulting from detachment of the jewel from the pipette. This can be done by forming the aperture directly in the wall of the pipette, provided that the wall thickness is sufficiently small.
In still another modification of the apparatus, openings are provided at the bottoms of the wells in the well plates, and filters are situated in the openings. A vacuum head is situated underneath the path of the distribution head and engageable with the undersides of the well plates. A vacuum is drawn continuously though the vacuum head, and is used to remove liquid form the wells. This keeps the wells from overflowing, and is an alternative to the previously described withdrawal of liquid from the upper end of the pipette at the same rate at which it enters the pipette through aperture 54.
In the embodiment of FIG. 11, various alternative valves and flow passage configurations can be used, and fluidic control can be utilized to divert the flow of liquid from one passage to another.
Still other modifications can be made to the apparatus and process without departing from the scope of the invention as defined in the following claims. | Substrate beads for combinatorial synthesis are selected individually from a mixture by suspending the mixture in an electrically conductive liquid, in a bead selection vessel, causing the liquid to flow at a controlled rate through an aperture in the side wall of a pipette extending through the vessel, and detecting the passage of a bead through the aperture by monitoring an electrical resistance across the aperture. In an alternative embodiment, beads are passed through a tube into a collection passage in which a continuous laminar flow takes place. Detection takes place at the tip of the tube, and, in response to the detection of a bead, the flow through the collection passage is diverted to cause the bead to be deposited. In both cases, the selected bead is deposited into a well of a plate having rows and columns of wells in a rectangular array, while a vacuum is drawn through a filter in the bottom of the well. The bead selection head is moved from well to well in each column, and the well plate is indexed to position the columns successively underneath the path of the bead selection vessel. A plate handling mechanism retrieves plates from a supply stack, moves them laterally underneath the bead selection vessel, and elevates them into another stack. | 1 |
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application is a continuation of co-pending U.S. patent application Ser. No. 13/195,744, filed on Aug. 1, 2011, the entirety of which is incorporated herein by reference.
FIELD
[0002] The disclosure pertains to devices and methods for storing and dispensing fluids. More particularly, the disclosure pertains to a flexible hair color bottle for mixing and applying fluid hair color chemicals using an asymmetric, bi-directional valve assembly.
BACKGROUND
[0003] The success of a hair color treatment depends on safe and controlled application of chemical dyes in a timely manner. Such chemical dyes, especially fluids, or those that contain volatile components such as solvents, may be allergenic, irritating, or even toxic if handled incorrectly. In addition, chemical dyes of the type used in hair color products can leave permanent stains if they are spilled on clothing, furniture, countertops, or floors. Moreover, skin can become stained or irritated if the color is allowed to make contact with bare skin for prolonged periods.
[0004] Hair color products are typically packaged with detailed application instructions, but it is often left up to the professional hair colorist to assemble the necessary tools for applying the product safely and consistently. For example, some instructions direct the user of the product to mix chemicals in a glass or plastic container, and to apply the chemical with a brush. If an open container such as a color bowl is used, product may be lost to evaporation and the resulting fumes may be unpleasant or even unsafe. Hair products intended for consumers are generally packaged with a color bottle or other application tools along with hair color (dye) and developer (peroxide). Consumers at home may be supplied a brush that is attached to the hair bottle to create lighter streaks in the hair or to retouch grey roots. While application with a brush typically permits better control and is appropriate for salon applications, brush application is difficult for consumers and home users of hair color almost always use a bottle having a short cone for product delivery.
[0005] The success of a hair color treatment relies on the precision of the application to the areas of the hair one desires and the speed at which one can apply the color. The color/dye is stored in a separate container from the developer/peroxide which activates the color when the two are mixed together. The dye and peroxide solutions are mixed immediately before application and as soon as the developer and color are mixed, a chemical process begins that changes the quality of the finished product. As the mixed product ages, it becomes more oxidized and less effective. In products intended to lighten hair color, the capability of the product to lighten decreases as the mixed product ages. Products intended to darken hair color, produce darker, muddier, and less attractive hair color as the mixed product ages. Consequently, the speed at which the product is applied can determine the quality of the resulting hair color. The degradation of the dye/peroxide mixture is especially problematic for home consumers who typically must rapidly, accurately, and uniformly apply the mixture to their own hair to produce satisfactory results.
[0006] Some hair color products are shipped with a small squeeze bottle having a screw cap closure with a simple cone-shaped nozzle that must be inverted to apply the product. Such a method of delivery is cumbersome for self-use, slows the delivery process, and is prone to leakage and spills. Furthermore, after initially squeezing the bottle, and upon release of manual pressure, a one-way nozzle tends to suck product back into the bottle while the air pressure is equilibrating, thus interrupting continuous flow of product during application. Also, in the case of fluids of higher viscosity or gels, some product inevitably remains in the bottom of the bottle and is wasted.
[0007] In general, fluid chemicals such as cleaning fluids or laboratory chemicals are often packaged and sold in, or may be mixed and stored by a user in, flexible squeeze bottles made from a soft, high density polyethylene. Some laboratory squeeze bottles have a wide mouth that is easy to fill, and that is covered by a screw cap having a conical tapered polypropylene nozzle coupled to a tube (pickup tube) that extends into the fluid reservoir. The tapered nozzle provides a simple way either to control the application of fluid chemical, or to use the chemical as a wash. The user controls the amount of fluid dispensed by simply squeezing the flexible bottle. Such bottles are, however, prone to dripping and chemical evaporation in response to changes in ambient air temperature and barometric pressure. Also, they must be maintained in an upright position, or the fluid will simply spill out of the dispensing cap. What is needed for safe and effective application of hair color products is a hair color delivery system suitable for mixing and storing the product in a closed container, and for applying the hair color in a continuous and controlled manner in either a salon setting or at home.
[0008] Existing vented squeeze bottle valves (for example, annular valves of the type commonly used for sports drinks or condiments) typically exhibit axial or rotational symmetry so that outside air passes through the cap around the perimeter of the dispenser as fluid chemical is squeezed out of the dispenser. Conventional dispensing bottles include those disclosed in U.S. Pat. No. 5,125,543 to Rohrbacher, U.S. Pat. No. 4,133,457 to Klassen, and U.S. Pat. No. 4,408,702 to Horvath, U.S. Pat. No. 4,474,314 to Roggenburg and U.S. Pat. No. 4,747,518 to Laauwe.
SUMMARY
[0009] The present disclosure concerns hair color bottled equipped with dispensing caps containing a bi-directional valve assembly that lacks axial or rotational symmetry.
[0010] A hair color delivery system includes a flexible bottle, a dispensing cap having a tapered nozzle, an asymmetric bi-directional valve assembly situated between the flexible bottle and the dispensing cap, and a tube having a proximal end coupled to the valve and a distal end that extends into the flexible bottle. The dispensing cap is secured to the mouth of, and preferably seals, the flexible bottle, for example, by a threaded closure and using a portion of the valve assembly as a gasket situated between the bottle mouth and the dispensing cap.
[0011] According to some examples, asymmetric bi-directional valve assemblies used to dispense fluid from within a container include a platform for covering an opening to the container, an exit valve comprising a first tapered extension in the platform, and a first aperture through which fluid may be expelled from the container in an outward direction along a first axis, and an input valve comprising a second tapered extension in the platform, preferably opposing the first tapered extension, and a second aperture through which ambient air may enter the container in an inward direction along a second axis. The first and second axes are offset, or spaced apart, from each other, so that the valves are not co-axial. The tapered extensions are preferably in the shape of circular or flattened cones, having top openings that may be circular or linear slits, respectively.
[0012] Representative methods of substantially continuous delivery of a fluid to a target area include the steps of providing a flexible bottle, at least partially filling the flexible bottle with the fluid, expelling fluid from the flexible bottle, in response to application of external pressure on the flexible bottle by directing the fluid through a first tapered extension, dispensing the fluid to the target area through a tapered nozzle, and permitting air to enter into the flexible bottle through a second tapered extension spaced apart from, and opposing, the first tapered extension, so as to adjust internal and external pressures on the flexible bottle, thereby maintaining a supply of fluid in the tapered nozzle. When the fluid is a hair coloring agent, delivery of the coloring agent as disclosed results in a safe and effective hair color treatment.
[0013] There are many advantages of the disclosed methods and the disclosed systems. For example, it is easy and safe to accurately self-apply the hair color, while holding the bottle upright to reduce the chance of drips or spills. The tapered nozzle stays fully charged with product because, due to the bi-directional valve assembly, the tapered nozzle does not admit air when pressure is removed from the bottle. An opaque, closed bottle protects chemical from light and evaporation, and has a stylish appearance for use in salons. Such a bottle also protects the color product from exposure to air. A tapered nozzle also acts to cleanly part the hair, and may be used to spread the product along hair shafts. In other examples, transparent or translucent materials are used. Finally, the tube ensures that chemical remaining at the bottom of the bottle is accessible, to reduce waste.
[0014] The foregoing and other features, and advantages of the invention will become more apparent from the following detailed description, which proceeds with reference to the accompanying figures.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] FIG. 1 is a pictorial side elevation view of a stylized representative example of a hair color bottle showing interior parts, including a hollow dispensing tube, a dispensing screw cap assembly that includes a tapered nozzle, and an asymmetric bi-directional valve assembly.
[0016] FIG. 2 is an exploded view of the hair color bottle of FIG. 1 .
[0017] FIG. 3 is a top plan view of the dispensing screw cap assembly shown in FIGS. 1-2 .
[0018] FIG. 4 is a side elevation view of the dispensing screw cap assembly shown in FIGS. 1-3 .
[0019] FIG. 5 is a bottom perspective view of the dispensing screw cap assembly shown in FIGS. 1-4 .
[0020] FIG. 6 is a perspective view of the asymmetric, bi-directional valve assembly shown in FIGS. 1-2 .
[0021] FIG. 7 is a bottom plan view of the asymmetric bi-directional valve assembly shown in FIG. 6 .
[0022] FIG. 8 is a schematic cross-sectional view of the asymmetric bi-directional valve assembly shown in FIGS. 6-7 .
[0023] FIG. 9 is a bottom plan view of a representative asymmetric bi-directional valve assembly in which end slits of opposing outward and inward tapered extensions are perpendicular with respect to one another.
[0024] FIG. 10 is a bottom plan view of a representative asymmetric bi-directional valve assembly in which end slits of opposing outward and inward tapered extensions are parallel and along a common axis.
[0025] FIG. 11 is a flow diagram showing steps in a method of substantially continuous delivery of fluid to a target area.
DETAILED DESCRIPTION
[0026] As used in this application and in the claims, the singular forms “a,” “an,” and “the” include the plural forms unless the context clearly dictates otherwise. Additionally, the term “includes” means “comprises.” Further, the term “coupled” does not exclude the presence of intermediate elements between the coupled items.
[0027] The disclosed systems, devices and methods described herein should not be construed as limiting in any way. Instead, the present disclosure is directed toward all novel and non-obvious features and aspects of the various disclosed embodiments, alone and in various combinations and sub-combinations with one another. The disclosed systems, devices, and methods are not limited to any specific aspect or feature or combinations thereof, nor do the disclosed systems, devices, or methods require that any one or more specific advantages be present or problems be solved. Any theories of operation are to facilitate explanation, but the disclosed systems, devices, and methods are not limited to such theories of operation. The disclosed hair color delivery system is furthermore not limited to use with hair color chemical or health and beauty products. The terms “fluid,” “chemical,” “hair color,” and “coloring agent” are meant to encompass fluids, water, mixtures, gels, slurries, pastes, and other flowing substances that may be ejected from a container by means of pressurization. The examples below are described with reference to hair colorants, but the disclosed apparatus can be used to dispense other materials as well.
[0028] According to some examples disclosed herein, a color bottle is provided for use as held in an upright position. Such an upright bottle can allow the person applying hair treatment products greater visibility and access to hard to reach areas, permitting easier application. Constant flow of color product through a delivery nozzle can provide consistent product flow, permitting more precise application. A two-way valve allows product to be applied more quickly with better results because there is no pause to allow air to depart from the chamber that retains the color product. A long tapered nozzle allows the user to cleanly part the hair before squeezing the color along the root line, and reach difficult areas more readily. In addition, the shaft of the nozzle may also be used as a tool to spread the product along the hair shaft. With such color bottles, the average home consumer may be able to reduce application time on their hair color and achieve greater accuracy. Because the color product can be less oxidized with the improved application speed that the disclosed methods and apparatus can provide, hair color results can be improved. More measured, precise application also reduces product dripping and mess, providing a more satisfactory consumer experience. The examples below pertain to a color bottle with a single nozzle assembly, but additional nozzles (such as interchangeable nozzles) can be provided as well.
[0029] With reference to FIGS. 1-2 , a representative example of a stylized hair color delivery system 100 is configured to facilitate directing and controlling the application of hair color products. Delivery system 100 comprises a flexible bottle 102 , a dispensing screw cap assembly 104 , and an asymmetric bi-directional valve assembly 106 that attaches to a proximal end 107 of a hollow delivery tube 108 having a distal end 110 that extends into the bottle 102 . According to a representative example, the bottle 102 has a circularly cylindrical shape that may feature tapered shoulders 112 and a tapered base 114 . However, the shape of the bottle 102 generally does not influence utility of the delivery system 100 and therefore containers such as the bottle 102 can be provided in arbitrary shapes. Embodiments of the bottle 102 are characterized by their flexibility, and in particular their elastic flexibility, so that when the bottle 102 is deformed by application of external pressure, the bottle 102 recovers from the compression and can return to an original shape, or at least partially return towards an initial shape or volume. Suitable elastic materials for the bottle 102 include but are not limited to low-density polyethylene-type materials commonly used for squeeze bottles. The volume capacity of the bottle 102 may reasonably be, but is not limited to, a range of volumes up to about 1 liter, wherein smaller bottles might preferably be packaged with hair color products for end user consumers, and larger bottles might preferably be sold to professional colorists or salons. Unlike conventional chemical wash bottles that are typically transparent or translucent, stylized hair color bottle 102 is preferably opaque, and available in a variety of designer colors and textures, with or without labels or indicia. However, the bottle 102 can be transparent or translucent.
[0030] Dispensing screw cap assembly 104 preferably features a tapered nozzle 115 for directing the release of hair color chemical contained in the bottle 102 and is configured to be coupled to the dispensing tube 108 . The tapered nozzle 115 is shown as part of the screw cap assembly and can be formed in a molding process with other portions of the screw cap assembly 104 , but in other examples, the tapered nozzle 115 can be a separate piece that is secured to the screw cap assembly 104 . The bottle 102 preferably has a threaded mouth 116 for accommodating corresponding threads 118 on the screw cap assembly 104 . The bottle mouth 116 has a circular cross section that fits the interior threads 118 that can be molded into an inside surface 120 of the screw cap assembly 104 . The screw cap assembly 104 may have an outer perimeter 122 of arbitrary shape, for example, egg-shaped as shown in FIG. 2 . Furthermore, the top surface 124 of the screw cap assembly 104 may be horizontal or tilted from horizontal with the bottle 102 in an upright position, and sides 126 of the screw cap assembly 104 may be vertical or tilted with the bottle 102 in an upright position, and the sides 126 can be straight or curved. As shown in FIG. 2 , apertures 127 , 128 , 129 are provided in the screw cap assembly. The aperture 128 permits gas flow in and out of the bottle 102 so as to manage pressure adjustment in the bottle 102 . The apertures 127 , 129 are configured to receive corresponding protrusions 127 A, 129 A in the valve assembly 106 so as to prevent or impede rotation of the valve assembly 106 as the dispensing cap assembly 104 is secured to the bottle 102 . The aperture 128 is generally configured to admit air to the bottle 102 .
[0031] With reference to the exploded view of delivery system 100 of FIG. 2 , the valve assembly 106 is situated between the flexible bottle 102 and the screw cap assembly 104 . The valve assembly 106 comprises a disc-shaped platform 200 , an exit valve 202 configured to extend into the screw cap assembly 104 and an input valve 204 configured to extend into the bottle 102 . The disc-shaped platform 200 may be sized to substantially match the size of the opening of mouth 116 , so that platform 200 is secured to the mouth 116 of bottle 102 preferably forming a seal between the bottle 102 and the screw cap assembly 102 . The platform 200 preferably is formed of an elastic material so as to serve as a compliant gasket.
[0032] FIGS. 3-5 illustrate additional features of the screw cap assembly 104 . In the top plan view shown in FIG. 3 , the shape of the outer perimeter 122 is visible, as are the positions of the aperture 128 that is provided to admit air or other gas into the bottle 102 when the bottle recovers from compression. The aperture 128 is situated to be coupled to the input valve 204 and the apertures 127 , 129 are configured to receive protrusions 127 A, 129 A on the valve assembly. The screw cap assembly 104 preferably includes tapered nozzle 115 as a fixed portion of the assembly, and the nozzle 115 typically includes a tapered segment 300 , a tip segment 301 , and an elbow segment 302 . As shown in FIG. 4 , the elbow segment 302 is preferably bent at an elbow angle 400 that exceeds 90 degrees so that, when the delivery system 100 is held upright, hair colorant or other product can be dispensed in a convenient direction. For delivery of hair colorant products, horizontal delivery or delivery at a slight upward angle with respect to horizontal is convenient. Typical upward angles from the horizontal are in ranges from 0 degrees to about 30 degrees, such as 0 to 30 degrees, 0 to 10 degrees, or 0 to 5 degrees. The elbow angle 400 can be selected so that an upward delivery angle of 5-45 degrees is provided with the bottle 102 held upright. This arrangement permits convenient dispensing.
[0033] The sectional view of FIG. 4 shows the interior structure of the screw cap assembly 104 , specifically, the degree of taper along the length of nozzle 115 , and the degree of taper within the tip segment 301 , where hair colorant product or other materials exit the delivery system 100 for application to a target area. The screw cap assembly 104 includes a hollow space 402 for receiving the threaded mouth 116 of the bottle 102 . Referring to the bottom perspective view of FIG. 5 , the screw cap assembly 104 also includes an aperture 500 at which elbow segment 302 joins screw cap assembly 104 and configured to receive the exit valve 202 .
[0034] A magnified perspective view in FIG. 6 illustrates details of a representative embodiment of the asymmetric bi-directional valve assembly 106 . Each of the two valves, exit valve 202 and input valve 204 , is formed by an aperture in platform 200 and a corresponding tapered extension. For example, the input valve 204 is formed by the intake aperture 128 and an inward tapered extension 601 , and the exit valve 202 is formed by an exit aperture (not visible in the view of FIG. 6 ) and an outward tapered extension 602 . The exit valve 202 includes an outward tapered extension 602 that extends along a first axis 604 to linear end slit 605 in an exit surface 606 . The exit surface 606 is configured to direct fluid from the hollow tube 108 into the tapered nozzle 115 . The slit 605 is configured to open in response to a positive pressure applied to the interior of the exit valve 202 and otherwise to remain substantially closed. Typically, the exit valve 202 is formed of a flexible, elastic material that is responsive to slight pressure provided by compression of the bottle 102 . A lower portion 607 of exit valve 202 is configured to attach snugly to the proximal (top) end 107 of the tube 108 . The exit valve 202 also includes a reinforcing collar 608 that extends outward form the platform 202 and is coupled to the outward tapered extension 602 .
[0035] As shown in FIG. 6 , the tapered extension 602 of the exit valve 202 includes opposing flat surfaces such as surface 603 A and curved or cylindrical surfaces such as surface 603 B. Surfaces such as the surface 603 A generally taper from the platform 200 to the exit surface 605 so that the exit surface 605 is approximately rectangular. Curved surfaces such as the surface 603 B can be similarly tapered. A taper angle and overall length of the tapered extension 602 can be selected as convenient, and generally so as to be accommodated by the elbow segment 302 of the nozzle 115 . If desired, an external diameter of the reinforcing collar 608 is selected to seal to the nozzle 115 as secured to the bottle 102 .
[0036] Similarly, the input valve 204 is typically configured to admit air from outside the bottle 102 via the air intake channel 600 through an inward tapered extension 601 that extends along and is tapered with respect to a second axis 609 which is offset from the first axis 604 . The axes 609 and 604 are typically but not necessarily parallel. Accordingly, the tapered extensions 601 and 602 are generally oppositely directed, but they need not be anti-parallel. Entry of air into the bottle 102 through the narrow linear end slit 608 tends to equalize internal and external air pressures exerted on bottle 102 , and maintains a headspace above the fluid reservoir within bottle 102 . To prevent or reduce twisting or rotation of valve assembly 106 in the attachment of the screw top assembly 104 to the bottle 102 , the valve assembly 106 includes the protrusions 127 A, 129 A that are configured to be inserted into corresponding apertures 127 , 129 in the screw top assembly 104 . The valve assembly 106 is preferably made of silicone or of a similar flexible elastic, chemically inert material. In some examples, the valve assembly is formed as a single piece in a molding or other process. Alternatively, input and exit valves and a suitable gasket platform can be formed separately, and retained in a suitable configuration as attached to a bottle. Input and exit valves can have the same dimensions, or can be different. Typically, neither of the valves is centered with respect to an axis of the bottle as assembled, but, if convenient, an input or exit valve can be centered.
[0037] In FIG. 7 , a bottom plan view is presented, showing the various openings in the underside of disc-shaped platform 200 that supports the valve assembly 106 . The orientation of slits 605 and 610 is understood to be substantially parallel in this representative example. An air intake channel 600 may have a different circumference than the circumference of the base of tapered extension 202 .
[0038] Referring to FIG. 8 , a cross-section of valve assembly 106 is shown, highlighting further structural asymmetries between exit valve 202 and input valve 204 . FIG. 8 shows internal dimensions of the valves 202 and 204 relative to a first tip cavity 800 and a second tip cavity 802 , respectively, that comprise valve passageways through which fluids such as hair colorants or gases such as air move in response to compression and relaxation of the bottle 102 . The volume of the tip cavities 800 , 802 can be based on desired dispense pressures or volumes, bottle sizes, or different dispense material viscosities. According to one embodiment, walls 822 , 824 of the valves 202 , 204 , respectively, meet at a junction 808 , the location of which does not coincide with the platform 200 . As shown in FIG. 8 , the thickness of the wall 822 of the valve 202 at the reinforcing collar 608 is preferably greater than that a thickness of the wall 824 of the valve 204 . The thickness of the wall 822 of the valve 202 at the reinforcing collar 608 is generally non-uniform, tapering so as to become thinner from the junction 808 in both directions. The reinforcing collar 608 also elevates the base of the outward tapered extension 602 of the valve 202 above the platform 200 whereas the location of the base of inward tapered extension 601 of the valve 204 coincides with platform 200 .
[0039] In general, valve assemblies may include a pair of opposing tapered extensions of arbitrary relative orientation. Referring to FIGS. 9-10 , additional exemplary alternative embodiments of valve assemblies are shown in which pairs of opposing tapered extensions have different orientations. For example, according to one alternative embodiment shown in FIG. 9 , a valve assembly 900 includes a first valve 902 and second valve 904 that include slits 903 , 905 , respectively, that are configured to control fluid flow. The slits 903 , 905 extend along perpendicular axes 908 and 910 , respectively. The valves 902 , 904 extend from a compliant platform 906 that can serve as a gasket. The valve 902 includes a tapered extension 912 having flat surfaces 912 A, 912 B that taper from the platform 906 to the slit 903 and curved tapered surfaces 912 C, 912 D. The valve 904 can be similarly constructed, and the valve assembly 900 can be formed as a single molded part, or constructed of separated valves and gasket.
[0040] An alternative representative valve assembly 1000 is illustrated in FIG. 10 . The valve assembly includes a gasket base 1002 configured to provide a seal between a color bottle and dispensing cap. Valves 1004 , 1006 are provided for delivery of a product such as a hair color product from the bottle and admission of air to the bottle. The valve 1004 includes a tapered portion 1008 having an approximately circular cross section at the gasket base and a substantially rectangular cross-sectional area at an exit surface 1010 . In some examples, portions of tapered extensions that define valves retain some curvature at the exit surface. For convenience, surfaces such as the exit surface 1010 are referred to as substantially rectangular as any curvature in shorter sides increase surface perimeter by less than about 20%, 10%, or 5% and when viewed, tend to appear rectangular.
[0041] As shown in FIG. 10 , sidewall sections 1011 A- 1011 B of the valve 1004 correspond approximately to portions of a conical surface, while sidewall sections 1012 A- 1012 B are defined by flat surfaces that taper to the exit surface 1010 . The sidewall sections 1011 A- 1012 B can be formed of a flexible material having a constant or variable thickness, and are conveniently formed in a molding process that includes formation of the gasket base 1002 . The valve 1006 can be similarly constructed, and in the example of FIG. 10 , includes an exit slit and exit surface 1005 situated along a common axis 1020 with the exit surface 1010 . For convenient illustration, exit slits in the valve exit surfaces are not shown in FIG. 10 . Typically two valves and the gasket base 1002 are formed as a single molded part, but one or more or all can be formed separately by a molding or other fabrication process and secured as needed.
[0042] Slits in the exit surfaces 1010 , 1005 permit fluid passage in response to a pressure difference between a pressure at the gasket base and at the exit surfaces. The valves are formed of a suitable flexible, elastic material so that such a pressure difference causes the slit to open and then to close when the pressure difference is removed. A slit length and exit surface area can be selected so as to permit ready delivery of a hair color product or other material in response to pressures available upon hand compression of a squeeze bottle. The valve assembly 1000 can also include a cylindrical extension (not shown in FIG. 10 ) that is configured for coupling to a tube that extends into a bottle to receive a hair color or other product. However, such an extension can be omitted, and the tube coupled directly to the gasket base 1002 .
[0043] The representative valve assembly 1000 is shown as a flattened, cylindrical taper, but other shapes can be used. For example, a conical taper can be used, and a circular exit surface can be provided with a rectangular slit for fluid passage. Other exit surface treatments can also be used in which exit surface can provide an aperture for fluid passage in response to pressure and remain sealed in the absence of pressure. In addition, a slit or other prospective exit surface opening need not be centered in the exit aperture, and the exit aperture need not be centered with respect to an input aperture.
[0044] As shown in the examples, the bottle cap and a delivery tube are of one piece, unitary construction, but other arrangements can be used. For example, a bottle cap can be provided with one or more apertures to be fluidically coupled to a delivery tube that is provided as a separate part and, for example, retained against the gasket when the cap is secured to the bottle.
[0045] In the examples above, fluid delivery is via a rectangular slit aligned on a rectangular exit surface, but in other examples, exit slits can be provided on circular, ovoid, polygonal exit surfaces or exit surfaces of other shapes.
[0046] With reference to FIG. 11 , a representative method 1100 by which a user may achieve substantially continuous delivery of a fluid to a target area includes a step 1102 in which a flexible bottle is provided. In a step 1104 , the bottle is at least partially filled with a fluid to be dispensed. At 1106 , a user positions the bottle so that a fluid delivery nozzle tip is situated at a suitable location (for example, a location at which hair colorant is to be applied). The bottle can be held substantially upright and external pressure is applied to the bottle at 1108 so as to expel fluid from the bottle. At 1112 , pressure can be released from the bottle so as to admit air into the bottle while retaining the fluid to be dispensed in the fluid delivery nozzle, even at the tip of the nozzle. If additional fluid such as hair colorant is to be applied, steps 1106 - 1112 can be repeated until the supply of fluid is exhausted or until selected areas are treated. The method 1100 applies generally to delivery of a fluid to a target area, for example, as an improvement in applications in which conventional squeeze bottles are used (e.g., food service, laboratory chemical use, and the like). In a specific example, the method 1100 provides steps by which a consumer can safely and effectively apply hair colorant with uniform delivery of a coloring agent without having to refill a dispensing nozzle every time a bottle is fully compressed and is allowed to return to its uncompressed shape.
[0047] In view of the many possible embodiments to which the principles of the disclosure may be applied, it should be recognized that the illustrated embodiments are only preferred examples and should not be taken as limiting the scope of the disclosure. We therefore claim all that comes within the scope and spirit of the appended claims. | A hair color delivery system includes a flexible bottle, a dispensing cap having a tapered nozzle, an asymmetric bi-directional valve assembly, and a dispensing tube. The valve assembly comprises a platform, and a pair of valves, comprising tapered extensions through which fluid may be expelled from the bottle and ambient air may enter the bottle. The valves are offset from each other so that they are not co-axial or rotationally symmetric. The delivery system enables a method of substantially continuous delivery of a fluid chemical, yielding a hair treatment that it is easy and safe to use in which the tapered nozzle stays fully charged with product as air can be admitted to a dispensing bottle through a different valve than that used for dispensing. | 0 |
CROSS-REFERENCE TO RELATED PATENT APPLICATIONS
[0001] The present disclosure is a continuing application of and claims the benefit of commonly-owned, co-pending U.S. patent application Ser. No. 12/7636,444 filed Dec. 11, 2009, the entire contents and disclosure of each of which is expressly incorporated by reference herein as if fully set forth herein.
BACKGROUND
[0002] The present invention is related generally to hierarchical organization of an entity's merchandise, i.e., product/inventory, and more specifically, to a method and system for merchandise hierarchy refinement by incorporating product correlation. More specifically, the present invention relates to a method and system of incorporating product correlation information discovered in customers' shopping profiles (records) to adjust an existing merchandise hierarchy with a constraint on the consistency with the existing hierarchy.
[0003] Merchandise hierarchy is a tree-like structure for organizing merchandise categories and products of an entity, e.g., a product wholesaler/retailer. It plays a key role in the business decision-making process. First, merchandise hierarchy is the base of management and operation structure: departments are usually organized according to the merchandise hierarchy and are responsible for all business related but sub-categories and products under the category, e.g., procurement, forecasting, shelf layout, etc. Moreover, merchandise analytics at levels defined in the hierarchy are the basis of business strategy adjustment, such as statistics, reporting, performance evaluation, etc.
[0004] Currently, there is no mechanism for incorporating customers' shopping behavior (e.g., a shopping profile or history) in such merchandise analytics. Such information is useful to facilitate improvement of the business structure and make it truly customer-oriented.
SUMMARY
[0005] The present invention is a system and method for refining an entity's merchandise hierarchy, particularly by generating a more comprehensive merchandise hierarchy for an entity (e.g., a product retailer or wholesaler) that incorporates information representing the shopping behavior of customer(s).
[0006] According to one aspect of the invention, there is provided a method of merchandise hierarchy refinement comprising: extracting first data representing a predetermined merchandise hierarchy and second data representing transaction records having a plurality of transactions related to a plurality of products; clustering the plurality of products based on the plurality of transactions; and updating the predetermined merchandise hierarchy representation based on the clustering, wherein a program using a processor unit performs one or more of the extracting, clustering and updating.
[0007] Further to this aspect of the invention, the step of clustering comprises: setting a current level of the merchandise hierarchy as a bottom level of the merchandise hierarchy, initializing a new membership matrix to an existing membership matrix; applying a Genetic Algorithm to minimize an objective function, wherein in each step of the Genetic Algorithm, a new generation group of the new membership matrix satisfies a consistency constraint; repeating the initializing and applying at a next upper level of the current level until a next highest level of the merchandise hierarchy is reached; and outputting the new membership matrix.
[0008] The comprehensive merchandise hierarchy helps to improve the business structure and make it truly customer-oriented which will, in turn, increase customer's satisfaction, improve operational efficiency, and reduce the cost of management.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] The accompanying drawings are included to provide a further understanding of the present invention, and are incorporated in and constitute a part of this specification. The drawings illustrate embodiments of the invention and, together with the description, serve to explaining the principles of the invention. In the drawings,
[0010] FIG. 1 illustrates an overview of the system and method for merchandise hierarchy refinement according to a preferred embodiment of the present invention;
[0011] FIG. 2 illustrates an example of a predefined merchandise hierarchy;
[0012] FIG. 3 illustrates an example of a transaction record data table;
[0013] FIG. 4 illustrates an example of the refined merchandise hierarchy based on the transaction record data illustrated in FIG. 3 , according to one embodiment; and
[0014] FIG. 5 illustrates the flow chart for the method for the merchandise hierarchy refinement; and,
[0015] FIG. 6 illustrates an exemplary hardware configuration for implementing the flow charts depicted in FIGS. 1 and 5 according to one embodiment of the present invention.
DETAILED DESCRIPTION
[0016] FIG. 1 illustrates an overview of a system and computer-implemented method 100 for merchandise hierarchy refinement according to a preferred embodiment of the present invention. In the system 100 , there is employed at least three processing modules: a data extraction module 101 , a cluster model with consistency constraints module 102 , and a merchandise hierarchy updater module 103 .
[0017] The data extraction module ( 101 ) receives two data feeds: a first data input 11 for receiving data representing a predefined merchandise hierarchy; and, second data input 12 for receiving customers' transaction records. As will be described, the received customer transaction records are preprocessed by the data extraction module 101 to obtain item similarity.
[0018] The cluster model with consistency restraints 102 performs clustering over the items of each level of merchandise hierarchy by adding consistency restraints based on a ratio of mutual information.
[0019] The merchandise hierarchy updater 103 performs updating of the corresponding items and updating of the links between the corresponding levels of merchandise hierarchy.
[0020] FIG. 2 illustrates an example of a predefined merchandise hierarchy 200 having a tree-like structure that comprises the first data input 11 to the data extraction module ( 101 ). In particular, any common hierarchical tree representation can be input that includes representation of nodes, e.g., with pointers to their children, their parents, or both, or as items in an array with relationships between them determined by their positions in the array is input. For purposes of discussion, the merchandise hierarchy 200 is provided for an example merchandise retail entity, e.g., “J-mart,” which may be a chain of retail stores. The chain J-Mart ( 201 ) is arranged in a hierarchical manner with the top node of the tree 201 indicating the retail entity (chain). The retail entity at the top node is divided into several departments 202 , indicated as child nodes 202 a, 202 b, 202 c. As shown in FIG. 2 , for example, a first child node represents a Shoes department ( 202 a ). Departments in the hierarchy are further divided into classes 203 . For example, as shown in FIG. 2 , the Shoes department ( 202 a ) is further divided into classes including a Men's summer shoes class ( 203 a ). Classes 203 in the hierarchy are further divided into items 204 . For example, Men's summer shoes class 203 a in the hierarchy includes products of merchandise such as the walker shoes ( 204 a ).
[0021] FIG. 3 presents an example of a transaction record data table 300 that comprises the second data input 12 to the data extraction module ( 101 ). FIG. 3 in particular gives the attributes of a transaction record, and these records with attributes are stored into a database or like memory storage structure. The example table includes main attribute columns: Transaction ID ( 301 ) and Merchandise Category ( 302 ). Merchandise Category column 302 includes items or products of the retailer that may have been subject to purchase in particular customers' transactions (indicated by the Transaction ID). For example, the merchandise category shown in FIG. 3 indicates three products: bread ( 303 ), milk ( 304 ) and fruit ( 305 ) for the merchandise category. In the transaction record data table 300 , for each transaction, a ‘1’ entry in the column represents that the product is bought and ‘0’ represents that the product is not bought. Note that the times any two products are bought together are counted as similarities between the two products. In this example table, it can be seen that milk and bread are bought together 2 times, milk and fruit are bought together 2 times, and bread and fruit are bought together 1 time. Intuitively, the more times two products are bought together, the more they complement each other.
[0022] As mentioned, the data extractor module 101 preprocesses the received customer transaction records to generate item similarities, i.e., a similarities count.
[0023] This similarities count data is input to the cluster model with consistency constraints module ( 102 ) in FIG. 1 . The similarities are real numbers without complex data structures, and the manner in which they are calculated is explained in greater detail herein below. The cluster model with consistency constraints ( 102 ) in FIG. 1 performs clustering over products of each level of the merchandise hierarchy by adding consistency constraints based on a ratio of mutual information between the predefined merchandise hierarchy and the refined hierarchy that reflects their difference. Thus, in this phase ( 102 ), the merchandise hierarchy has been refined.
[0024] First, the notations used in the clustering model implemented by the consistency constraints module ( 102 ) are introduced as follows:
[0025] N=number of products (e.g., N i+1 is the number of products of the level i+1 that is determined by predefined merchandise hierarchy);
[0026] M=number of original categories;
[0027] K=number of new categories;
[0028] W={W ij }=N×N similarity matrix;
[0029] D=diag {d 1 , . . . , d N }, where d i =Σ j W ij ;
[0030] C=N×K new member matrix, wherein C i =ith row of C;
[0031] T=existing category labels defined by the existing hierarchy (e.g., Tij=1 whenever product i belongs to category j. Otherwise, Tij=0. The size of matrix T is subject to the existing hierarchy that may be different from the size of C);
[0032] p ij =fraction of sales volume of products in new category i and existing category j;
[0033] p i * =Σ j p ij =fraction of sales volume of products in new category I;
[0034] p* j =Σ i p ij =fraction of sales volume of products in existing category j;
[0000]
H
(
T
)
=
-
∑
j
=
1
M
p
j
*
log
(
p
j
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)
=
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entropy
of
T
;
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(
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=
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i
=
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(
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ij
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i
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j
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=
the
mutual
information
between
C
and
T
;
[0035] Q(C,T)=H(T)/I(C,T)=ratio of mutual information;
[0036] η≧1=control parameter.
[0037] It is understood that data N, M, D, K, W, p, H( ) I( ) Q( )are extracted from the transaction records.
[0038] Using the definitions given above, finding a clustering assignment operation is performed whereby each product is assigned a cluster label, i.e. the output matrix C, such that similar items have similar assignments is tantamount to finding a solution to the new member matrix “C” which satisfies the following objective function:
[0000]
min
∑
i
,
j
=
1
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W
ij
C
i
-
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2
=
trace
(
C
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,
[0039] such that Q(C,T)≧η.
[0040] The objective function which makes use of the complementary information between products means that similar products have similar cluster assignments. A description of a clustering technique that can be used is presented herein below in greater detail.
[0041] The consistency constraint leverages expertise to control the extent of hierarchy change. It can be found that Q(C,T) is minimized to 1 if and only if the sales distributions with the new and existing categories are identical. The higher the confidence level of the predefined merchandise hierarchy, i.e., the confidence level that can be mirrored by parameter η and adopted to only show the degree of belief in the predefined merchandise hierarchy, the smaller the value of η. In practice, the confidence level of predefined hierarchy is determined by tuning the control parameter η which is a presupposed positive constant based on the expertise to predefined merchandise hierarchy (i.e. its confidence level) before clustering. Hence, for a given η the whole bottom-up process is performed once.
[0042] Accordingly, in one embodiment, an optimization algorithm is implemented for the cluster model with the following consistency constraints: Initialization: C=T. The algorithm includes:
1. Applying a Genetic Algorithm (GA) (e.g., see reference to Holland, John H entitled Adaptation in Natural and Artificial Systems, University of Michigan Press, Ann Arbor (1975), incorporated by reference herein) to minimize the objective function. Generally, GA algorithms are implemented in a computer simulation in which a population of abstract representations of candidate solutions to an optimization problem evolves toward better solutions. The evolution usually starts from a population of randomly generated individuals (binary representation) and happens in generations. In each generation (iteration), multiple individuals are stochastically selected from the current population based on their fitness (i.e. the corresponding value of objective function), and modified (recombined and randomly mutated) to form a new population that is then used in the next iteration. Commonly, the algorithm terminates when either a maximum number of generations has been produced, or a satisfactory fitness level has been reached. However, slightly different from the above original GA, in each iteration of the present method, it is demanded that the new generation group of variable C must satisfy the consistency constraints. Hence, in each generation those individuals breaking consistency constraints must be removed. 2. Output the final cluster assignments C, i.e., the matrix C is just the structure output. Cij=1 means product i belongs to category j and otherwise Cij=0. Therefore, the refined merchandise hierarchy may be re-drawn in terms of C such as described herein with respect to FIG. 4 .
[0045] The final cluster assignments C are output to the Merchandise Hierarchy updater ( 103 ) as shown in FIG. 1 , which updates the clustering of the corresponding items according to the result computed by the Cluster Model, and updates the links between the corresponding levels of the merchandise hierarchy such as the merchandise hierarchy 200 shown in FIG. 2 .
[0046] FIG. 4 shows an example of updates 400 performed by the Merchandise Hierarchy Updater module 103 . As shown in FIG. 4 , the original categories in the middle level only included Staple food ( 401 ) and Dairy ( 402 ). After implementing the cluster modeling performed by module 102 , besides two existing categories, a new category ‘Cluster 3 ’ ( 403 ) is generated according to cluster assignments. The new category contains two products bread ( 404 ) and milk ( 405 ) that originally belong to the Staple food ( 401 ) and Dairy ( 402 ) respectively Here, Merchandise Hierarchy Updater performs three things: first, give Cluster 3 a title, e.g. Breakfast ( 406 ) that is in accordance with the meanings of bread and milk and create a new category node Breakfast; second, discard the links from bread to Staple food ( 401 ) and from milk to Dairy ( 402 ), and add links from bread and milk to Breakfast ( 406 ); third, add a link from Breakfast ( 406 ) to its upper level nodes, e.g. create a link from Breakfast to Foodline ( 407 ).
[0047] In summary, a bottom-up strategy to adjust the predefined merchandise hierarchy is adopted. The method implementing the strategy in the Merchandise Hierarchy Updater module 103 is as follows:
1) choose a starting level in the existing hierarchy; 2) sequentially implement the three modules: the data extractor, the cluster model with consistency constraints and the merchandise hierarchy updater; 3) return to perform the second step on the upper category level of the current level; 4) output the refined merchandise hierarchy until the next highest level is reached.
[0052] FIG. 5 illustrates a flow chart for the method 450 for the merchandise hierarchy refinement according to the present invention. In step 455 , given a hierarchy with n levels, the method includes: setting the bottom level as the current level (i.e. set current level as level i and initialize i=1). In step 460 , the clustering method is performed on the current level i and the links between the current level i and the upper level i+1 are performed. In step 465 , the links between the upper level i+1 and the next upper level I+2 are updated. After the updates in step 465 , a determination is made as to whether the current value is the next highest level in step 470 . If the current level is not the next highest level, then the upper level is set as the current level at 471 and the clustering updating in steps 460 and 465 are repeated; otherwise, the refined hierarchy is output at 475 and the process terminates. The updating of the predetermined merchandise hierarchy representation thus includes adding a new node and corresponding link connecting the new node to a parent node of said first lower or second next lower level node.
[0053] In one example, as a result of implementing the present invention, the comprehensive merchandise hierarchy helps to improve the business structure and make it truly customer-oriented which will, in turn, increase customer's satisfaction, improve operational efficiency, and reduce the cost of management. For example, a new category may be created for young mothers that often buy products for themselves together with products for their baby, and baby products are no longer separately located in individual categories, such as baby milk in the diary department, or baby clothing in clothing department.
[0054] FIG. 6 illustrates an exemplary hardware configuration of a computing system 500 running and/or implementing the method steps in FIGS. 1 and 5 . The hardware configuration preferably has at least one processor or central processing unit (CPU) 511 . The CPUs 511 are interconnected via a system bus 512 to a random access memory (RAM) 514 , read-only memory (ROM) 516 , input/output (I/O) adapter 518 (for connecting peripheral devices such as disk units 521 and tape drives 540 to the bus 512 ), user interface adapter 522 (for connecting a keyboard 524 , mouse 526 , speaker 528 , microphone 532 , and/or other user interface device to the bus 512 ), a communication adapter 534 for connecting the system 500 to a data processing network, the Internet, an Intranet, a local area network (LAN), etc., and a display adapter 536 for connecting the bus 512 to a display device 538 and/or printer 539 (e.g., a digital printer of the like).
[0055] Although the embodiments of the present invention have been described in detail, it should be understood that various changes and substitutions can be made therein without departing from spirit and scope of the inventions as defined by the appended claims. Variations described for the present invention can be realized in any combination desirable for each particular application. Thus particular limitations, and/or embodiment enhancements described herein, which may have particular advantages to a particular application need not be used for all applications. Also, not all limitations need be implemented in methods, systems and/or apparatus including one or more concepts of the present invention.
[0056] The present invention can be realized in hardware, software, or a combination of hardware and software. A typical combination of hardware and software could be a general purpose computer system with a computer program that, when being loaded and run, controls the computer system such that it carries out the methods described herein. The present invention can also be embedded in a computer program product, which comprises all the features enabling the implementation of the methods described herein, and which—when loaded in a computer system—is able to carry out these methods.
[0057] Computer program means or computer program in the present context include any expression, in any language, code or notation, of a set of instructions intended to cause a system having an information processing capability to perform a particular function either directly or after conversion to another language, code or notation, and/or reproduction in a different material form.
[0058] Thus the invention includes an article of manufacture which comprises a computer usable medium having computer readable program code means embodied therein for causing a function described above. The computer readable program code means in the article of manufacture comprises computer readable program code means for causing a computer to effect the steps of a method of this invention. Similarly, the present invention may be implemented as a computer program product comprising a computer usable medium having computer readable program code means embodied therein for causing a function described above. The computer readable program code means in the computer program product comprising computer readable program code means for causing a computer to affect one or more functions of this invention. Furthermore, the present invention may be implemented as a program storage device readable by machine, such as a processing device, microprocessor, processor unit, etc., tangibly embodying a program of instructions operated by the machine to perform method steps for causing one or more functions of this invention.
[0059] The present invention may be implemented as a computer readable medium (e.g., a compact disc, a magnetic disk, a hard disk, an optical disk, solid state drive, digital versatile disc) embodying program computer instructions (e.g., C, C++, Java, Assembly languages, Net, Binary code) run by a processor (e.g., Intel® Core™, IBM® PowerPC®) for causing a computer to perform method steps of this invention. The present invention may include a method of deploying a computer program product including a program of instructions in a computer readable medium for one or more functions of this invention, wherein, when the program of instructions is run by a processor, the computer program product performs the one or more of functions of this invention.
[0060] It is noted that the foregoing has outlined some of the more pertinent objects and embodiments of the present invention. This invention may be used for many applications. Thus, although the description is made for particular arrangements and methods, the intent and concept of the invention is suitable and applicable to other arrangements and applications. It will be clear to those skilled in the art that modifications to the disclosed embodiments can be effected without departing from the spirit and scope of the invention. The described embodiments ought to be construed to be merely illustrative of some of the more prominent features and applications of the invention. Other beneficial results can be realized by applying the disclosed invention in a different manner or modifying the invention in ways known to those familiar with the art. | A system for adjusting a representation of a merchandise hierarchy associated with an entity such as a retailer or wholesaler of products. Product correlation information discovered in that entity's customers' shopping records are obtained and incorporated into an existing merchandise hierarchy with a constraint on the consistency with the existing hierarchy. | 6 |
CROSS-REFERENCED APPLICATIONS
This application claims the benefit of the disclosure of European Patent Application No EP10290267.3 filed on May 19, 2010 incorporated by reference in its entirety.
BACKGROUND
The statements in this section merely provide background information related to the present disclosure and may not constitute prior art.
This disclosure relates to equipment and methods for completing subterranean wells; in particular, wells that produce fluids originating within shale formations.
During completion of a subterranean well, drilling and cementing operations are performed to provide a conduit through which desirable fluids originating within the formation may flow. The cementing operation involves placing a competent cement sheath inside the annular region between the external surface of a tubular body such as well casing, and the borehole wall. The cement sheath supports the casing and provides a hydraulic seal between producing formations. The presence of a hydraulic seal is commonly referred to as zonal isolation.
Operators gain access to desired formation fluids by creating perforations that penetrate the casing and cement sheath, and extend into the formation. Formation fluid then flows into the casing interior and travels through the casing until it reaches a collection facility.
The formation-fluid production rate may be increased by performing stimulation treatments. Such treatments usually involve the injection of fluids through the perforations into the producing formation, with the goal of increasing the formation permeability. The treatments may involve matrix acidizing, hydraulic fracturing or both.
The aforementioned procedures are well known in the industry and have become highly sophisticated after decades of innovation and development. More complete information regarding the aforementioned procedures may be found in the following publications: Economides M C, Watters L T and Dunn-Norman S (eds.): Petroleum Well Construction , John Wiley & Sons (1988); Nelson E B and Guillot D (eds.): Well Cementing, 2 nd Edition, Schlumberger (2006); Economides M C and Nolte K G (eds.): Reservoir Stimulation , 3 rd Edition, John Wiley & Sons (2000).
Despite the advancements in well-completion technologies, difficulties frequently arise when the industry begins to exploit new types of formations. For example, it has been known for many years that large deposits of natural gas reside in some very low permeability shale formations. Notable examples are the Barnett Shale in Texas, the Woodford Shale which extends from Kansas to West Texas, and the Horn River Basin/Muskwa Shale in British Columbia, Canada. Such formations, whose permeabilities are in the microdarcy range, could not be exploited economically until horizontal-well technologies became widely available in the early 2000s. Today they are commonly called “unconventional gas” reservoirs.
One of the difficulties associated with completing unconventional gas reservoirs is related to hydraulic fracturing operations. The horizontal well usually extends through a shale stratum, and numerous sets of perforations are created along the wellbore to maximize exposure to the gas. Some of the perforations may not be aligned with the minimum stress plane, which defines the direction the fracture will tend to extend outward, away from the wellbore, as the fracturing fluid flows through the perforations. In such cases, the cement sheath often interferes with fracturing-fluid flow. The fluid must find a path around the cement sheath before reaching the preferred flow direction; as a result, there may be a choke effect. This condition is known as “near-wellbore tortuosity,” and is particularly problematic when the producing formation has low permeability. Failure to overcome this problem may significantly limit the effectiveness of the hydraulic fracturing treatment, and reduce the economic viability of the well.
For several years, the industry has overcome the stimulation problem by substituting conventional Portland cements with acid-soluble cements (ASCs). The most common ASCs are magnesium oxychloride (or Sorel) cement or conventional cements embedded with acid-soluble particles such as calcium carbonate. After the well is perforated, a matrix acidizing treatment is performed. The acid dissolves some of the cement around the perforations, thereby minimizing the choke effect and improving the outcome of the subsequent hydraulic-fracturing treatment.
There are some drawbacks associated with the use of ASCs. For example the method requires the step of performing an acidizing treatment before the fracturing treatment; furthermore, there is a risk that the acid may dissolve the cement sheath between two or more sets of perforations, leading to reduced control of the fracturing treatment.
As apparent, despite the valuable contributions of the prior art, it would be beneficial to have techniques that overcome the aforementioned drawbacks.
SUMMARY
The present disclosure pertains to an apparatus and methods that allow the use of conventional well cements, eliminate the need for an acidizing treatment before a hydraulic-fracturing treatment, and eliminate the risk of hydraulic communication between two or more sets of perforations.
In an aspect, embodiments relate to an apparatus for completing a subterranean well, comprising a tubular body and a degradable coating along the external surface of the tubular body, wherein the coating becomes unstable and undergoes degradation upon exposure to a well cement.
In further aspects, embodiments aim at methods for cementing a subterranean well comprising a borehole wall.
In yet further aspects, embodiments aim at methods for completing a subterranean well comprising a borehole wall.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 depicts a tubular body, coated by a degradable coating along its outside surface.
FIG. 2 is a top view of the tubular body coated by the degradable coating.
DETAILED DESCRIPTION
At the outset, it should be noted that in the development of any such actual embodiment, numerous implementation—specific decisions must be made to achieve the developer's specific goals, such as compliance with system related and business related constraints, which will vary from one implementation to another. Moreover, it will be appreciated that such a development effort might be complex and time consuming but would nevertheless be a routine undertaking for those of ordinary skill in the art having the benefit of this disclosure. In addition, the composition used/disclosed herein can also comprise some components other than those cited. In the summary and this detailed description, each numerical value should be read once as modified by the term “about” (unless already expressly so modified), and then read again as not so modified unless otherwise indicated in context. Also, in the summary and this detailed description, it should be understood that a concentration range listed or described as being useful, suitable, or the like, is intended that any and every concentration within the range, including the end points, is to be considered as having been stated. For example, “a range of from 1 to 10” is to be read as indicating each and every possible number along the continuum between about 1 and about 10. Thus, even if specific data points within the range, or even no data points within the range, are explicitly identified or refer to only a few specific points, it is to be understood that inventors appreciate and understand that any and all data points within the range are to be considered to have been specified, and that inventors possessed knowledge of the entire range and all points within the range.
As discussed earlier, improved equipment and procedures for completing unconventional gas wells would be beneficial. The present disclosure is aimed at a less onerous technique whereby the effects of near-wellbore tortuosity during hydraulic-fracturing operations may be mitigated. The disclosure is also aimed at preventing hydraulic communication between sets of perforations during hydraulic-fracturing operation.
As illustrated in FIGS. 1 and 2 , the present disclosure relates to an apparatus comprising a tubular body 101 and a degradable coating 102 that is applied to the external surface of the tubular body. The coating is designed to be unstable and degradable when exposed to a well cement. It will be appreciated that the tubular body may be drillpipe, casing, coiled tubing or a combination thereof. The coating may be continuous along the entire tubular body, or discontinuous—applied only at strategic locations where the operator plans to perforate. The coating is preferably applied to the tubular body before installation inside a subterranean well.
The degradable coating may be selected from one or more members of the list comprising polyamides, polycarbonates and polyesters. Of these, polyglycolic acid and polylactic acid are preferred. The polymer molecular weight may be between about 1000 and 1,000,000, preferably between about 5000 and 100,000. The coating thickness may be between about 40 μm and 1 cm, preferably between about 0.2 mm and 5 mm.
The aforementioned coatings become unstable and degrade when exposed to an alkaline-pH environment. Without wishing to be bound by any theory, it is believed that the degradation mechanism is hydrolysis, leading to a molecular-weight reduction. Such an environment may be provided by many well cements, comprising one or more members of the list comprising Portland cement, calcium aluminate cement, fly ash, blast furnace slag, lime-silica blends and chemically bonded phosphate ceramics.
After a cementing treatment, the coating degrades in the presence of the cement sheath, liberating space and creating a gap between the external casing surface and the cement sheath. In addition, the coating-hydrolysis products are generally acidic, and thus provide for additional cement degradation around the coating, resulting in a further widening of the gap. As described earlier, the gap minimizes near-wellbore tortuosity, thereby improving the efficiency of a hydraulic-fracturing treatment. It will be appreciated that complete coating degradation is not required in the present context.
In further aspects, the disclosure relates to methods for cementing a subterranean well comprising a borehole wall. A coating is applied to the external surface of a tubular body, wherein, in the presence of a well cement, the coating undergoes degradation. Generally, the tubular body is then installed in the subterranean well. When cement is place in the annular region between the external surface of the tubular body and the borehole wall it creates a cement sheath. This cement sheath creates an alkaline environment allowing the coating to degrade, thereby creating a gap between the cement sheath and the external surface of the tubular body.
Yet further aspects relate to methods for completing a subterranean well comprising a borehole wall. A coating is applied to the external surface of a tubular body, wherein, in the presence of a well cement, the coating undergoes degradation. Generally, the tubular body is then installed in the subterranean well. When cement is place in the annular region between the external surface of the tubular body and the borehole wall it creates a cement sheath. This cement sheath creates an alkaline environment allowing the coating to degrade, thereby creating a gap between the cement sheath and the external surface of the tubular body. At this point, one or more hydraulic-fracturing treatments can be performed through the perforations.
It will be appreciated that the casing may be perforated at any time within the period from when the cement sheath has hardened, to when the hydraulic-fracturing treatment is performed. It will also be appreciated that an acidizing treatment may, in some situations, be necessary before performing the hydraulic-fracturing treatment. Such situations include the need to remove perforating debris or near-wellbore formation damage.
For all methods disclosed herein, the degradable coating may be selected from one or more members of the list comprising polyamides, polycarbonates and polyesters. Of these, polyglycolic acid and polylactic acid are preferred. The polymer molecular weight may be between about 1000 and 1,000,000, preferably between about 5000 and 100,000. The coating thickness may be between about 40 μm and 1 cm, preferably between about 0.2 mm and 5 mm The well cement, may comprise one or more members of the list comprising Portland cement, calcium aluminate cement, fly ash, blast furnace slag, lime-silica blends and chemically bonded phosphate ceramics.
For all aspects, the tubular body may comprise one or more members of the list comprising drillpipe, casing and coiled tubing.
EXAMPLES
The following examples are further illustrative. Examples 1 and 2 involve coatings that degrade when exposed to an alkaline-pH environment. Examples 3 and 4 are comparative examples and involve coatings that do not degrade when exposed to an alkaline-pH environment.
All examples employed the following testing procedure. External surfaces of 25-mm, stainless-steel tubing samples were wrapped with one or more layers of a film or resin sheet. The resin sheets were held in place with cable ties. The coated tubes were vertically placed at the center of plastic containers and glued to the bottom with silicone sealant. A 1890-kg/m 3 Class G cement slurry was then poured around the tubes. The cement was covered with a layer of water, and the containers were placed in an oven and allowed to cure at various temperatures at time periods.
Example 1
The external surface of three pieces of metal tubing was wrapped with one layer of polylactic-acid resin sheet. Each piece of tubing was wrapped with a different thickness of resin sheet: 40 μm, 100 μm and 350 μm. A fourth piece of metal tubing was left uncoated as a control.
After the tubes were glued in place, the annuli between the metal tubes and the container walls were filled with cement slurry, a layer of water was poured on the cement-slurry surface, and the containers were placed in a 60° C. oven. The containers were cured for approximately 40 hours.
Upon removal from the oven, no gap was observed between the exterior surface of the uncoated tubing and the cement sheath. Gaps were observed between the exterior surfaces of the coated tubing samples and their respective cement sheaths. It was also possible to remove the coated tubes from the set cement. The tube coated with 350-μm resin sheet was the easiest to remove.
Example 2
Three layers of 350-μm-thick polylactic-acid resin sheet were wrapped around one piece of metal tubing, providing a layer with a thickness of approximately 1 mm After the tube was glued in place, the annulus between the metal tube and the container wall was filled with cement slurry, and the water layer was applied, and the container was placed in an 85° C. oven. The container was cured for approximately 10 days.
Upon removal from the oven, a gap was observed between the exterior surface of the tubing and the cement sheath. The tube was easily removed from the cement sheath. Residual resin film was also observed on the surface of the metal tube, as well as the cement sheath.
Example 3
A layer of 0.74-mm-thick Parafilm M tape was wrapped around one piece of metal tubing. After the tube was glued in place, the annulus between the metal tube and the container wall was filled with cement slurry, and the water layer was applied, and the container was placed in a 60° C. oven. The container was cured for approximately one week.
Upon removal from the oven, no gap was observed between the exterior surface of the tubing and the cement sheath. The cement was tight against the layer of tape. However, the tube could slide out of the container from the inside of the tape layer. The thickness the tape was measured at several locations, and found to be 0.75 mm Within experimental error, this is the original tape thickness, indicated that no degradation occurred upon exposure to cement.
Example 4
Several layers of 0.09-mm-thick PTFE tape was wrapped around one piece of metal tubing to obtain a combined thickness of 0.74 mm Cable ties were not necessary in this instance. After the tube was glued in place, the annulus between the metal tube and the container wall was filled with cement slurry, and the water layer was applied, and the container was placed in a 60° C. oven. The container was cured for approximately one week.
Upon removal from the oven, no gap was observed between the exterior surface of the tubing and the cement sheath. The cement was tight against the layer of tape. The tube was easily removed from the cement sample; however, the tape came away with the tube owing to its adhesive nature. The PTFE tape maintained its properties and did not degrade. | The external surface of a tubular body such as well casing is coated with a substance that, upon exposure to cement, is unstable and degrades. After installation in a subterranean well and subsequent cementation, the coating degrades and forms a gap between the external surface of the tubular body and the cement sheath. Forming the gap is useful for obtaining optimal stimulation during the hydraulic fracturing of unconventional shale-gas formations. | 2 |
This is a divisional of Ser. No. 08/791,814, filed Jan. 30, 1997, now U.S. Pat. No. 5,892,095.
BACKGROUND OF THE INVENTION
The present invention relates to a novel chemical-sensitization photoresist composition or, more particularly, to a chemical-sensitization photoresist composition used in the photolithographic patterning process for the manufacture of various kinds of electronic devices capable of giving a patterned resist layer having excellent cross-sectional profile and high fidelity as well as high heat resistance of the patterned resist layer with high photosensitivity and exposure dose latitude. The invention also relates to a novel oxime sulfonate compound useful as an acid-generating agent in the chemical-sensitization photoresist composition.
It is a trend in recent years in the photolithographic patterning works for the manufacture of various kinds of electronic devices such as semiconductor devices and liquid crystal display panels that the patterning work is performed by using a chemical-sensitization photoresist composition which contains a relatively small amount of a compound capable of releasing an acid by irradiation with actinic rays and a resinous ingredient susceptible to the changes of solubility behavior in a developer solution induced by the acid. Chemical-sensitization photoresist compositions in general are characterized by high sensitivity to actinic rays and excellent pattern resolution.
Chemical-sensitization photoresist compositions are classified into positive-working compositions and negative-working compositions depending on the type of the solubility change of the resinous ingredient to an aqueous alkaline developer solution by the radiation-generated acid. Namely, the alkali-solubility of the resist layer of a positive-working photoresist composition is increased while the alkali-solubility is decreased in the negative-working photoresist composition by exposure to actinic rays.
The film-forming resinous ingredient in a positive-working photoresist composition is typically an alkali-soluble polyhydroxystyrene resin, of which at least a part of the hydroxy groups are substituted by acid-dissociable substituent groups such as tert-butoxycarbonyl groups, tetrahydropyranyl groups and the like, so as to decrease the solubility of the resin in an alkaline developer solution. In the negative-working photoresist composition, on the other hand, the film-forming resinous ingredient is a combination of an acid-induced crosslinking agent such as melamine resins and urea resins with a polyhydroxystyrene resin, optionally substituted by the above-mentioned acid-dissociable solubility-reducing substituent groups for a part of the hydroxy groups.
The other essential ingredient in the chemical-sensitization photoresist compositions is a compound capable of releasing an acid by irradiation with actinic rays, of which various classes of compounds have been heretofore proposed and actually tested. A class of the most promising acid-generating agents includes oxime sulfonate compounds, in particular, having a cyano group in the molecule. Several compositions containing an oxime sulfonate compound and methods using the same are proposed. For example, European Patent Application 44115 A1 discloses a heat-curable coating solution containing an acid-curable amino resin and an oxime sulfonate compound. Japanese Patent Kokai 60-65072 discloses a method in which a bake-finishing composition containing a heat-curable resin and an oxime sulfonate compound is cured by irradiation with short-wavelength light. Japanese Patent Kokai 61-251652 discloses oxime sulfonate compounds having a substituent group such as ethylenically unsaturated polymerizable groups, epoxy group, hydroxy group and the like, and polymers thereof. Japanese Patent Kokai 1-124848 teaches an image-forming method by the use of a photosensitive composition containing a film-forming organic substance, an oxime sulfonate compound and a photosensitive compound having an aromatic group. Japanese Patent Kokai 2-154266 discloses a photoresist composition containing an alkali-soluble resin, oxime sulfonate compound and sensitivity enhancing crosslinking agent. Japanese Patent Kokai 2-161444 teaches a negative-patterning method by the use of an oxime sulfonate compound. Further, Japanese Patent Kokai 6-67433 discloses a photoresist composition for i-line exposure containing an oxime sulfonate compound.
The oxime sulfonate compounds having a cyano group in the molecule disclosed in the above-mentioned patent documents include:
α-(p-toluenesulfonyloxyimino)phenyl acetonitrile;
α-(4-chlorobenzenesulfonyloxyimino)phenyl acetonitrile;
α-(4-nitrobenzenesulfonyloxyimino)phenyl acetonitrile;
α-(4-nitro-2-trifluoromethylbenzenesulfonyloxyimino)phenyl acetonitrile;
α-(benzenesulfonyloxyimino)-4-chlorophenyl acetonitrile;
α-(benzenesulfonyloxyimino)-2,4-dichlorophenyl acetonitrile;
α-(benzenesulfonyloxyimino)-2,6-dichlorophenyl acetonitrile;
α-(benzenesulfonyloxyimino)-4-methoxyphenyl acetonitrile;
α-(2-chlorobenzenesulfonyloxyimino)-4-methoxyphenyl acetonitrile;
α-(benzenesulfonyloxyimino)-2-thienyl acetonitrile;
α-(4-dodecylbenzenesulfonyloxyimino)phenyl acetonitrile;
α-(p-toluenesulfonyloxyimino)-4-methoxyphenyl acetonitrile;
α-(4-dodecylbenzenesulfonyloxyimino)-4-methoxyphenyl acetonitrile;
α-(p-toluenesulfonyloxyimino)-3-thienyl acetonitrile; and the like.
The molecules of these sulfonate compounds are susceptible to scission of the sulfonate ester linkage by irradiation with actinic rays to generate a corresponding sulfonic acid so that they are useful as an acid-generating agent in the chemical-sensitization photoresist compositions.
It should be mentioned that, while a sulfonic acid is generated from the oxime sulfonate compound by exposure to light, the number of the sulfonic acid molecules released from a molecule of the above-named oxime sulfonate compounds is necessarily limited to one, so that the amount of the acid is also limited. When such an oxime sulfonate compound is used as an acid-generating agent in a negative-working photoresist composition, accordingly, no satisfactory patterned resist layer can be obtained because the width of a line-patterned resist layer cannot be broad enough at the top and the dimensional fidelity and heat resistance of the patterned resist layer cannot be as high as desired along with a relatively low exposure dose latitude.
SUMMARY OF THE INVENTION
The present invention, accordingly, has a primary object to provide novel and improved positive-working and negative-working chemical-sensitization photoresist compositions capable of giving a patterned resist layer having good cross-sectional profile, high dimensional fidelity and excellent heat resistance with excellent photosensitivity and exposure dose latitude.
The present invention further has an object to provide a novel cyano group-containing oxime sulfonate compound which is useful as an acid-generating agent in a chemical-sensitization photoresist composition exhibiting a high efficiency for the generation of an acid upon irradiation with actinic rays.
Thus, the cyano group-containing oxime sulfonate compound of the present invention useful as an acid-generating agent in a chemical-sensitization photoresist composition is a novel compound not known in the prior art nor described in any literature as represented by the general formula
A[C(CN)═N--O--SO.sub.2 --R].sub.n, (I)
in which each R is, independently from the others, an unsubstituted or substituted monovalent hydrocarbon group, A is a divalent or tervalent organic group and the subscript n is 2, when A is a divalent group, or 3, when A is a tervalent group.
The positive-working chemical-sensitization photoresist composition provided by the present invention comprises, as a uniform solution in an organic solvent:
(a1) an alkali-soluble hydroxy-containing resin, of which at least a part of the hydroxy groups are substituted by acid-dissociable groups so as to decrease the alkali-solubility of the resin in an aqueous alkaline solution; and
(b) the cyano group-containing oxime sulfonate compound defined above as an acid-generating agent, of which the subscript n in the general formula (I) is preferably 2.
The negative-working chemical-sensitization photoresist composition provided by the present invention, on the other hand, comprises, as a uniform solution in an organic solvent:
(a2) an alkali-soluble resin or an alkali-soluble hydroxy-containing resin, of which a part of the hydroxy groups are substituted by acid-dissociable groups;
(b) the cyano group-containing oxime sulfonate compound defined above as an acid-generating agent, of which the subscript n in the general formula (I) is preferably 2; and
(c) a crosslinking agent which is a compound capable of forming crosslinks in the presence of an acid.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
As is described above, each of the positive-working and negative-working photoresist compositions of the invention is characterized by the use of a specific cyano group-containing oxime sulfonate compound as an acid-generating agent, i.e., the component (b). In the positive-working photoresist composition of the invention, an acid is released from the component (b) by exposure to actinic rays so that the acid-dissociable substituent groups in the component (a1) are dissociated so as to increase the solubility of the resist layer in an aqueous alkaline developer solution pattern-wise in the areas exposed to actinic rays. In the negative-working photoresist composition of the invention, on the other hand, the acid-crosslinking ingredient as the component (c) causes crosslinking of the resinous ingredient as the component (a2) when an acid is generated from the acid-generating agent as the component (b) in the resist layer so as to decrease the solubility of the resist layer in an aqueous alkaline developer solution pattern-wise in the areas exposed to actinic rays.
The above-mentioned alkali-soluble resin as the component (a2) is exemplified by novolac resins obtained by the condensation reaction of a phenolic compound such as phenol, m- and p-cresols, xylenols, trimethylphenols and the like, with an aldehyde compound such as formaldehyde in the presence of an acidic catalyst, hydroxystyrene-based resins, e.g., homopolymeric polyhydroxystyrene resins, copolymeric resins of hydroxystyrene and other styrene monomers and copolymeric resins of hydroxystyrene and (meth)acrylic acid or a derivative thereof and (meth)acrylic acid-based resins, e.g., copolymeric resins of (meth)acrylic acid and a derivative thereof.
The alkali-soluble hydroxy-containing resin from which the component (a1) is derived by substitution of acid-dissociable groups for at least a part of the hydroxy groups is exemplified by homopolymeric polyhydroxystyrene resins, copolymeric resins of hydroxystyrene and other styrene monomers, copolymeric resins of hydroxystyrene and (meth)acrylic acid or a derivative thereof and copolymeric resins of (meth)acrylic acid and a derivative thereof having carboxylic hydroxy groups.
The above-mentioned styrene monomers to be copolymerized with hydroxystyrene include styrene, α-methylstyrene, p- and o-methylstyrenes, p-methoxystyrene, p-chlorostyrene and the like. The above-mentioned derivatives of (meth)acrylic acid to be copolymerized with hydroxystyrene or (meth)acrylic acid include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylamide, (meth)acrylonitrile and the like.
The acid-dissociable groups substituting for at least a part of the hydroxy groups in the above-mentioned alkali-soluble hydroxy-containing resins are exemplified by alkoxycarbonyl groups such as tert-butoxycarbonyl group and tert-amyloxycarbonyl group, tertiary alkyl groups such as tert-butyl group, alkoxyalkyl groups such as ethoxyethyl group and methoxypropyl group, acetal groups such as tetrahydropyranyl group and tetrahydrofuranyl group, benzyl group, trimethylsilyl group and so on.
The degree of substitution of the above-mentioned acid-dissociable groups for the hydroxy groups in the hydroxy-containing resin is usually in the range from 1 to 60% or, preferably, from 10 to 50%.
In the positive-working chemical-sensitization photoresist composition of the present invention, the resinous ingredient as the component (a1) is preferably a polyhydroxystyrene resin substituted by tert-butoxycarbonyl groups, tetrahydropyranyl group or alkoxyalkyl groups such as ethoxyethyl and methoxypropyl groups for a part of the hydroxy groups in the starting polyhydroxystyrene resin or a combination of these resins.
In the negative-working chemical-sensitization photoresist composition of the present invention, the alkali-soluble resinous ingredient as the component (a2) used in combination with the acid-crosslinking agent as the component (c) can be selected from the group consisting of novolac resins, hydroxystyrene-based polymeric resins and (meth)acrylic acid-based polymeric resins as well as these resins substituted by acid-dissociable groups for a part of the hydroxy groups in the resins. The component (a2) is preferably a cresol novolac resin, polyhydroxystyrene resin, a copolymeric resin of hydroxystyrene and styrene or a resin obtained by substitution of tert-butoxycarbonyl groups for a part of the hydroxy groups in a polyhydroxystyrene resin.
The acid-crosslinking agent as the component (c) compounded in the negative-working chemical-sensitization photoresist composition of the invention in combination with the above-described component (a2) can be selected from those known in the conventional negative-working chemical-sensitization photoresist compositions without particular limitations. Examples of the component (c) include amino resins having hydroxy and/or alkoxy groups such as melamine resins, urea resins, guanamine resins, acetoguanamine resins, benzoguanamine resins, glycoluryl-formaldehyde resins, succinylamide-formaldehyde resins, ethyleneurea-formaldehyde resins and the like. These resins can be easily obtained by the reaction of melamine, urea, guanamine, acetoguanamine, benzoguanamine, glycoluryl, succinylamide or ethyleneurea in boiling water with formaldehyde to effect methylolation optionally followed by an alkoxylation reaction with a lower alcohol. Commercial products of several grades are available for these resins including those sold under the trade names of Nicalacs Mx-750, Mw-30 and Mx-290 (each a product by Sanwa Chemical Co.).
Besides the above-mentioned resinous compounds, the component (c) can be selected from the group consisting of benzene compounds having alkoxy groups such as 1,3,5-tris(methoxymethoxy)benzene, 1,2,4-tris(isopropoxymethoxy)benzene and 1,4-bis(sec-butoxymethoxy)benzene and phenol compounds having hydroxy and/or alkoxy groups such as 2,6-di(hydroxymethyl)p-cresol and 2,6-di(hydroxymethyl)-p-tert-butyl phenol.
The above-described acid-crosslinking agents can be used in the negative-working photoresist composition of the invention either singly or as a combination of two kinds or more according to need.
The amount of the acid-crosslinking agent as the component (c) in the negative-working chemical-sensitization photoresist composition of the invention is usually in the range from 3 to 70 parts by weight or, preferably, in the range from 5 to 50 parts by weight per 100 parts by weight of the component (a2). When the amount of the component (c) is too small, the photoresist composition cannot be imparted with high photosensitivity while, when the amount thereof is too large, the resist layer formed from the photoresist composition on a substrate surface cannot be uniform along with a decrease in the developability not to give a patterned resist layer of high quality.
The alkali-soluble resin for the component (a1) or (a2) should preferably have an average molecular weight in the range from 2000 to 20000. Further, it is preferable that the alkali-soluble resin has a molecular weight distribution as narrow as possible in order to obtain a patterned resist layer of high quality in the pattern resolution and heat resistance of the resist layer. The molecular weight distribution of the resin can be represented by the ratio of the weight-average molecular weight Mw to the number-average molecular weight Mn, i.e., Mw:Mn, which should preferably be 3.5 or smaller or, more preferably, 3.0 or smaller for novolac resins and preferably should be 3.5 or smaller or, more preferably, 2.5 or smaller for polyhydroxystyrene-based resins.
The inventive chemical-sensitization photoresist composition, which is either of the positive-working type or of the negative-working type, is characterized by the use of a very specific acid-generating agent which is a novel cyano group-containing oxime sulfonate compound represented by the general formula (I) given before, in which R is an unsubstituted or substituted monovalent hydrocarbon group, A is a divalent or tervalent organic group and the subscript n is 2, when A is divalent, or 3, when A is tervalent, or, in particular, 2.
The monovalent hydrocarbon group denoted by R is an aryl group having 6 to 14 carbon atoms or a non-aromatic hydrocarbon group including alkyl groups, cycloalkyl groups, alkenyl groups and cycloalkenyl groups having 12 or less carbon atoms. When R is a substituted hydrocarbon group, the substituent group can be a halogen atom, hydroxy group, alkoxy group or acyl group or, in particular, a halogen atom when R is an alkyl group having 1 to 4 carbon atoms.
The above-mentioned aryl group having 6 to 14 carbon atoms is exemplified by phenyl, tolyl, methoxyphenyl, xylyl, biphenyl, naphthyl and anthryl groups. The above-mentioned alkyl group, which can be straightly linear or branched, having 1 to 12 carbon atoms is exemplified by methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-octyl and n-dodecyl groups. The alkenyl group is exemplified by ethenyl, propenyl, butenyl, butadienyl, hexenyl and octadienyl groups. The cycloalkyl group is exemplified by cyclopentyl, cyclohexyl, cyclooctyl and cyclododecyl groups. The cycloalkenyl group is exemplified by 1-cyclobutenyl, 1-cyclopentenyl, 1-cyclohexenyl, 1-cycloheptenyl and 1-cyclooctenyl groups.
The above-described monovalent aromatic or non-aromatic hydrocarbon groups as R in the general formula (I) can be substituted by substituents for one or more of the hydrogen atoms in a molecule. The substituent is selected from the group consisting of halogen atoms, i.e., atoms of fluorine, chlorine and bromine, hydroxy group, alkoxy groups and acyl groups. Halogenated alkyl groups as a class of the non-aromatic substituted hydrocarbon groups should preferably have 1 to 4 carbon atoms including chloromethyl, trichloromethyl, trifluoromethyl and 2-bromopropyl groups.
The group denoted by A in the general formula (I) is a divalent or tervalent organic group which is preferably an aliphatic or aromatic hydrocarbon group. More preferably, the group denoted by A is an o-, m- or p-phenylene group.
Since the cyano group-containing oxime sulfonate compound of the invention, which can be used as an acid-generating agent in the inventive photoresist composition, has two or three sulfonate ester groups per molecule, two or three molecules of sulfonic acid are generated from a molecule of the sulfonate compound by exposure to actinic rays so that the efficiency of acid generation can be high so much with the same exposure dose. Each of the groups denoted by R in the general formula (I) representing the oxime sulfonate compound is preferably a halogen-substituted or unsubstituted non-aromatic hydrocarbon group because the heat resistance of the patterned photoresist layer is somewhat decreased as a trend when the group R or hence the oxime sulfonate molecule is bulky. In addition, a halogen-substituted or unsubstituted non-aromatic hydrocarbon group has low absorptivity to ultraviolet light so that the transparency of the photoresist layer to the exposure light is little decreased even by increasing the amount of the acid-generating agent in the photoresist composition with an object to increase the photosensitivity of the composition along with advantageous effects on the pattern resolution and cross-sectional profile of the patterned resist layer. When the inventive photoresist composition is patternwise exposed to KrF excimer laser beams having a wavelength of 248 nm, the group denoted by A in the general formula (I) is preferably an alkylene group in view of the high transparency of alkylene groups to the light of this wavelength, while a phenylene group is preferred as the group A when the photoresist composition is for pattern-wise exposure to i-line ultraviolet light having a wavelength of 365 nm.
Further, the halogen-substituted or unsubstituted non-aromatic hydrocarbon group as the group denoted by R is preferably a halogen-substituted or unsubstituted alkyl group having 1 to 4 carbon atoms in consideration of the high diffusibility of the acid generated from the acid-generating agent in the resist layer in the post-exposure baking treatment after pattern-wise exposure of the resist layer to actinic rays.
Examples of the cyano group-containing oxime sulfonate compound of the invention, which can be the acid-generating agent as the component (b) in the inventive photoresist composition, include those expressed by the following structural formulas:
Me--SO.sub.2 --O--N═C(CN)--pPn--C(CN)═N--O--SO.sub.2 --Me,
Me--SO.sub.2 --O--N═C(CN)--mPn--C(CN)═N--O--SO.sub.2 --Me,
Et--SO.sub.2 --O--N═C(CN)--pPn--C(CN)═N--O--SO.sub.2 --Et,
Bu--SO.sub.2 --O--N═C(CN)--mPn--C(CN)═N--O--SO.sub.2 --Bu,
Bu--SO.sub.2 --O--N═C(CN)--pPn--C(CN)═N--O--SO.sub.2 --Bu,
CF.sub.3 --SO.sub.2 --O--N═C(CN)--pPn--C(CN)═N--O--SO.sub.2 --CF.sub.3,
CF.sub.3 --SO.sub.2 --O--N═C(CN)--mPn--C(CN)═N--O--SO.sub.2 --CF.sub.3,
Ch--SO.sub.2 --O--N═C(CN)--pPn--C(CN)═N--O--SO.sub.2 --Ch,
Ph--SO.sub.2 --O--N═C(CN)--pPn--C(CN)═N--O--SO.sub.2 --Ph,
Me--pPh--SO.sub.2 --O--N═C(CN)--pPn--C(CN)═N--O--SO.sub.2 --pPn--Me,
Me--pPn--SO.sub.2 O--N═C(CN)--mPn--C(CN)═N--O--SO.sub.2 --pPn--Me,
Me--O--pPn--SO.sub.2 --O--N═C(CN)--mPn--C(CN)═N--O--SO.sub.2 --pPn--O--Me,
Me--SO.sub.2 --O--N═C(CN)--(CH.sub.2).sub.3 --C(CN)═N--O--SO.sub.2 --Me,
and
Bu--SO.sub.2 --O--N═C(CN)--(CH.sub.2).sub.5 --C(CN)═N--O--SO.sub.2 --Bu
as the examples of the compound in which the linking group A in the general formula (I) is a divalent hydrocarbon group such as phenylene and alkylene groups; and ##STR1## as the examples of the compound in which the linking group A in the general formula (I) is a tervalent hydrocarbon group, in which Me, Et, Bu, Ch and Ph are methyl, ethyl, butyl, cyclohexyl and phenyl groups, respectively, and mPn and pPn are m-phenylene and p-phenylene groups, respectively.
The above-named oxime sulfonate compounds can be used either singly or as a combination of two kinds or more according to need as the acid-generating agent, i.e., component (b), in the chemical-sensitization photoresist composition of the invention.
The amount of the cyano group-containing oxime sulfonate compound as the acid-generating agent, i.e., component (b), in the inventive chemical-sensitization photoresist composition is in the range from 0.1 to 30 parts by weight or, preferably, from 1 to 20 parts by weight per 100 parts by weight of the component (a1), when the photoresist composition is of the positive-working type, or the total amount of the components (a2) and (c), when the photoresist composition is of the negative-working type, in respect of obtaining good balance of film-forming behavior of the composition, image-forming behavior and developability. When the amount of the component (b) is too small, complete patterning can hardly be obtained while, when the amount thereof is too large, a decrease is caused in the uniformity of the resist layer formed from the photoresist composition on the substrate surface along with a decrease in the developability of the resist layer after pattern-wise exposure to actinic rays.
The chemical-sensitization photoresist composition of the invention is used preferably in the form of a uniform solution prepared by dissolving the above-described essential components in an organic solvent. Examples of suitable organic solvents include ketone compounds such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone and 2-heptanone; monoethers of polyhydric alcohols such as monomethyl, monoethyl, monopropyl, monobutyl and monophenyl ethers of ethylene glycol, diethylene glycol, propylene glycol or dipropylene glycol and monoacetates thereof; cyclic ethers such as dioxane; ester compounds such as methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate and ethyl ethoxypropionate; and amide compounds such as N,N-dimethyl formamide, N,N-dimethyl acetamide and N-methyl-2-pyrrolidone. These organic solvents can be used either singly or as a mixture of two kinds or more according to need.
Besides the above-described essential components, it is optional that the photoresist composition of the present invention is admixed with various kinds of known additives used in conventional photoresist compositions and having compatibility with the essential ingredients including auxiliary resins to modify or improve the properties of the resist layer, plasticizers, stabilizers, coloring agents, surface-active agents, carboxylic acid compounds, amine compounds and the like.
The procedure for the photolithographic patterning of a resist layer using the photoresist composition of the invention can be conventional as in the prior art technology. In the first place, namely, a substrate such as a semiconductor silicon single crystal wafer is coated with the photoresist composition in the form of a solution by using a suitable coating machine such as a spinner followed by drying to form a uniform coating film of the photoresist composition, which is then exposed pattern-wise to actinic rays such as ultraviolet light, deep-ultraviolet light, excimer laser beams and the like through a pattern-bearing photomask or irradiated pattern-wise with electron beams by scanning according to the desired pattern to form a latent image of the pattern followed by a post-exposure baking treatment. The latent image of the pattern formed in the resist layer is then developed by dipping the substrate in an aqueous alkaline developer solution such as an aqueous solution of tetramethylammonium hydroxide in a concentration of 1 to 10% by weight followed by rinse with water and drying to give a resist layer patterned with good fidelity to the photomask pattern.
In the following, the present invention directed to the novel cyano group-containing oxime sulfonate compounds and chemical-sensitization photoresist compositions is illustrated in more detail by way of Examples and Comparative Examples, in which the term of "parts" always refers to "parts by weight".
EXAMPLE 1
A cyano group-containing oxime sulfonate compound expressed by the formula
CH.sub.3 --SO.sub.2 --O--N═C(CN)--pPn--C(CN)═N--O--SO.sub.2 --CH.sub.3,
in which pPn is a p-phenylene group, was synthetically prepared in the following manner. Thus, 20.0 g (0.093 mole) of bis(α-hydroxyimino)-p-phenylene diacetonitrile and 22.6 g (0.233 mole) of triethylamine dissolved in 200 ml of tetrahydrofuran were introduced into a reaction vessel to form a uniform solution which was chilled to and kept at -5° C. and to which 26.7 g (0.233 mole) of mesyl chloride were added dropwise under agitation over a period of 2 hours followed by further continued agitation at -5 ° C. for 2 hours and then at about 25° C. for 20 hours to complete the reaction. The reaction mixture was subjected to distillation at 30° C. under reduced pressure for the removal of tetrahydrofuran to obtain a crude product. A 22 g portion thereof was subjected to purification by repeating recrystallization from acetonitrile to obtain 12.5 g of a white crystalline compound having a melting point at 263° C. as the product which could be identified to be the above-mentioned target compound as being supported by the analytical results shown below. The above-mentioned yield of the product corresponds to 36.3% of the theoretical value.
The infrared absorption spectrum of the product compound had absorption bands having peaks at wave numbers of 769 cm -1 , 840 cm -1 , 1189 cm -1 , 1382 cm -1 and 2240 cm -1 . The proton nuclear magnetic resonance ( 1 H-NMR) spectrum of the compound in dimethyl sulfoxide-d 6 had absorptions at δ values of 3.68 ppm and 8.15 ppm. The ultraviolet absorption spectrum of the compound in tetrahydrofuran as the solvent had absorption bands having peaks at wavelengths λ max of 220 nm and 301 nm with molar absorption coefficients of 7900 and 12200, respectively.
EXAMPLE 2
A cyano group-containing oxime sulfonate compound expressed by the formula
CH.sub.3 --SO.sub.2 --O--N═C(CN)--mPn--C(CN)═N--O--SO.sub.2 --CH.sub.3,
in which mPn is a m-phenylene group, was synthetically prepared in substantially the same manner as in Example 1 excepting for the replacement of the bis(α-hydroxyimino)-p-phenylene diacetonitrile with the same amount of bis(α-hydroxyimino)-m-phenylene diacetonitrile. A 30 g portion of the crude reaction product was subjected to purification by repeating recrystallization from acetonitrile to obtain 25.8 g of a white crystalline compound having a melting point at 196° C. as the product which could be identified to be the above-mentioned target compound as being supported by the analytical results shown below. The above-mentioned yield of the product corresponds to 72.0% of the theoretical value.
The infrared absorption spectrum of the product compound had absorption bands having peaks at wave numbers of 782 cm -1 , 844 cm -1 , 1191 cm -1 , 1382 cm -1 and 2238 cm -1 . The proton nuclear magnetic resonance ( 1 H-NMR) spectrum of the compound in dimethyl sulfoxide-d 6 had absorptions at δ values of 3.65 ppm, 7.89 ppm, 8.27 ppm and 8.29 ppm. The ultraviolet absorption spectrum of the compound in tetrahydrofuran as the solvent had absorption bands having peaks at wavelengths λ max of 211 nm and 269 nm with molar absorption coefficients of 6500 and 12100, respectively.
EXAMPLE 3
A cyano group-containing oxime sulfonate compound expressed by the formula
C.sub.4 H.sub.9 --SO.sub.2 --O--N═C(CN)--mPn--C(CN)═N--O--SO.sub.2 --C.sub.4 H.sub.9,
in which mPn is a m-phenylene group, was synthetically prepared in substantially the same manner as in Example 1 excepting for the replacement of the bis(α-hydroxyimino)-p-phenylene diacetonitrile with the same amount of bis(α-hydroxyimino)-m-phenylene diacetonitrile and replacement of 26.7 g of mesyl chloride with 36.3 g (0.233 mole) of 1-butanesulfonyl chloride. A 32 g portion of the crude reaction product was subjected to purification by repeating recrystallization from acetonitrile to obtain 20.5 g of a white crystalline compound having a melting point at 98° C. as the product which could be identified to be the above-mentioned target compound as being supported by the analytical results shown below. The above-mentioned yield of the product corresponds to 48.5% of the theoretical value.
The infrared absorption spectrum of the product compound had absorption bands having peaks at wave numbers of 783 cm -1 , 844 cm -1 , 1191 cm -1 , 1382 cm -1 and 2239 cm -1 . The proton nuclear magnetic resonance ( 1 H-NMR) spectrum of the compound in acetone-d 6 had absorptions at δ values of 0.98 ppm, 1.52 ppm, 1.92 ppm, 3.70 ppm, 7.91 ppm, 8.27 ppm and 8.40 ppm. The ultraviolet absorption spectrum of the compound in tetrahydrofuran as the solvent had absorption bands having peaks at wavelengths λ max of 211 nm and 268 nm with molar absorption coefficients of 7100 and 13500, respectively.
EXAMPLE 4
A cyano group-containing oxime sulfonate compound expressed by the formula
CH.sub.3 --pPn--SO.sub.2 --O--N═C(CN)--mPn--C(CN)═N--O--SO.sub.2 --pPn--CH.sub.3,
in which mPn is a m-phenylene group and pPn is a p-phenylene group, was synthetically prepared in the following manner. Thus, 10.0 g (0.0465 mole) of bis(α-hydroxyimino)-m-phenylene diacetonitrile and 11.3 g (0.116 mole) of triethylamine dissolved in 200 ml of tetrahydrofuran were introduced into a reaction vessel to form a uniform solution which was chilled to and kept at -5° C. and to which 22.1 g (0.116 mole) of p-toluenesulfonyl chloride were added dropwise under agitation over a period of 2 hours followed by further continued agitation at -5° C. for 2 hours and then at about 25° C. for 20 hours to complete the reaction. The reaction mixture was subjected to distillation at 30° C. under reduced pressure for the removal of tetrahydrofuran to obtain a crude product. A 12 g portion thereof was subjected to purification by repeating recrystallization from acetonitrile to obtain 10.0 g of a white crystalline compound having a melting point at 205° C. as the product which could be identified to be the above-mentioned target compound as being supported by the analytical results shown below. The above-mentioned yield of the product corresponds to 41.3% of the theoretical value.
The infrared absorption spectrum of the product compound had absorption bands having peaks at wave numbers of 773 cm -1 , 836 cm -1 , 1197 cm -1 , 1394 cm -1 and 2237 cm -1 . The proton nuclear magnetic resonance ( 1 H-NMR) spectrum of the compound in dimethyl sulfoxide-d 6 had absorptions at δ values of 2.42 ppm, 7.52 ppm, 7.77 ppm and 7.98 ppm. The ultraviolet absorption spectrum of the compound in tetrahydrofuran as the solvent had absorption bands having peaks at wavelengths λ max of 230 nm and 270 nm with molar absorption coefficients of 24000 and 17300, respectively.
EXAMPLE 5
A cyano group-containing oxime sulfonate compound expressed by the formula
CF.sub.3 --SO.sub.2 --O--N═C(CN)--mPn--C(CN)═N--O--SO.sub.2 --CF.sub.3,
in which mPn is a m-phenylene group, was synthetically prepared in substantially the same manner as in Example 2 excepting for the replacement of 26.7 g of the mesyl chloride with 64.7 g (0.233 mole) of trifluoromethanesulfonic acid anhydride.
EXAMPLE 6
A cyano group-containing oxime sulfonate compound expressed by the formula
CH.sub.3 O--pPn--SO.sub.2 --O--N═C(CN)--mPn--C(CN)═N--O--SO.sub.2 --pPn--OCH.sub.3,
in which mPn is a m-phenylene group and pPn is a p-phenylene group, was synthetically prepared in substantially the same manner as in Example 4 excepting for the replacement of 22.1 g of the p-toluenesulfonyl chloride with 24.0 g (0.116 mole) of 4-methoxybenzenesulfonyl chloride.
EXAMPLE 7
A negative-working photoresist composition was prepared by dissolving, in a mixture of 384 parts of propyleneglycol monomethyl ether acetate and 96 parts of N-methyl-2-pyrrolidone, 100 parts of a copolymeric resin of hydroxystyrene and styrene having a weight-average molecular weight of 2500 and 15 parts of a melamine resin (Mw-30, a product by Sanwa Chemical Co.) and further admixing the solution with 3 parts of the oxime sulfonate compound prepared in Example 2 as an acid-generating agent.
The thus-prepared photoresist solution was applied onto the surface of a silicon wafer on a spinner followed by drying on a hotplate at 90° C. for 90 seconds to give a photoresist layer having a thickness of 1.0 μm. The resist layer was exposed pattern-wise to i-line ultraviolet light of 365 nm wavelength through a Levenson phase-shift mask on a minifying projection exposure machine (Model NSR-2005i10D, manufactured by Nikon Co.) and subjected to a post-exposure baking treatment at 100° C. for 90 seconds followed by a development treatment in a 2.38% by weight aqueous solution of tetramethylammonium hydroxide at 23° C. for 65 seconds, rinse with water for 30 seconds and drying to give a line-and-space pattern of the resist layer.
The cross-sectional profile of a line-and-space pattern of the resist layer having a line width of 0.30 μm was excellently orthogonal standing upright on the substrate surface as examined on a scanning electron microscopic photograph. The exposure dose latitude as expressed by Eop/Eg was 1.70, in which Eop is the exposure dose required for the reproduction of a line-and-space pattern of 0.30 μm line width with a line width:space width of 1:1, and Eg is the exposure dose for the incipient pattern formation in the exposed area of a line-and-space pattern of 0.30 μm line width.
COMPARATIVE EXAMPLE 1
The experimental procedure for the preparation and testing of a negative-working photoresist composition was substantially the same as in Example 7 described above excepting for the replacement of the oxime sulfonate compound prepared in Example 2 with the same amount of α-(p-toluenesulfonyloxyimino)-4-methoxyphenyl acetonitrile.
The results of the evaluation tests were that the cross-sectional profile of a line-and-space patterned resist layer having a line width of 0.30 μm was not orthogonal but had a width narrowed toward the top of the cross-section and the exposure dose latitude Eop/Eg was 1.60.
EXAMPLE 8
A negative-working photoresist composition was prepared by dissolving, in 270 parts of propyleneglycol monomethyl ether acetate, 100 parts of a cresol novolac resin as a condensation product of m-cresol and formaldehyde having a weight-average molecular weight of 10000 and 10 parts of a melamine resin (Mw-30, a product by Sanwa Chemical Co.) and further admixing the solution with 1.5 parts of the oxime sulfonate compound prepared in Example 2 as an acid-generating agent.
The thus-prepared photoresist solution was applied onto the surface of a silicon wafer on a spinner followed by drying on a hotplate at 90° C. for 90 seconds to give a photoresist layer having a thickness of 2.0 μm. The resist layer was exposed pattern-wise to i-line ultraviolet light of 365 nm wavelength on a minifying projection exposure machine (Model NSR-2005i10D, manufactured by Nikon Co.) and subjected to a post-exposure baking treatment at 100° C. for 90 seconds followed by a development treatment in a 2.38% by weight aqueous solution of tetramethylammonium hydroxide at 23° C. for 65 seconds, rinse with water for 30 seconds and drying to give a line-and-space pattern of the resist layer.
As a measure of the photosensitivity of the photoresist composition, the minimum exposure dose was measured for the formation of a line-and-space pattern of 0.80 μm line width in a line:space width ratio of 1:1 to find an exposure dose of 75 mJ/cm 2 .
A scanning electron microscopic examination was undertaken for the cross-sectional profile of a line-patterned resist layer having a line width of 0.80 μm by taking a microscopic photograph to find that the cross-sectional profile was excellently orthogonal standing upright on the substrate surface. The ratio of the exposure dose with which a line-and-space pattern of 1 μm line width could be reproduced to have a line:space width ratio of 1:1 to the above-mentioned exposure dose as a measure of the photosensitivity was 1.15 which could be a measure for the dimensional fidelity of pattern reproduction. Further, the heat stability of the patterned resist layer was examined by heating the resist layer on a hotplate to determine the lowest temperature for incipient flowing of a line-and-space pattern of 0.8 μm line width to obtain a temperature of 200° C.
COMPARATIVE EXAMPLE 2
The experimental procedure for the preparation of a photoresist composition was substantially the same as in Example 8 described above excepting for the replacement of 1.5 parts of the oxime sulfonate compound prepared in Example 2 with 3 parts of α-(p-toluenesulfonyloxyimino)phenyl acetonitrile.
As a result of the evaluation tests of the composition undertaken in the same manner as in the preceding examples, the photosensitivity thereof was found to be 300 mJ/cm 2 . The cross-sectional profile of a line-and-space patterned resist layer having a line width of 0.80 μm was not orthogonal but had a width narrowed toward the top of the cross-section. The dimensional fidelity of the patterned resist layer was 1.35 and the temperature for heat resistance was 140° C.
EXAMPLE 9
The experimental procedure for the preparation of a photoresist composition was substantially the same as in Example 8 described above excepting for the replacement of the oxime sulfonate compound prepared in Example 2 with the same amount of another oxime sulfonate compound prepared in Example 3.
As a result of the evaluation tests of the composition undertaken in the same manner as in the preceding examples, the photosensitivity thereof was found to be 65 mJ/cm 2 . The cross-sectional profile of a line-and-space patterned resist layer having a line width of 0.80 μm was orthogonal standing upright on the substrate surface. The dimensional fidelity of the patterned resist layer was 1.18 and the temperature for heat resistance was 200° C.
EXAMPLE 10
A positive-working photoresist composition was prepared by dissolving, in 400 parts of propyleneglycol monomethyl ether acetate, 30 parts of a first polyhydroxystyrene substituted by tert-butoxycarbonyloxy groups for 39% of the hydroxy groups and having a weight-average molecular weight of 8000 and a molecular weight distribution Mw:Mn of 1.5, 70 parts of a second polyhydroxystyrene substituted by ethoxyethoxy groups for 39% of the hydroxy groups and having a weight-average molecular weight of 8000 and a molecular weight distribution Mw:Mn of 1.5, 2 parts of the oxime sulfonate compound prepared in Example 2 as an acid-generating agent, 0.3 part of triethylamine, 0.2 part of salicylic acid and 5 parts of N,N-dimethylacetamide followed by filtration of the solution through a membrane filter of 0.2 μm pore diameter.
This photoresist solution was applied to the surface of a silicon wafer on a spinner followed by drying on a hotplate at 80° C. for 90 seconds to form a dried photoresist layer having a thickness of 0.7 μm, which was exposed pattern-wise on a minifying projection exposure machine (Model NSR-2005EX8A, manufactured by Nikon Co.) in doses stepwise increased with increments of each 1 mJ/cm 2 by varying the exposure time followed by a post-exposure baking treatment at 110° C. for 90 seconds and developed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide at 23° C. for 65 seconds followed by rinse with water for 30 seconds and drying. Recording was made there for the minimum exposure dose in mJ/cm 2 , which was 4 mJ/cm 2 in this case, as a measure of the sensitivity by which the resist layer in the exposed areas was completely dissolved away in the development treatment.
A scanning electron microscopic photograph was taken of the cross-sectional profile of the patterned resist line of 0.25 μm width to find that the cross-sectional profile was excellently orthogonal standing upright on the substrate surface.
Further, the heat stability of the patterned resist layer was tested by heating the resist layer on a hot plate to determine the lowest temperature for incipient flowing of a line-and-space pattern of 100 μm line width but no flow of the line-patterned resist layer could be detected at a temperature of 120° C. | Disclosed is a novel positive-working or negative-working chemical-sensitization photoresist composition useful in the photolithographic patterning works for the manufacture of electronic devices. The photoresist composition is characterized by a unique acid-generating agent capable of releasing an acid by the pattern-wise exposure of the resist layer to actinic rays so as to increase or decrease the solubility of the resist layer in an aqueous alkaline developer solution. The acid-generating agent proposed is a novel cyano group-containing oxime sulfonate di- or triester compound represented by the general formula
A[C(CN)═N--O--SO.sub.2 --R].sub.n,
in which each R is, independently from the others, an unsubstituted or substituted monovalent hydrocarbon group such as alkyl groups, A is a divalent or tervalent organic group or, preferably, phenylene group and the subscript n is 2, when A is a divalent group, or 3, when A is a tervalent group or, preferably 2. Since more than one of sulfonic acid molecules are released from one molecule of the sulfonate compound by the exposure to actinic rays, the chemical-sensitization photoresist composition exhibits high photosensitivity. | 2 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to the passivation of metallic medical implants and passivated metallic medical implants produced by these methods; and, in particular, to passivation methods that result in superior corrosion resistance and performance characteristics, as compared to conventional nitric acid passivation.
2. Background
The majority of metals are thermodynamically unstable in aqueous solutions and tend to oxidize easily in the presence of hydrogen ions, oxygen, and water because the free energy change during the formation of oxides has a significantly negative value. Nevertheless, certain metals such as iron, aluminum, chromium, nickel, titanium, zirconium, niobium, and tantalum as well as their alloys react very slowly with the above substances, due to the presence of a protective surface film that markedly reduces the corrosion rate. Passive surface films are those thin films (up to roughly 10 nanometers, depending on the material) which spontaneously form to maintain surface passivity. For example, stainless steel is stainless because of the thin protective chromium oxide/hydroxide passive film which can form in air.
The occurrence of passivity makes it possible to use metals in chemically aggressive media, even in the physiological environment which is particularly hostile to metals. Virtually all metallic medical implants (such as, for instance, stainless steels, Co--Cr--Mo alloy, titanium, and Ti--6Al--4V alloy, tantalum, etc.) must exhibit a minimum level of self-maintained passivity in the human body. That is, the passive oxide/hydroxide film on the metallic implant must not only withstand chemical attack by damaging species, like chloride ions which are abundantly available in the body fluids, but it also must effectively redevelop if mechanically removed, i.e. it must spontaneously repassivate.
Mechanical disruption of the passive film may occur from abrading against adjacent bone due to motion of the implant, or from articulation against counter bearing surfaces, such as ultra high molecular weight polyethylene. During repassivation, significant amounts of dissolved metal ions can be produced, depending on the degree of surface destruction and on the quality of the passive film on the undisturbed surface portion of the implant. The long-term consequences of metal ion release into the body environment are not well understood; however, it is generally accepted that such release should be minimized. Thus, the effectiveness of a passive surface film is an important aspect of implant biocompatibility.
The nature of the passive film primarily depends on the metal and the conditions under which it develops. The protection provided by this surface layer in a specific environment is mainly determined by the stability of the passive film in the specific environment.
The unique feature of biomedical applications is that the implant metal or alloy must not only be safeguarded, but its effects on the physiological environment must also be considered. Commonly used implant metals include low carbon austenitic stainless steel (AISI types 316L, 316, 303, and 304); cobalt-chromium alloy (ASTM F-75, F-90, F-799); and titanium and titanium alloys such as Ti--6Al--4-V alloy (ASTM F-136), PROTASUL 100 (Ti--6Al--7Nb).
For adequate biocompatibility , the effectiveness of the passive film on a metallic implant is extremely important because adverse action between the implant material and the body fluids has to be prevented. It is desirable that the implant should not corrode and, if it does corrode, then the biological environment should not be adversely affected by the corrosion products. This latter requirement highlights the need for a unique, entirely different approach to the use of metal and coated metals in biomedical systems.
In addition to conventional corrosion considerations, the release of corrosion products into the physiological environment should also be minimized based on a biological scale. Creating overly positive initial corrosion potentials by enforced, drastic passivation should also be avoided in order to eliminate the formation of metal ions (e.g., Cr 6+ ions) with undesirable biological effects, or not to induce processes such as blood clotting on the implant surface, which may further result in thrombosis and inadequate blood compatibility. An effective passivation method, therefore, must produce a protective layer in the metallic implant which is similar to the one that develops spontaneously in body fluids, and which undergoes the least structural and compositional changes after implantation (hence, minimizing metal ion release into the body).
The passivation method currently used for metallic biomedical implants is essentially routine passivation by nitric acid, according to ASTM F-86 "Standard Practice for Surface Preparation and Marking of Metallic Surgical Implants." This practice provides a description of final surface treatment with nitric acid, using the following procedure: "Immerse in 20 to 40 volume % nitric acid (specific gravity 1.1197 to 1.2527) at room temperature for a minimum of 30 min. For an accelerated process, this acid solution, heated from 120° to 140° F. (49° to 60° C.), may be used for a minimum of 20 min.--Employ thorough acid neutralizing and water rinsing process and a thorough drying process."
The initial oxide/hydroxide layer that develops spontaneously on the metallic implant prior to the final passivation may considerably affect the quality of the passive film. That is, if a metal is covered by a non-coherent surface layer that has formed during processing and cleaning procedures, exposure to a powerful oxidizing agent like nitric acid can easily result in a thick but considerably rough passive layer, depending on how uniform the previously developed spontaneous surface layer was.
In the late 1960's and early 1970's, efforts were made to evaluate the effectiveness of the nitric acid passivation performed according to ASTM F-86. Revie and Green (Corrosion Science, vol. 9 p. 763-770 (1969) contend that prepassivation in oxygenated NaCl solution markedly improves the corrosion resistance of implant materials (except for titanium). The authors recommended this passivation method in preference to any form of HNO 3 treatment for types 304 and 316 stainless steels and Vitallium (cobalt) alloy. They also stated that routine storage of all metallic implants in oxygenated isotonic NaCl could easily be adopted because of its ease of handling and its availability in all hospitals. Similar conclusions were drawn by Aragon and Hulbert for Ti--6Al--4V alloy. J. Biomed. Mater. Res., vol. 6 p. 155-164 (1972). These researchers suggested that preparation techniques for Ti and Ti-alloys, other than the ASTM recommended practice F-86(68), should be explored and storage of the prosthesis in isotonic saline solution should give good results.
The saline passivation of metallic surfaces has never been introduced as a routine industrial passivation procedure. While the Revie and Green results indicate that nitric acid passivation does not result in optimum performance characteristics for biomedical applications, saline passivation does not produce the best protective layer either.
In Sato, "Toward a More Fundamental Understanding of Corrosion Processes," 45 Corrosion 354 (1989), the author discloses that, in the presence of a neutral chloride solution, an anion-selective precipitate film is formed on the surface of corroding metal due to selective mass transport in anodic corrosion processes. When the anodic metal corrosion proceeds under such a precipitate film, the internal occluded solution (i.e. the solution layer between the metal and the passivated layer) will become enriched in both metal ions and chloride ions, because the anodic current throughout the anion-selective precipitate film is carried mainly by the chloride ion migrating from the external bulk solution to the occluded solution. Both the accumulation of metal chloride, leading to acidification, and the continuous electro-osmotic flow of water molecules into the occluded solution, will provide conditions favorable for localized corrosion to take place under an anion-selective corrosion precipitate. Hence, a less uniform passive film is likely to develop in the presence of aggressive chloride ions.
Sato also contends that the presence of cation-selective corrosion precipitates on the surface of corroding metals is favorable. In this instance, chloride ions are prevented from migrating into the occluded solution. Instead, the anodic corrosion current through the precipitate film is carried by predominantly mobile cations, such as hydrogen ions, which migrate outward leaving dissolved metal ions in the occluded solution. This eventually results in the formation of metal hydroxides at a rate controlled by the inward diffusion of water through the corrosion precipitate film. Under these conditions, there is no accelerated corrosion propagation and corrosion will be retarded. Most of the non-aggressive oxyanions in common use, such as sulfate, borate, chromate, molybdenate, and tungstate, are capable of converting anion-selective hydrated metal oxides to cation-selective phases by their adsorption or incorporation into the phases.
There exists a need for metallic implants surface passivated with a tightly adherent coating that exhibits improved long term corrosion resistance in the body. Further, the passivated surface should be easily formed by conventional manufacturing processes and be resistant to those conventional sterilization techniques that implants undergo before surgical implantation.
SUMMARY OF THE INVENTION
The invention provides passivated metal implants with superior in vivo corrosion resistance and methods of passivating metal implant surfaces for corrosion resistance in the body. The invention implants are covered with a thin, uniform tightly adherent oxide/hydroxide coating (i.e. coating of oxide, coating of hydroxide or coating of a mixture of oxide and hydroxide) that is resistant to corrosion in the body. In the invention methods, the metallic implant surfaces are either spontaneously or galvanically passivated in aqueous water soluble salt solutions, preferably alkaline metal salt solutions, containing non-aggressive oxyanions such as sulfate, phosphate, di-hydrogen phosphate, mono-hydrogen phosphate, borate, and the like. Galvanic passivation in these electrolytic solutions may be achieved by galvanic coupling of the metal or alloy implant with an electrochemically more noble material, such as carbon. Such passivation methods, utilizing non-aggressive oxyanions, provide a thin and uniform passivated surface on the metal implant, thereby rendering the implant more stable in the biological environment, and therefore more biocompatible.
In both the spontaneous and galvanic surface passivation methods, aggressive oxyanions and chloride ions are excluded from the passivating solutions resulting in a more uniform barrier film which is less prone to localized breakdown processes when placed into the biological environment. Additionally, since the nature of the inventive passivating solutions is more similar to that of body fluids, than nitric acid, the protective ability of the invention passive film, when exposed to the body fluids, undergoes much less alteration. The inventive methods also reduce the disadvantageous effects of initial surface conditions on the effectiveness of passivation. This is largely due to the absence of aggressive species that may further enhance the non-uniform character of the initial surface film.
In the galvanic method there is galvanic coupling of the metal or alloy implant with, for instance, carbon. Without being bound, it is theorized that the macroscopic separation of anodic and cathodic processes may give rise to a lower local pH at the metal surface and, this may assist in the removal of undesirable corrosion products from the passive film. Since the breakdown potential in the passivating solution is much more positive than the potential at which anodic dissolution takes place, no specific restriction on the metal/carbon surface area ratio is necessary.
The invention provides relatively inexpensive methods of treating metallic implants to produce the invention coated implants that offer significant advantages in terms of corrosion resistance and that minimize the production of corrosion by-products in the body.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1a and 1b show the effect of initial and passivating conditions on two different samples of 316L stainless steel coupons.
FIGS. 2a and 2b show the effect of initial and passivating conditions on two different samples of Cobalt-Chromium-Molybdenum alloy coupons.
FIG. 3a and 3b show the effect of initial and passivating conditions on two different samples of Titanium-6 Aluminum-4 Vanadium alloy coupons.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The invention surface passivation methods are generally useful for passivating the surface of metallic implants. For example, the inventive surface passivation methods may appropriately be used for treating those metals and their alloys typically used as implant materials. These include, but are not limited to, stainless steels such as, for example, low carbon austenitic stainless steels such as AISI types 316, 316L, 303 and 304, cobalt-chromium alloys, cobalt-chromium-molybdenum alloys, and the like. Further, the method may be used to passivate the surface of implants fabricated from more exotic metals and their alloys, such as for instance, the Group 4 and 5 metals including zirconium, titanium, tantalum, and niobium.
As used in the specification and claims, "non-aggressive oxyanions" refer to chemically stable oxyanions whose presence promotes the formation of a uniform passive layer on the implant surface but does not chemically react with the implant surface. Further, "spontaneous passivation" refers to passivation without the macroscopic separation of the anodic and cathodic processes. Also, "galvanic passivation" refers to passivation with the macroscopic separation of the anodic and cathodic processes, but without the need for an outer current source. The term "thin" as applied to the passive oxide/hydroxide coatings refers to coatings of thickness from about 1 to about 20 nm, preferably from about 2 to about 3 nm.
Prior to passivation, the metallic implant surface should be prepared by the methods that are known in the prior art and that are prescribed for use with nitric acid passivation, but without the use of nitric acid. The implant should be wiped clean of any large debris and then cleaned to remove grease, coolant, or other shop debris. Optimum passivation results are obtained when the implant surface is first thoroughly cleaned (i.e. as clean as the implant would need to be for plating). Typical cleaning procedures are known to those skilled in the art, and include solvent cleaning (the solvent containing a degreaser), followed by an alkaline soak cleaning, and thorough water rinsing. In order to clean the implant, the implant may be immersed in the cleaning solution, swabbed with the cleaning solution, or the solution may be applied to the implant by pressure spraying.
An aqueous passivation solution is then prepared from the salts of water soluable metals, preferably alkali metals, with non-aggressive oxyanions. The non-aggressive oxyanion may be a sulfate, phosphate, mono-hydrogen phosphate, di-hydrogen phosphate, borate, and the like. The salt concentration of these passivation solutions may vary within a wide range, with the preferred concentration range being from about 0.05 equivalents per liter to about 0.25 equivalents per liter. The preparation of such solutions is well known to those of ordinary skill in chemistry and does not require any special skills or precautions, which are often necessary in the preparation of nitric acid passivation solutions.
The natural pH value of the solutions as set by the dissolution of the particular salts is preferred. However, the pH may also be adjusted by the corresponding acid, if desirable. Furthermore, the passivation solution may be oxygenated, e.g. by bubbling with purified air or oxygen, to improve the passivation processes.
After the passivating solution is prepared, the metallic implant is immersed in the solution, which is then preferably heated to a temperature is 20° C. to about 50° C. The preferred temperature is 37° C. (human body temperature). While temperatures greater than 50° C. can be employed, the greater the temperature, the faster is the passivation rate, resulting in a less uniform passive layer.
Depending upon the initial surface activity, spontaneous passivation may require that the metallic implant remain in the solution from about 2 hours to about 36 hours, depending upon the solution temperature. The preferred time during which the implant typically remains in the passivating solution, in order for spontaneous passivation to occur, is about 24 hours when the temperature is about 35°-40° C.
During the passivation process, a thin oxide/hydroxide film spontaneously forms on the metallic surface of the implant. The maximum film thickness that results is about 10 nm; however, the usual resulting thickness is from about 1 to about 8 nm, with the preferred passivating film layer thickness being 2-3 nm. The thinner film surface is preferred because it is usually more uniform and therefore provides better protection for the alloy surface. After a time sufficient to form the oxide/hydroxide film, the metallic implant is removed from the passivating solution, water rinsed, and dried.
In an alternative embodiment, the galvanic coupling of the metal or alloy implant with electrochemically more noble materials, such as carbon, is carried out in the previously described passivation solutions, using, for example, carbon racks. After the passivation solution is prepared, a mechanically coupled graphite rod and the metallic implant are both immersed in the electrolytic solution and heated to the same temperatures as specified for spontaneous passivation. The mechanical contact of this system establishes a natural galvanic couple with the resultant separation of the anode and cathode processes.
The effect of various initial and passivating conditions are illustrated in FIGS. 1-3, for two samples for each material (SS-316L, Co--Cr--Mo, and Ti--6Al--4V). The anodic polarization curves, one day after passivation, were determined potentiodynamically in lactated Ringer's solution open to air. Such a determination was obtained by applying varying potential differences (in millivolts) and measuring the reulting currents in microamps. In performing these tests, we used an AG & G Princeton Applied Research Model 173 Potentiostat and SoftCorr Model 332 Software. The resultant current density reading (x-axis, microamps cm 2 ) was then recorded and plotted against the particular applied potential difference versus a saturated calomel reference electrode (y-axis, millivolts) to obtain the polarization curve. This curve was then extrapolated to determine the passive corrosion current density (icorr). The icorr for the implant passivated by the example method (i.e. "icorr, example pass".) was then compared to the icorr for nitric acid passivation (i.e. icorr, HNO3 pass.) in the form of a ratio: ##EQU1##
A small ratio corresponds to a low corrosion current indicating the presence of a more protective passive film, as compared to the standard nitric acid passivation method. The less the polarization curves are affected by the initial surface conditions, the more effective the passivation method is for practical use.
The following examples do not limit the scope of the invention, but are intended to illustrate the effectiveness of the invention as described above and claimed hereafter.
EXAMPLE 1
A polished (mirror finish) stainless steel metallic coupon of AISI type 316L was wiped clean of debris and then thoroughly cleaned by typical cleaning methods, and thorough water rinsing.
A passivating solution of 25 grams per liter of Na 2 SO4.10H 2 O (pH7) was prepared. The cleaned, metal coupon was then immersed in this solution, which was maintained at a temperature of approximately 22° C. for 16 hours to produce a spontaneous passive thin, uniform film on the coupon's surface.
EXAMPLE 2
A metallic coupon as described in Example 1 was cleaned according to Example 1 and then immersed in a passivating solution of 20 grams per liter of Na 3 PO 4 .12H 2 O (pH4), which was maintained at a temperature of approximately 22° C. as for Ex. 1 for 16 hours, to produce a spontaneously passivated thin, uniform film on the surface of the coupon.
EXAMPLE 3
A polished (mirror finish) metallic coupon formed of cobalt-chromium-molybdemum was cleaned as described in Example 1. The coupon was then immersed in a passivating solution of 20 grams per liter Na 3 PO 4 .12H 2 O to which had been added phosphoric acid to adjust the pH to pH4. The coupon was then maintained at a temperature of approximately 22° C. for 16 hours, to produce a spontaneously passivated thin, uniform film on the coupon's surface.
EXAMPLE 4
A metallic coupon as described in Example 3 was cleaned as described in Example 1. The coupon was then immersed in a passivating solution of 20 grams per liter Na 3 PO 4 .12H 2 O (pH12), which was maintined at a temperature of approximately 22° C. for 16 hours, to produce a spontaneously passivated thin, uniform film on the coupon surface.
EXAMPLE 5
A metallic coupon as described in Example 1 was cleaned according to Example 1. The coupon was then immersed in a passivating solution of 25 grams per liter Na 2 SO 4 .10H 2 O (pH7). The solution was heated to a temperature of 37° C., and the coupon was maintained in this heated solution for 24 hours, to produce a spontaneously passivated thin, uniform film on the coupon surface.
EXAMPLE 6
A metallic coupon as described in Example 3 was cleaned as described in Example 1. The coupon was then immersed in a passivating solution of 25 grams per liter Na 2 SO 4 .10 H 2 O (pH7). The solution was heated to a temperature of 37° C., and the coupon was maintained in this solution for 24 hours to produce a spontaneously passivated thin, uniform film on the coupon surface.
EXAMPLE 7
A metallic coupon described in Example 1 was cleaned as described in Example 1. The coupon was then immersed in a passivating solution of 25 grams per liter Na 2 SO 4 .10H 2 O (pH7) which was also aerated. A graphite rod, which was also immersed in this passivating solution, was mechanically coupled to the metallic coupon. The solution was heated to a temperature of 37° C., and the mechanically coupled coupon and graphite rod system were maintained in the solution for 24 hours. This mechanical contact established a natural galvanic couple with the resultant separation of the anode and cathode processes to produce a thin, uniform passivated film on the coupon surface.
EXAMPLE 8
A metallic coupon as described in Example 3 was cleaned according to Example 1. The coupon was then immersed in a passivating solution of 25 grams per liter Na 2 SO 4 .10 H 2 O (pH7), which was also aerated. A graphite rod, which was also immersed in this passivating solution, was mechanically coupled to the metallic coupon. The solution was heated to 37° C., and the mechanically coupled coupon and graphite rod system was maintained in this solution for 24 hours to produce a thin, uniform passivated film on the coupon surface.
EXAMPLE 9
A polished (mirror finish) metallic coupon of titanium-6 aluminum-4 vanadium was cleaned according to the procedure described in Example 1. The coupon was then mechanically coupled to a graphite rod, and subsequently immersed in a passivating solution of 25 grams per liter Na 2 SO 4 .10 H 2 O (pH7), which was also aerated. The solution was heated to a temperature of 37° C., and the mechanically coupled coupon and graphite rod system were maintained in the solution for 24 hours to produce a thin, uniform passivated film on the coupon surface.
EXAMPLE 10
The ratios of the passive current density (icorr) compared to the icorr for nitric acid passivation for each metallic coupon and passivation method described in Example 1-9 are listed in the Table 1 below. The nitric acid passivation procedure was performed in 20 vol. % nitric acid at a temperature of about 22° C. for 30 minutes. The potentiodynamic curves were determined in Lactated Ringer's solution open to air one day after passivation.
TABLE 1______________________________________Passive Current Density Comparison icorr, example pass.Example icorr, HNO.sub.3 pass.______________________________________1 0.602 0.673 0.104 0.095 0.476 0.087 0.338 0.069 0.17______________________________________
Table 1 reveals that the inventive method resulted in significantly improved performance characteristics as compared to nitric acid passivation, as indicated by the lower ratio values. Samples passivated by the inventive method exhibited significantly lower corrosion current densities (I) and less positive corrosion potentials (E). Furthermore, the samples passivated by the inventive method were also less sensitive to the initial (i.e. prior to passivation) surface conditions.
EXAMPLE 11
FIGS. 1a and 1b show potentiodynamic curves obtained for two 316L stainless steel coupons. Each coupon was used twice, once to test nitric acid passivation and then, after polishing, to test the inventive method of non-aggressive anion passivation. The passivation methods were as follows for each coupon:
Test 1: The coupon was polished and then passivated by immersing the coupon in a solution of 20 vol. % HNO 3 at a temperature of 23° C., for 30 minutes.
Test 2: The coupon was polished and then stored in air for a period of 24 hours prior to passivation. The coupon was then immersed in a passivating solution of 20 vol. % HNO 3 , at a temperature of 50° C., for 20 minutes.
Test 3: The coupon used in test 1 was repolished and then passivated by galvanic coupling by immersing the coupon, coupled with a graphite rod, in an aerated passivating solution of 25 grams per liter 1672XNa 2 SO 4 .10H 2 O for a period of 24 hours.
Test 4: The coupon of test 2 was repolished and then stored in the air for a period of 24 hours prior to passivation via galvanic coupling as conducted for sample 3.
All of the above tests were conducted in a Lactated Ringer's solution conditioned at 37° C. for one hour. The potential was changed at a rate of 1 mV/sec.
EXAMPLE 12
FIGS 2a and 2b show potentiodynamic curves obtained for two cobalt-chromium-molybdenum alloy coupons. Each coupon was used twice, once to test nitric acid passivation and then, after polishing, to test the inventive method of non-aggressive anion passivation. The passivation methods are as follows:
Test 1: The coupon was polished and then passivated by immersing the coupon in a passivating solution of 20 vol. % HNO 3 , at a temperature of 23° C., for 30 minutes.
Test 2: The coupon was polished and stored in air for a 24-hour period prior to passivation. The coupon was then immersed in a passivting solution of 20 vol. % HNO 3 , at a temperature of 50° C., for 20 minutes.
Test 3: The coupon used in Test 1 was repolished and then passivated by galvanic coupling by immersing the coupon, coupled with a graphite rod, in an aerated passivating solution of 25 grams per liter Na 2 SO 4 .10H 2 O for a period of 24 hours.
Test 4: The coupon used in Test 2 was repolished and then stored in air for a period of 24 hours prior to galvanic coupling as conducted for Test 3.
All of the above tests were conducted in a Lactated Ringer's solution conditioned at 37° C. for one hour. The potential was changed at a rate of 1 mV/sec.
EXAMPLE 13
FIGS. 3a and 3b show potentiodynamic curves obtained for two Titanium-6 Aluminum-4 Vanadium alloy coupons. Each coupon was used twice, once to test nitric acid passivation and then, after polishing, to test the inventive method of non-aggressive anion passivation. The passivation methods are as follows:
Test 1: The coupon was polished and then passivated by immersing the coupon in a solution of 20 vol. % HNO 3 , at a temperature of 23° C., for 30 minutes.
Test 2: The coupon was polished and then stored in air for a period of 24 hours prior to passivation. The coupon was then immersed in a passivating solution of 20 vol. % HNO 3 , at a temperature of 50° C., for 20 minutes.
Test 3: The coupon used in test 1 was repolished and then passivated by galvanic coupling by immersing the coupon, coupled with a graphite rod, in an aerated passivating solution of 25 grams per liter Na 2 SO 4 .10H 2 O for a period of 24 hours.
Test 4: The coupon of test 2 was repolished and then stored in air for a period of 24 hours prior to passivation via galvanic coupling as conducted for sample 3.
All of the above tests were conducted in Lactated Ringer's solution conditioned at 37° C. for one hour. The potential was change at a rate of 1 mV/sec.
The invention has been described with reference to its preferred embodiments. A person of ordinary skill in the art, having read the above specification, may appreciate modifications that are within the scope of the invention as described above and claimed here below. | Passivated implants and passivation methods that provide superior corrosion resistance and surface performance characteristics as compared to conventional nitric acid passivation are disclosed. The method uses either the spontaneous or galvanic passivation of metallic prosthetic implants in aqueous alkali salt solutions containing non-aggressive oxyanions to produce a thin and uniform passive coating on the metal implant, thereby rendering the implant more stable in the biological environment. | 2 |
BACKGROUND OF THE INVENTION
The present invention relates to wear disks for crimping machines for manufacturing synthetic fibers.
Such wear disks, which are to prevent the sideways escape of the tow from the nip of the stuffer box, are known; their requirements have been discussed at great length for example in DE-A-2 113 886.
According to said reference, wear disks must be highly heat conductive, since in crimping, in particular dry crimping, the moving fiber bundles create friction which is converted into heat. To perform their function, wear disks must be in frictional contact with the end surfaces of the intake rolls, and the fiber plugs stuffed in the crimping box are moved along them under high pressure. In this process, the frictional area of the disks, i.e. a relatively small portion of their surfaces, additionally develops a great deal of heat. The material of the wear disks must therefore be highly heat conductive to ensure rapid dissipation of the heat generated and to prevent a fiber-damaging increase in the temperature of the friction surface. The high level of friction also leads to rapid wear of the disks, which is why it is an advantage to use a very abrasion-resistant material to make these parts. Abrasion-resistant, hard materials which have been proposed for the manufacture of wear disks are for example brass or ceramics (U.S. Pat. No. 4,395,804) or alumina mixed ceramics, e.g. (R) ALSIMAG (U.S. Pat. No. 2,311,174). The conventional materials which have this property, for example sinter ceramics formed from alumina or zirconia/silica, however, are not sufficiently heat conductive. A further disadvantage of these very hard materials is that any isolated instances of damage to the frictional surfaces of rotating disks are no longer repaired (worn away) in use and that the end surfaces of the intake rolls may be damaged.
Examples of softer materials recommended for wear disks are bronze, aluminum, nylon and PTFE (DE-A-3 503 447, DE-A-2 604 505, U.S. Pat. No. 3,237,270 and DE-A-1 435 441) and even graphite (DE-A-2 113 886). A problem with the current wear disks made of graphite is not only their high rate of wear but also their staining of the filaments, which is highly undesirable.
It is true that the widely used brass wear disks are highly heat conductive, but they still do not have a sufficiently long life or adequate self-repair properties. Plastics disks possess inadequate thermal conductivity.
SUMMARY OF THE INVENTION
It is an object of the present invention to manufacture wear disks of optimal abrasion resistance and high thermal conductivity which in addition have the advantage over conventional materials that they do not discolor the fiber bundles.
Wear disks must be manufactured to high precision and advantageously either consist of a relatively abrasion-resistant material or have been provided with a specific surface treatment in order that the tow or multifilament yarn may survive the crimping process with a minimum of fiber damage.
If the stress on the wear parts is not excessively high, it is frequently the case that surface treatment techniques, for example flame hardening, induction hardening and case hardening, already provide adequate wear protection.
However, a high surface hardness alone does not guarantee a high abrasion resistance, and, what is more, the layers formed by this process are very thin, so that they do not survive for a long period. In certain cases, even wear-resistant layers applied by the metal spraying technique have proved useful. An important prerequisite is firm adhesion to the basic material and inadequate toughness of the sprayed-on layer, which must not tend to deform or crumble off. Such surface treatments are difficult to carry out and raise the cost of friction disks considerably. In addition, it is not possible to remove the abrasion problems in full by this measure. Surface treatments are thus likewise not a satisfactory solution.
DETAILED DESCRIPTION OF THE INVENTION
By contrast, the above-described problems are substantially overcome by the wear disks according to the present invention. The wear disks according to the present invention are made of a sinter material which is formed from carbon and a metal or an alloy thereof and which combines optimal self-healing properties with a very high resistance to wear from friction stresses.
The friction materials required here convert kinetic energy into thermal energy. Such friction materials are these days also widely required in automotive construction and general mechanical engineering. They comprise multicomponent sinter materials, in some instances of an extremely complicated composition. Even sintered materials as used in the present invention are already known. They optionally contain for example from 5 to 70% of graphite, from 85 to 30% of copper and possibly up to 10%, preferably from 8 to 10% of tin, up to 15% of lead and up to 12% of zinc. In the formation according to the present invention, it is advantageous to have a high copper content within the range of between 70 and 90%, preferably above 80%. It is particularly preferred if the metal component consists of copper only. The high copper content makes it possible to increase the thermal conductivity a great deal; it should exceed 80 W×K 1 ×m -1 . It is preferably from 80 to 200, in particular 100-150 W×K -1 ×m -1 . In some particularly highly suitable materials, the "metal coals" mentioned hereinafter by way of example, the thermal conductivity is 125±15.
In principle, however, the copper can also be replaced by other metals in order that the properties of the sintered wear disks may be modified according to the desired use. For instance, it can be of advantage, for example, to replace the copper by iron, tin, zinc or lead or else only to combine it with these elements; but even the high-melting metals of subgroups 4, 5 and 6, combined with carbon into sinter materials, show advantageous ductile, wear-resistant properties.
The structure also has an effect on the properties of the sinter materials required, and it can be expressed for example in terms of the apparent density. Preference is given to sinter materials having an apparent density between 4 and 7 g cm 3 , in particular between 5 and 6 g cm 3 .
The apparent density is the ratio of the mass and the macroscopic volume of the material.
A particularly highly suitable material for the wear disks according to the present invention has surprisingly been found to be the so-called "metal coals", which are among the oldest sintered composites and which had hitherto been predominantly used as collector brushes for electrical motors.
Metal coals which are particularly highly suitable for use as the material for the wear disks according to the present invention comprise 80-85% of copper, 10-16% of lead and 5-9% of graphite. Very highly suitable commercial materials of this kind are for example the metal coal standard grades BDB and NL from W. L. Eichberg, Berlin.
The wear disk according to the present invention represents an optimal combination of wear resistance and self-healing properties, is highly heat conductive and surprisingly, unlike conventional materials, does not cause any staining of the yarns. This combination of positive properties leads to a long trouble-free running time of the crimping machines equipped therewith. Tows processed therewith are particularly uniform across the entire cross-section, whereas conventional processes frequently produce in practice a non-uniform sinusoidal or angular toothed shape of crimp. The uniform crimp arc guarantees good textile processing, including in particular on cutting and stretch-breaking tow converters. | A wear disk for a crimping machine used in the manufacture of synthetic fibers comprises a sinter material of metal and carbon having an apparent density of from 4 to 7 g/cm 3 . The metal of the sinter material is particularly copper or an alloy thereof and therefore highly heat conductive. | 3 |
TECHNICAL FIELD OF THE INVENTION
[0001] The present invention relates to the field of scrolling in sets of items, for instance lists provided in portable electronic devices, and more particularly to a method and a device for varying the scrolling speed for a set of items.
DESCRIPTION OF RELATED ART
[0002] The cellular phones of today have more and more different functions and applications in them. In order to sort between different functions and data relating to functions, the phones are normally provided with a menu system, in which a user can scroll in order to find data or functions that are grouped together. An example of such a group or set is for instance a telephone book, which lists a number of contacts and their corresponding phone numbers.
[0003] In the phones of today, there does not to the best of our knowledge exist the possibility to scroll lists with different speeds, they all use the same scrolling speed. This is a disadvantage, because different users might have different needs for scrolling fast, either because of personal differences or because of differences related to the items scrolled. One user might for instance need a faster scrolling speed than another user. The one and same user might also have a need for different scrolling speeds because for instance the number of items scrolled can be many, which might give rise to the need of a high scrolling speed, whereas in some other instances a slower scrolling speed might be needed because the items scrolled are few. Another reason for varying scrolling speed is that a user might be alert with quick reactions at one point in time and tired with slow reactions at another point in time, which gives rise to the need to provide different scrolling speeds also for a single user. In short there is a need to provide personalised scrolling speeds.
[0004] In the art of computers it is known to provide varied scrolling speeds automatically. Here the scrolling speed is increased automatically when a user is for instance scrolling a long text document. The user does however not have full control of this scrolling, and will in many cases feel that the scrolling goes too slowly in the beginning and too fast in the end to be able to control the scrolling properly.
[0005] There is thus a need for providing varied scrolling speeds that can be fully controlled by a user in a simple manner.
SUMMARY OF THE INVENTION
[0006] The present invention is thus directed towards providing varied scrolling speeds that can be fully controlled by a user in a simple manner.
[0007] This is achieved by detecting a scrolling action selection and a scrolling speed variation selection and changing the scrolling speed in dependence of these selections.
[0008] One object of the present invention is to provide a method enabling varied scrolling speeds that can be fully controlled by a user in a simple manner.
[0009] According to a first aspect of the present invention, this object is achieved by a method of varying the scrolling speed provided for a set of items comprising the steps of:
providing a set of items of information that can be scrolled by a user, detecting a scrolling action selection from a user, detecting a scrolling speed variation selection from said user, and changing the scrolling speed in dependence of the selections made by the user.
[0014] A second aspect of the present invention is directed to a method including the features of the first aspect, wherein the step of changing is made based on simultaneous detection of scrolling action and scrolling speed variation.
[0015] A third aspect of the present invention is directed towards a method including the features of the first aspect, wherein the scrolling speed is varied with a certain step size and the scrolling speed is varied with said step size each time a scrolling speed variation selection is detected during detection of a scrolling action selection.
[0016] A fourth aspect of the present invention is directed towards a method including the features of the first aspect, wherein the scrolling speed is varied linearly when a scrolling speed variation selection is detected during detection of a scrolling action selection.
[0017] A fifth aspect of the present invention is directed towards a method including the features of the first aspect, wherein the scrolling speed variation is either an increase or a decrease of the scrolling speed.
[0018] A sixth aspect of the present invention is directed towards a method including the features of the fifth aspect, wherein a first user input unit allows actuation for a first direction and for a second opposite direction, each allowing scrolling in said direction, and a second user input unit allows actuation for the first and the second opposite directions, wherein the detection of a scrolling action selection by an actuation of the first input unit for one direction together with the detection of a scrolling speed variation selection by an actuation of the second user input unit for the same direction provides a scrolling speed increase and the detection of a scrolling action selection by an actuation of the first input unit for one direction together with the detection of a scrolling speed variation selection by an actuation of the second user input unit for the opposite direction provides a scrolling speed decrease.
[0019] A seventh aspect of the present invention is directed towards a method including the features of the first aspect, further comprising the step of saving a scrolling speed setting based on the changed scrolling speed.
[0020] An eighth aspect of the present invention is directed towards a method including the features of the seventh aspect, wherein the step of saving is performed automatically.
[0021] A ninth aspect of the present invention is directed towards a method including the features of the seventh aspect, wherein the step of saving is performed after detecting a selection of saving scrolling speed from the user.
[0022] A tenth aspect of the present invention is directed towards a method including the features of the seventh aspect, wherein the step of saving is performed for said set of items.
[0023] An eleventh aspect of the present invention is directed towards a method including the features of the tenth aspect, wherein the step of saving is also performed for at least one other set of items.
[0024] Another object of the present invention is to provide a device, which provides varied scrolling speeds that can be fully controlled by a user in a simple manner and which gives the user a feeling of full control of the scrolling.
[0025] According to a twelfth aspect of the present invention, this object is achieved by a device for varying the scrolling speed provided for a set of items comprising:
an information presentation unit providing a set of items of information that can be scrolled by a user, a first user input unit, for allowing a scrolling action selection by the user, a second user input unit for allowing a scrolling speed variation selection by the user, and a control unit arranged to:
provide said set of items of information on the information presentation unit, detect a scrolling action selection by a user via said first user input unit, detect a scrolling speed variation selection via said second user input unit, and change the scrolling speed in dependence of the selections made by the user.
[0034] A thirteenth aspect of the present invention is directed towards a device including the features of the twelfth aspect, wherein the control unit is arranged to change the scrolling speed based on simultaneous detection of scrolling action and scrolling speed variation.
[0035] A fourteenth aspect of the present invention is directed towards a device including the features of the twelfth aspect, wherein the control unit is further arranged to vary the scrolling speed with a certain step size and the scrolling speed is varied with said step size each time a scrolling speed variation selection is detected during detection of a scrolling action selection.
[0036] A fifteenth aspect of the present invention is directed towards a device including the features of the twelfth, wherein the control unit is further arranged to vary the scrolling speed linearly when a scrolling speed variation selection is detected during a detection of a scrolling action selection.
[0037] A sixteenth aspect of the present invention is directed towards a device including the features of the twelfth aspect, wherein the scrolling speed variation is either an increase or a decrease of the scrolling speed.
[0038] A seventeenth aspect of the present invention is directed towards a device including the features of the sixteenth aspect, wherein the first user input unit allows actuation for a first direction and for a second opposite direction, each allowing scrolling in said direction, and the second user input unit allows actuation for the first and the second opposite direction, wherein the control unit in detecting a scrolling action selection by actuation of the first input unit for one direction together with detecting of a scrolling speed variation selection by an actuation of the second user input unit for the same direction provides a scrolling speed increase and in detecting of a scrolling action selection by detection of an actuation of the first input unit for one direction together with detecting of a scrolling speed variation selection by an actuation of the second user input unit for the opposite direction provides a scrolling speed decrease.
[0039] An eighteenth aspect of the present invention is directed towards a device including the features of the twelfth aspect, further comprising a scroll speed storage and wherein the control unit is further arranged to save a scrolling speed setting in the scroll speed storage based on the changed scrolling speed.
[0040] A nineteenth aspect of the present invention is directed towards a device including the features of the eighteenth aspect, wherein the control unit is arranged to automatically save the scrolling speed setting.
[0041] A twentieth aspect of the present invention is directed towards a device including the features of the eighteenth aspect, wherein the control unit is arranged to save the scrolling speed setting after detecting a selection of saving scrolling speed from the user.
[0042] A twenty-first aspect of the present invention is directed towards a device including the features of the eighteenth aspect, wherein the control unit is arranged to save the scrolling speed setting for said set of items.
[0043] A twenty-second aspect of the present invention is directed towards a device including the features of the eighteenth aspect, wherein the control unit is arranged to save the scrolling speed setting for at least one other set of items.
[0044] A twenty-third of the present invention is directed towards a device including the features of the twelfth aspect, wherein the first user input unit is provided as at least one navigation key for navigating in a menu system of the device and the second user input unit is provided as at least one button on the side of the device normally used for volume settings or vice versa.
[0045] A twenty-fourth aspect of the present invention is directed towards a device including the features of the twelfth aspect, wherein the first user input unit is provided as at least one button on the side of the device normally used for volume settings and the second user input unit is provided as at least one navigation key for navigating in a menu system of the device.
[0046] A twenty-fifth aspect of the present invention is directed towards a device including the features of the twelfth aspect, wherein the device is a portable electronic device.
[0047] A twenty-sixth aspect of the present invention is directed towards a device including the features of the twenty-fifth aspect, wherein the device is a portable communication device.
[0048] A twenty-seventh aspect of the present invention is directed towards a device including the features of the twenty-sixth aspect, wherein the device is a cellular phone.
[0049] The invention has the following advantages. A user can directly and in a simple manner control the scrolling speed when he is in the process of scrolling. The invention is also very inexpensive to implement, because it can be implemented using the user input units already provided in the device and the speed variation function can be provided with just some extra software in addition to the scrolling software already existing.
[0050] The embodiment according to aspects six and seventeen has the further advantage that the increasing of the scrolling speed when the actuations corresponding to the same directions coincide, and otherwise decreasing the scrolling speed also gives a user a natural and intuitive feeling that selection of change of scrolling speed matches with the scrolling direction.
[0051] The embodiment according to aspects ten and twenty-one has the further advantage that by storing the scrolling speed for a particular set of items, different scrolling speeds tailored after the different sets can be provided for a user.
[0052] It should be emphasized that the term “comprises/comprising” when used in this specification is taken to specify the presence of stated features, integers, steps or components, but does not preclude the presence or addition of one or more other features, integers, steps, components or groups thereof.
BRIEF DESCRIPTION OF THE DRAWINGS
[0053] The present invention will now be described in more detail in relation to the enclosed drawings, in which:
[0054] FIG. 1 shows a front view of a portable electronic device in the form of a cellular phone,
[0055] FIG. 2 shows a block schematic of the relevant parts of the invention inside the phone in FIG. 1 , and
[0056] FIG. 3 shows a flow chart of a method according to the invention.
DETAILED DESCRIPTION OF EMBODIMENTS
[0057] A device according to the invention, which here is a portable electronic device 10 is shown in a front view in FIG. 1 . In the preferred embodiment the device is a cellular phone 10 having an information presentation unit in the form of a display 14 , a first user input unit 20 in the form of a navigation key in a keypad 18 . The device also has an antenna. This is however not shown because it is provided in the interior of the phone. The device also includes a second user input unit 16 in the form of a key or button 16 provided on the side of the phone. The button 16 is a so called volume button, which can be used for adjusting the volume setting of the phone, but in the present invention it has one further function, which will be described in more detail below. The volume button 16 can be actuated in an upwards direction and in an opposite downwards direction, which is indicated by an arrow pointing in both these directions in the figure. Apart from making and receiving telephone calls, the keypad 18 is used for entering information such as selection of functions and applications and responding to prompts and the display 14 is used for displaying functions and prompts to a user of the phone. In order to do this, the keypad 18 includes the navigation key 20 , which can be used for navigating up and down through a menu system provided in the phone. This is also indicated by the navigation key 20 being provided with an arrow pointing both upwards and downwards. In the menu system sets of items are provided in the form of lists. In FIG. 1 one such list of items is shown. The list is here a list of contacts provided in a phone book of the phone, where the display 14 shows the name of the contact together with a phone number of the contact. In FIG. 1 the list is shown as having a first item 20 , showing the name of Eral and his phone number 1234 , a second item 22 , showing the name of Seven and his phone number 7893 , a third item 24 , showing the name of Tage and his phone number 3231 . Part of a fourth item 26 , which cannot be fully seen, is also shown for illustrative purposes. This list can be very long and in order for a user to find a contact, which he might want to call, he might have to scroll a long time through this list. A list can typically include as much as 200 contacts. The antenna 12 is further used for communication with other users via a network.
[0058] FIG. 2 shows a block schematic of the different parts of the phone 10 relevant to the present invention. The display 14 , the first user input unit 20 and the second user input unit 20 are here shown as separate boxes connected to a control unit 28 . The control unit 28 is furthermore connected to a scroll speed storage 30 .
[0059] The control unit is normally provided in the form of one or more processors with corresponding program memories containing suitable software code. The storage is also preferably provided in the form of a memory.
[0060] FIG. 3 shows a flow chart of the method according to the invention.
[0061] A preferred embodiment of the present invention will now be explained with reference to FIG. 1, 2 and 3 . This embodiment is also believed to be the best mode of the invention at the moment. Upon the selection of a list of items in the menu system of the phone, the control unit 28 retrieves the list of items 20 , 22 , 24 , 26 and presents it on the display 14 , step 32 . The control unit 28 thereafter awaits a scrolling action selection through inputs from the user via the navigation key 20 . If the key is not actuated or depressed, step 34 , the control unit continues to wait. If however the navigation key is actuated, step 34 , the control unit 28 goes on and scrolls the list with a stored step size, step 36 . This scrolling is performed as long as the navigation key is actuated or depressed. The step size used is retrieved from scroll speed storage 30 prior to the scrolling. As long as the navigation key is depressed the control unit 28 continues to scroll the list of items. At the same time it also awaits a scrolling speed variation selection through actuation of the volume button 16 by the user. If the volume button is not actuated, step 38 , the control unit goes back and monitors the navigation key, step 34 . If however the second key is actuated, step 38 , the control unit 28 changes the scrolling speed.
[0062] The navigation key 20 enables the possibility to navigate in an upward direction and in a downward direction as is indicated by the arrow pointing in two directions in FIG. 1 . This means that if a lower part of the key is depressed, scrolling is made downwards, while if an upper part is depressed scrolling is performed in a direction upwards. The volume button also has the possibility to provide two different inputs in the same way, where the actuation in a direction upwards provides a higher volume and the actuation in a direction downwards provides a decrease of the volume. This button will according to the invention be used in a different way. When the control unit 28 thus has determined that both keys are actuated simultaneously, steps 34 and 38 , it goes on and checks the direction of the scrolling selection of the first and second user input units, step 40 . If both have been selected to go in the same direction, step 40 , i.e. either upwards or downwards, the scrolling speed is increased with one step, step 42 . However, if they have been selected to go in different directions, step 40 , i.e. one in the upwards direction and the other in the downwards direction, the scrolling speed is decreased one step, step 44 . This means that an actuation of the volume button in the upwards direction will only lead to an increase of the scrolling speed if the list is scrolled in the same direction. This gives a user a natural and intuitive feeling for what a scrolling speed increase or decrease would correspond to. The alternative, that one direction would always provide an increased speed would in many cases make a user feel uncomfortable when scrolling is actually performed in the opposite direction. When the scrolling speed has been increased or decreased, steps 42 , 44 , the new scrolling speed is automatically stored in the scroll speed storage 30 by the control unit 28 , step 46 , which scrolling speed is thereafter used for scrolling in this list. Thereafter the control unit 28 goes back and monitors the navigation key, step 34 . This method is then continued as long as the user is present in the menu having this list and as long as he has not selected an item in the list.
[0063] The present invention has many advantages. It allows a user to get full control of the scrolling, which he would not otherwise have. One alternative less satisfactory way to provide different types of scrolling is for example to provide a scrolling setting possibility in a special settings menu. It is often not good to provide this type of solution though, because the user might feel that it is complicated to navigate to this special menu in order to set a scrolling speed. The settings would then also have to be made for every possible list of items provided, which is burdensome for a user if there are many such lists. It is preferred that the scrolling speed can be influenced directly when it is needed, i.e. when scrolling is performed. Another possible solution that has been discussed is the provision of automatic increase of the speed when the list is long. In this case the user feels he has no real control of the scrolling process. According to the present invention a user can directly and in a simple manner control the scrolling speed when he is in the process of scrolling. For a suitable selection of step size in the device, the scrolling speed can be incremented and decremented such that it suits the particular user at the particular time. By storing the scrolling speed for the particular list, different scrolling speeds tailored after the different lists can be provided for a user. The provision of increasing of the scrolling speed when the actuations corresponding to the same directions coincide, and otherwise decreasing the scrolling speed also gives a user a natural and intuitive feeling that selection of change of scrolling speed matches the scrolling direction. The invention is also very inexpensive to implement. By providing the scroll speed control with the volume button, there is furthermore no need for any additional buttons or keys on the phone and the speed variation function can be provided with just some extra software in addition to the scrolling software already existing.
[0064] The present invention can be varied in many ways. The scrolling speed was described as being varied stepwise. It should be realised that it can just as well be changed linearly. The saving of the scrolling speed might as an alternative be made after approval of the user, which approval could be made through depressing any of the keys in the keypad. The saved scrolling speed might furthermore be made to apply to more than one list, like for instance all lists. The keys described were keys, where one key can be used for indicating two directions. It is of course also possible to provide this functionality with two separate keys. The same is true for the volume button. This can also be provided as two separate buttons that either increase or decrease the volume. The navigation key was furthermore described in relation to providing navigation in only upwards and downwards directions. Naturally it is also possible to provide navigation sideways. It should also be understood that the scrolling control according to the invention could also be performed for navigation sideways. The use of the buttons described can furthermore be the opposite, in that the volume button can be used for scrolling and the navigation button be used for scrolling speed control. The invention is of course not limited to these types of buttons or keys at all, but can be used with any keys provided on a device. The set of items was described in relation to a list of contacts and their phone numbers. The invention is not limited to this, but can be provided for any set of items, such as a list of received or sent messages, a list of functions or a list of settings that can be made. It is also applicable to scrolling in for instance a text file. The invention was described in relation to a cellular phone. A cellular phone is just one example of a device in which the invention can be implemented. The invention can for instance also be used in a PDA (personal digital assistant), a palm top computer a lap top computer and a regular PC. Therefore the present invention is only to be limited by the following claims. | The present invention is directed towards a method and a device for varying the scrolling speed provided for a set of items. The device comprises a first user input unit for allowing a scrolling action selection by the user, a second user input unit for allowing a scrolling speed variation selection, and a control unit, which provides a set of items of information that can be scrolled by a user (step 32 ), detects a scrolling action selection by a user via the first user input unit (step 34 ), detects a scrolling speed variation selection via the second user input unit (step 38 ), and changes the scrolling speed in dependence of the selections made by the user, (steps 42, 44 ). In this way varied scrolling speeds that can be fully controlled by a user in a simple manner are provided. | 6 |
CROSS-REFERENCES TO RELATED APPLICATIONS
This application claims priority to U.S. Provisional Patent Application No 60/448,989 entitled “A Method Of Spot-Dyeing Textiles” and filed on Feb. 20, 2003 for Craig Donaldson and Edward E. Durrant, which is incorporated herein by reference. This application also claims priority to U.S. Provisional Patent Application No. 60/476,752 entitled “Method of spot-dyeing textiles and Such” and filed on Jun. 6, 2003 for Craig Donaldson and Edward E. Durrant, which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. The Field of the Invention
The invention relates to a method and system for spot-dyeing textiles. Specifically, the present illustrated embodiment(s) involve(s) the use of textile dyes, representing each of the three primary colors, color filters designed to transmit a narrow range of light corresponding to the three primary colors to facilitate matching the textile colors, and comparator gray scale cards to facilitate the determination of correct dilution levels of dye concentrates.
2. The Relevant Art
Many cleaning agents or products are damaging to dyes used in coloring textiles, such as carpet. When these damaging compounds come into contact with carpet, the carpet dyes will fade or completely discolor. A common cleaning product that is known to damage carpet dyes is an aqueous solution of hypochlorite, commonly known as chlorine bleach. Acne medication, containing benzoyl peroxide, is also known to cause damage to carpet dyes upon contact.
As a result, several carpet-cleaning services have developed spot-dyeing kits to re-color damaged areas or spots. Typically, these re-coloring dyes are added together in a solution until a color match is achieved. One particular kit provides more than a dozen different dye colors that can be added together in any sequence and amount to try and match the missing color on the carpet. This process is often extremely difficult because matching a solution color to the carpet color is not a process easily performed with the naked eye. Often, the re-coloring dyes look slightly different in solution than on a solid substrate, such as when applied to carpet fibers. To help overcome this, an uncolored piece of test carpet can be utilized. Dying this uncolored test carpet with the dye solution can help one discern what the dye solution will look like on a carpet fiber.
There are, however, still other problems associated with the process described above. Often, when the bleaching agent attacks a carpet dye, it will bleach the dyes most susceptible to bleaching. Some dyes in the carpet are not susceptible to bleaching and will remain unbleached. This means that a bleach spot on a carpet may leave the spot yellow or red or green or any other color other than colorless (white). In this case, trying to match the color on a colorless piece of carpet may be difficult, at best.
Other known carpet spot-dying procedures include the use of adding primary colors in sequence to a spot under naked eye inspection until a match is achieved. However, this method also involves a large amount of guesswork and/or trial and error in order to formulate a relatively close match. As a result, this method can be very time consuming and may also require re-bleaching a stained area for re-coloring where a mistake in judging the proper addition of colors has occurred.
Thus, it can be clearly recognized that there is a need for a method and system for spot-dyeing textiles, such as carpet, clothing, leather, or any other textile, that is easy to apply for any user, that reduces the amount of time required to achieve a color match, and that increases the accuracy of achieving a match while minimizing the margin of error.
SUMMARY OF THE INVENTION
The various elements of the present invention have been developed in response to the present state of the art, and in particular, in response to the problems and needs in the art that have not yet been fully solved by currently available methods of spot-dying textiles. Accordingly, the present invention provides an improved method for using textile dyes, representing each of the three primary colors, color filters designed to transmit a narrow range of light corresponding to the three primary colors to facilitate matching the textile colors, and gray scale comparator cards to determine working dye solutions.
More particularly, the present embodiments involve the use of three separate light filters for aiding an applicator's ability to accurately match a textile color. These filters include a blue loss filter, a red loss filter, and a yellow loss filter. Visible spots seen through the blue loss filter indicate a blue loss in the damaged area. While applying blue dye to a damaged area, the applicator looks through the blue loss filter so that only a narrow band of light wavelengths may be seen. The working blue dye solution is applied until all visible spots are made invisible through the filter. The process is repeated for red and yellow dyes, utilizing their respective filters, until a near perfect color match is achieved.
In another embodiment an applicator utilizes each of the loss filters to view the contrast between a white material and an undamaged area of a textile. The applicator compares a gray scale comparator card to the contrast between the white material and the undamaged area of textile to determine a correct concentration of working dye solution.
Additional features and advantages of the present invention will become more fully apparent from the following description and appended claims, or may be learned by the practice of the invention as set forth hereinafter.
BRIEF DESCRIPTION OF THE DRAWINGS
In order for the advantages of the invention to be readily understood, a more particular description of the invention briefly described above will be rendered by reference to specific embodiments thereof, which are illustrated in the appended drawing. Understanding that this drawing depicts only one typical embodiment of the invention and is not therefore to be considered to be limiting of its scope, the invention will be described and explained with additional specificity and detail through the use of the accompanying drawing in which:
FIG. 1 illustrates one embodiment of the gray scale comparator cards.
DETAILED DESCRIPTION OF THE INVENTION
Reference throughout this specification to “one embodiment,” “an embodiment,” or similar language means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, appearances of the phrases “in one embodiment,” “in an embodiment,” and similar language throughout this specification may, but do not necessarily, all refer to the same embodiment.
Furthermore, the described features, structures, or characteristics of the invention may be combined in any suitable manner in one or more embodiments. One skilled in the relevant art will recognize, however, that the invention can be practiced without one or more of the specific details, or with other methods, components, materials, and so forth. In other instances, well-known structures, materials, or operations are not shown or described in detail to avoid obscuring aspects of the invention.
The general procedure for treating damaged color textiles includes several steps. Preferably, but not necessary, the damaged area may be rinsed with hot water to extract any excess or remaining bleach, or similar chemicals. Next, the area may optionally be treated with a bleach neutralizing solution containing a reducing agent to neutralize any bleach left in the fibers of the textile. A clothes iron, a wallpaper steamer, or other source of steam or heat should be used to catalyze the neutralization reaction of the damaged area. Also, the area may optionally be treated with a surfactant to reduce the surface tension of the fibers so that a later application of dye will penetrate to all necessary areas. Finally, the damaged area may optionally be treated with a dye preparation solution containing a weak acid to prepare the fibers to bond more effectively with the dyes. Between each step it is recommended to extract, potentially using a vacuum, any excess chemicals or agents.
After preparing the damaged area, the material is ready to be dyed. In one embodiment, using a color loss filter, or a long-pass filter that only transmits light at certain wavelengths, a user can view the damaged area of the textile and determine the color loss. For example, for blue loss, the applicator would view the damaged area with a blue loss filter. For red loss and yellow loss, the applicator would view the damaged area with a red loss and yellow loss filter respectively. If the damaged area is visible through the blue loss filter it is an indication that there is a blue color loss. To repair the blue color loss, the damaged area is treated with a working blue dye solution and the excess is extracted.
Concentrated dye solutions are created by mixing a dye solution with a fixed amount of water. Concentrated dye solution compositions vary according to the color of the dye (blue, red, or yellow). In this particular embodiment the concentrated blue dye solution is composed of between 0.00016 to 0.0016 grams of blue dye per approximately 100 milliliters of water. The concentrated red dye solution is composed of between 0.0002 to 0.002 grams of red dye per approximately 100 milliliters of water. The concentrated yellow dye solution is composed of between 0.00008 to 0.0008 grams of yellow dye per approximately 100 milliliters of water. Typically, these concentrated dye solutions are provided to the applicator to create working dye solutions.
Working dye solutions are the solutions that are mixed by the applicator to be used in repairing the damaged area of the textile. Working dye solutions are created by mixing the concentrated dye solution with a fixed amount of water. For lightly colored carpets, i.e. beige, tan, yellow, the applicator creates the working dye solution by diluting the concentrated dye solutions to approximately 2 milliliters of concentrated dye solution per approximately 500 milliliters of water. For medium colored carpets, i.e. brown, pink, orange, the concentrated dye solution should be diluted to approximately 10 milliliters of dye per approximately 500 milliliters of water. Finally, for dark colored carpets, i.e., blue, green, gray, the concentrated dye solutions should be diluted to approximately 20 milliliters of dye per approximately 500 milliliters of water.
Once the working dye solutions are mixed, the dye application process is ready to begin. In a preferred embodiment, while viewing the damaged area through the blue loss filter, or a long-pass filter that transmits light of wavelengths longer than approximately 550 nanometers, the applicator applies the working blue dye solution to the damaged area repeatedly until the damaged area is invisible through the blue loss filter. The excess dye is extracted, preferably with a vacuum or dry cloth. If, after five or so applications and extractions, no change occurs, or only a slight change occurs, increase the concentration of the working dye solution by adding 1 milliliter of the concentrated dye solution and repeat the process. When the damaged area is invisible through the blue loss filter, the undamaged area and damaged area comprise substantially the same amount of blue dye. It is noted, because the damaged area is still red and yellow dye deficient, the damaged area may still be visible to the naked eye.
In one embodiment, following the blue dye application, the applicator next uses a red loss filter, or a band-pass filter that transmits only light of wavelengths between approximately 450 nanometers and approximately 550 nanometers, to indicate red loss in the damaged area. Similar to the application of the blue dye process, the applicator views the damaged area through the red loss filter and applies the working red dye solution to the damaged area. Again, after each application, the excess red dye is removed. The application and excess dye solution removal is repeated until the damaged area is no longer visible through the red loss filter. Again, it is noted that he damaged area is still visible to the naked eye as the undamaged area is still yellow dye deficient.
In one embodiment, following the blue dye and red dye application, the applicator uses a yellow loss filter, or a short-pass filter that transmits light of wavelengths shorter than approximately 450 nanometers, to determine yellow loss in the damaged are. When looking at the damaged area through the yellow loss filter, if a damaged area is still visible, it is an indication that there is yellow loss in the damaged area. Thus, while viewing the damaged area through the yellow loss filter the applicator repeatedly applies and extracts the working yellow dye solution to the damaged area until the damaged area is invisible through the yellow loss filter.
When the blue, red, and yellow working dyes have all been applied until the damaged area is invisible according the respective color loss filters, the damaged area should visually match the undamaged area.
FIG. 1 illustrates one embodiment of typical gray scale comparator cards to determine the proper working dye solution. In this additional embodiment, the gray scale system consists of ten cards indicating working solutions of 1 milliliter per 250 milliliters to 10 milliliters per 250 milliliters in 1 milliliter increments. The applicator begins by placing a white material on an undamaged area of the carpet to be dyed and looks through any of the color loss filters. If a damaged area is visible, it is an indication that there is color loss in the damaged area. While looking through the selected color loss filter, the applicator compares the contrast between the white material and the undamaged area with the contrast between the shaded and unshaded portions of the gray scale comparator card. The corresponding gray scale comparator card indicates a dilution level for dying the damaged area. As an example, for blue color loss, the applicator views the white material, the undamaged area and the comparator cards through the blue loss filter. The contrast between the white material and the undamaged area is compared to the gray scale comparator cards. When a match is found between the contrast of the undamaged area and the white material and the contrast on the gray scale comparator card, the dilution level shown on the card indicates the working dye solution composition. The same process is repeated to prepare the working dye solutions for the red and yellow dyes.
The working blue, red, and yellow dye solutions are applied while viewing the damaged area through the respective color loss filters, as described previously. The process may need to be repeated until the damaged area is invisible through the color loss filters.
To set the dyes and make them less prone to re-bleaching or fading due to residual bleaching agents, the applicator should heat the area with a clothes iron, a wallpaper steamer, or other source of steam or heat.
It is understood that the above-described arrangements are only illustrative of the application of the principles of the present invention. The present invention may be embodied in other specific forms without departing from its spirit or essential characteristics. The described embodiments are to be considered in all respects only as illustrative and not restrictive. The scope of the invention is, therefore, indicated by the appended claims rather than by the foregoing description. All changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.
For example, variations in the design of filters are envisioned. The filters may be designed in the shape of glasses, or safety goggles, to be worn by the applicator during use. Alternatively, the filters may be designed in the shape of a screen attached to a hat or helmet, similar to the design and shape of a welder's face shield or a dental hygienist's facial screen.
Although the mentioned embodiments discuss the user of ten gray scale cards, it is anticipated that any number of cards and gray scale hues may be utilized. This will enable a use to have more refined selection of dye mixing concentrations. Additionally, although cards are discussed to be used, any means of providing a visual view of the various gray scale shades will work. For example, a gray scale color wheel, chart, linear scale, or even an electronic color meter may work.
Furthermore, although the matching dye mixing dilution formulas are placed on the gray scale cards, any form of associating the matching formulas is contemplated. For example, just the dye amount may be associated therewith provided that a set amount of water is known to be mixed therewith. Additionally, the comparator gray cards may be individualized according to the respective filter, or they may be combined into one card with varying dilution rates for each color loss filter.
Finally, although gray scale is discussed as the comparative hue, other known colors may be used, like blues, reds, blacks, whites, etc. Also, although it is discussed to have a preferred gray scale card that calculates dilutions from 1 milliliter of dye per 250 milliliters of water, any amount of dilution variations are anticipated. For example, any amount of water may be used instead of a standard 250 milliliter, or any corresponding amount of dye may be mixed. All of the variations are known to one skilled in the art of mixing concentrations and dilutions, and are contemplated in this invention.
The general sequence of steps within the process may be performed in any order and/or combination to achieve the desired result. For example, any filter and dye may be employed at any time to alter the color of the affected area. Also, the entire process may be repeated as many times as is necessary to achieve an acceptable color match.
Thus, while the present invention has been fully described above with particularity and detail in connection with what is presently deemed to be the most practical and preferred embodiment(s) of the invention, it will be apparent to those of ordinary skill in the art that numerous modifications, including, but not limited to, variations in size, materials, shape, form, function and manner of operation, assembly and use may be made, without departing from the principles and concepts of the invention as set forth in the claims. | Methods for spot-dyeing a damaged area on a textile employing a selected color loss filter and utilizing at least one of a primary color dye. In one embodiment, the method can include the following: inspecting the damaged area through the selected color loss filter; determining whether a primary color is missing from the damaged area by being able to view the damaged area through the selected color loss filter to, thereby, confirm that the primary color is missing from the damaged area; and applying at least one of a primary color dye, corresponding to the selected color loss filter, to the damaged area, while viewing the damaged area through the color loss filter, until the damaged area is substantially invisible through the color loss filter. | 3 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The invention relates to moldable resin compositions and molded articles obtained therefrom.
[0003] The invention relates in particular to blow moldable resin compositions based on polyether ester elastomers or block copolymers in which rubber like polyether soft segments and plastic like hard segments are alternately linked to one another.
[0004] 2. Description of the Related Art
[0005] The blow molding of polyesters in particular polyether ester elastomers is known, but remains problematic especially for the blow molding of very long parts which requires specific rheological properties, in particular a closely controlled high melt strength to avoid unwanted sagging.
[0006] U.S. Pat. No. 4,010,222 reports that the addition of a copolymer containing polymerized ethylene units and polymerized carboxylic acid units to a copolyester elastomer improves its processing by blow molding.
[0007] U.S. Pat. No. 4,912,167 describes a blow moldable composition of a polyester such as polybutylene terephthalate (PBT), polyethylene terephthalate (PET) or a PBT/PET blend, an epoxide polymer and a source of catalytic ions.
[0008] U.S. Pat. No. 5,128,404 describes a blow moldable composition containing polybutylene terephthalate, an ethylene copolymer containing epoxide groups and an ionomer obtained by partially neutralizing with Na + of K + the carboxyl groups of an ethylene copolymer containing (meth)acrylic acid.
[0009] U.S. Pat. No. 5,523,135 describes the problems of blow molding thermoplastic polyester resins, and reports an improvement for a combination of a thermoplastic polyester resin, typically, PBT, with a styrenic copolymer. In Comparative Example 12 it reports that blow molding was impossible when the PBT was replaced with a PBT-containing polyester ether elastomer.
[0010] EP-A-0,577,508 aimed to improve the blow moldability of polyether ester elastomers (block copolymers) which hitherto were not considered suitable for blow molding, by mixing them with an epoxy compound and a phenol alkali metal salt.
[0011] Canadian Patent Application 2,039,132 proposed a general improvement in polyether ester elastomers (block copolymers) by mixing them with an aromatic thermoplastic polyester, like PBT, PET or blends thereof, a rubbery interpolymer and optionally a mineral filler.
[0012] Whereas certain polyether ester elastomer formulations have been successfully used for blow molding, it still remains problematic to provide a blow moldable resin composition based on polyether ester resin that has a high parison stability, with little tendency to sag, for the blow molding of very long parts, especially for sequential co-extrusion or 3-D parison manipulation techniques.
SUMMARY OF THE INVENTION
[0013] According to the invention a moldable resin composition with improved properties for blow molding comprises the following components (A)-(F).
[0014] (A) A blend of two polyether ester elastomers (A1) and (A2), (A1) with a hardness in the range 45-72 Shore D, in an amount 70-95 wt. % of the blend, and (A2) with a hardness in the range 25-40 Shore D, in an amount 5-30 wt. % of the blend.
[0015] (B) A copolymer comprising from 94 to 50 wt. % of ethylene, from 5 to 35 wt. % of at least one alkyl or cycloalkyl acrylate or methacrylate, in which the alkyl or cycloalkyl group has from 2 to 10 carbon atoms, and from 1 to 15 wt. % of at least one unsaturated epoxide.
[0016] At least one of (C) and (D), where (C) is a copolymer comprising from 88 to 60 wt. % of ethylene, from 11.5 to 40 wt. % of at least one alkyl or cycloalkyl acrylate or methacrylate, in which the alkyl or cycloalkyl group has from 2 to 10 carbon atoms, and from 0.5 to 6 wt. % of at least one anhydride of an unsaturated dicarboxylic acid; and (D) is at least one rubbery polymer that can be finely dispersed into the composition by extrusion.
[0017] (E) A calcium compound capable of reacting with acid end-groups of the polyether ester resins of blend (A).
[0018] (F) One or more optional additives.
[0019] In the composition according to the invention: the resin blend (A),is present in an amount of 60-90 wt. % of the composition. Copolymer (B) is present in an amount of 6-15 wt. % of the resin blend A. Copolymer (C) when present is in an amount up to 20 wt. % of the composition, and the rubbery polymer (D) when present is in an amount up to 20 wt. % of the composition, providing the sum of (C) and (D) is at least 2 wt. % of the composition. The calcium compound (E) is in an amount such as to provide up to 2 wt. % elemental calcium in the composition. Lastly, the optional additive(s) (F) when present is/are in an amount up to 20 wt. % of the composition.
[0020] The composition according to the invention provides a high parison stability, with little tendency to sag, enabling the successful blow molding of very long parts, which could not be achieved with prior polyether ester elastomer formulations, at the same time combining a good surface aspect of the molded part. This composition is especially advantageous for sequential co-extrusion and for 3-D parison manipulation techniques.
[0021] The copolyester elastomers (A) are advantageously copolyetheresters consisting essentially of a multiplicity of recurring long chain ester units and short chain ester units joined head-to-tail through ester linkages. The long chain ester units are represented by the formula
[0022] and the short chain ester units are represented by the formula
[0023] where G is a divalent radical remaining after removal of terminal hydroxyl groups from a poly(alkylene oxide) glycol having a molecular weight of about 400-6000 and a carbon-to-oxygen ratio of about 2.0-4.3; R is a divalent radical remaining after removal of carboxyl groups from a dicarboxylic acid having a molecular weight less than about 300 and D is a divalent radical remaining after removal of hydroxyl groups from a diol having a molecular weight less than about 250; provided said short chain ester units amount to about 15-95% by weight of the copolyetherester.
[0024] Alternatively, the copolyester elastomer is a copolyester ester.
[0025] Copolyetherester elastomers and copolyester ester elastomers are described for example in U.S. Pat. Nos. 4,981,908, 5,824,421 and 5,731,380, the descriptions whereof are incorporated herein by way of reference.
[0026] Polyetherester block copolymers and their preparation are also described in Encyclopedia of Polymer Science and Engineering, Volume 12, pages 76-177 (1985) and the references reported therein.
[0027] Various polyetherester block copolymers are commercially available from a number of companies under various tradenames, for example HYTREL of E.I. du Pont de Nemours, RITEFLEX of Ticona and ARNITEL of DSM.
[0028] Varying the ratio hard/soft segment and using different alkylene oxides and molar weights of the soft segments makes it possible to obtain block copolyesters having different hardnesses, for example between Shore D 25 and 80. The invention employs a blend of two polyether ester elastomers, one with a hardness in the range 45-72 Shore D, and the other with a hardness in the range 25-40 Shore D.
[0029] The employment of a blend of copolyester elastomers of high and low hardnesses is critical for the invention and gives benefit for the parison aspect (less melt fracture). Moreover, the blend used in the invention has been found to improve the surface aspect of the parison when coming out of the die, leading to less surface defects in the molded part.
[0030] Using a blend of copolyester elastomers of high and low hardnesses is not equivalent to using a single copolyester elastomer of median properties. This is because the length of the soft blocks in the copolyester elastomer tends to be longer for the softer grades, hence the presence of even a small fraction of long soft blocks can influence the crystallisation speed and density of entanglement retained when the material solidifies from the molten state.
[0031] Preferably the soft segments in the soft copolyester elastomer is polytetramethyleneglycol (PTMEG) with a molecular weight of the order of 2000, whereas the soft segment in the hard copolyester elastomer is PTMEG with a molecular weight of the order of 1000.
[0032] The relative amounts of the hard and soft copolyester elastomers are in the range 75-97 wt. %, preferably 84-94 wt. %, for the hard copolyester elastomer and 3-25 wt. %, preferably 6-16 wt. %, for the soft copolyester elastomer, based on the total weight of the blend.
[0033] Examples of alkyl acrylates and methacrylates that may in particular be employed as constituents of the copolymers (B) and (C) are: methyl methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate and 2-ethyl-hexyl acrylate.
[0034] Examples of unsaturated epoxides that may in particular be employed as constituents of copolymer (B) are: aliphatic glycidyl esters and ethers such as allyl glycidyl ether, vinyl glycidyl ether, glycidyl maleate and itaconate and glycidyl acrylate and methylacrylate; and alicylic glycidyl esters and ethers such as 2-cyclohexene-1-glycidyl ether, diglycidyl 4,5-cyclohexene-dicarboxylate, glycidyl 4-cyclohexene carboxylate, glycidyl 5-norbornene-2-methyl-2-carboxylate and diglycidyl endocdis-bicyclo(2.2.1)-5-heptene-2,3-dicarboxylate.
[0035] Examples of anhydrides of an usaturated dicarboxylic acid that can be employed as constituents of copolymer (C) are maleic anhydride, itaconic anhydride, citraconic anhydride and tetrahydrophthalic anhydride.
[0036] Further examples of copolymers (B) and (C) are given in U.S. Pat. Nos. 5,208,292 and 5,407,999. These patents describe thermoplastic polyester alloys usable particularly for injection molding of articles strengthened against impact, comprising a saturated polyester like PET or PBT reinforced with a copolymer. This reinforcing polymer includes a first copolymer comprising from 94 to 60 wt. % of ethylene, from 5 to 25 wt. % of at least one alkyl or cycloalkyl acrylate or methacrylate, in which the alkyl or cycloalkyl group has from 2 to 10 carbon atoms, and from 1 to 15 wt. % of at least one unsaturated epoxide from 84 to 60 wt. % of ethylene; a second copolymer comprising from 15 to 34 wt. % of at least one alkyl or cycloalkyl acrylate or methacrylate, in which the alkyl or cycloalkyl group has from 2 to 10 carbon atoms and from 1 to 6 wt. % of at least one anhydride of an unsaturated dicarboxylic acid; and a compound capable of accelerating the reaction between the epoxy group of the first copolymer and the anhydride group of the second copolymer.
[0037] Rubbery polymers which can be included in the composition of the present invention as component (D) include acrylate terpolymer rubbers as described in U.S. Pat. No. 5,380,785, such as those available from Goodyear Chemical under the trademark SUNIGUM, styrene-ethylene/butylene-styrene block copolymers such as those available from Shell Chemical Company under the tradename KRATON, and methacrylate/butadiene/styrene or butyl-acrylate/PMMA multiphase composite interpolymers such as those available from Rohm & Haas Co under the tradename PARALOID.
[0038] Examples of methacrylate/butadiene/styrene multiphase interpolymers of component (D) are those available from Atofina under the tradename METABLEN and those available from Sonepa Polymer Additives under the tradename of RAJALOID.
[0039] Further examples of component (D) are styrene-ethylene/butylene-styrene block copolymers available from Teknor Apex under the tradename TEKRON and those available from Multibase under the tradename MULTIFLEX.
[0040] Examples of the calcium compound (E) capable of reacting with acid groups of the polyether ester resins of blend (A) are: calcium oxide, calcium hydroxide, calcium salts of inorganic acids and calcium salts of mono-, di- or polycarboxylic acids. The presence of this calcium compound is important because it provides enhanced viscosity at a given level of the copolymers (B) and (C), hence enables a high viscosity to be obtained while avoiding problems associated with an excessive amount of copolymers (B) and (C). Furthermore, in order to keep the amount of this calcium compound to a minimum value in the composition, it is an advantage that the weight fraction of calcium in the calcium compound is high, which means for instance that calcium oxide or calcium hydroxide are preferred over calcium stearate.
[0041] The composition according to the invention may contain the usual additives, for example stabilizers, ultraviolet ray-absorbers, hydrolytic stabilizers, anti-static agents, dyes or pigments, fillers, fire-retardants, lubricants, processing aids, for example release agents, etc, in an optional amount. These additives may for example be included in either component of the polyetherester block copolymer blend.
[0042] The optional additives can include a compound capable of accelerating the reaction between the epoxy groups present in the copolymer (B) and the acid end-groups of the copolyester elastomer, for example a zinc compound in an amount of up to about 1.5 wt. % of the composition.
[0043] The composition according to the invention is useful in particular in blow molding processes but can also be used in other molding processes such as extrusion molding and generally any manufacturing method that includes the step of heating the composition above its melting temperature. The invention also pertains to shaped articles made using the given composition, in particular blow molded articles, especially long parts.
DETAILED DESCRIPTION
[0044] The invention will be further described and compared with prior art in the following Examples and Comparative Examples.
[0045] The compositions discussed below were prepared by mixing the components in the described proportions and melt blending the resulting mixtures on a 40 mm diameter twin screw extruder. Extrusion conditions were as follows: temperature profile of the extruder: decreasing from 250° C. at the hopper to 230° at the die; die temperature: 230° C.; screw speed: 300 rpm. Measured melt temperatures range from 240° C. to 275° C. for the various compositions. The extrudate was pulled into strands, cooled in a water bath and pelletized.
Description of the Measurement Methods
[0046] The melt flow rate of the materials was measured according to ISO 1133 at 230° C.; loads from 2.16 kg to 21.6 kg were used, to accommodate for the wide range of melt viscosities observed.
[0047] The blow molding evaluations were done on a Battenfeld Fischer machine equipped with a screw having 60 mm diameter and 20 L/D length. Barrel and die temperatures were set in a way that the melt temperature measured with a hand probe is 230 +/−2° C. With the screw turning at a constant speed of 31 rpm, the parison is extruded through a circular die with an outer diameter of 23.8 mm and a core pin diameter of 18.4 mm. During its descent from the die towards the floor, the advance of the parison is measured in the following way: the parison is cut at the die exit and this defines the time as zero, then the time is recorded when the lowest point of the parison has moved by 1 dm, repeatedly up to 12 dm. Four such measurements are made and averaged. The average times are used to extract the sag length, which is defined as the length at which the parison speed is twice its speed measured between 1 and 2 dm. The sag length can be obtained either by direct inspection of the data, or by fitting an appropriate equation through the raw data and calculating this length from the derivative of the fitted equation. A higher value of the sag length indicates that the material has less tendency to sag under its own weight, which translates into better suitability for the production of long parts by the blow molding process. This is especially important for blow molding techniques that involve parison manipulation and/or sequential extrusion of different materials.
[0048] Being a measurement of viscosity, the melt flow rate was sometimes taken as a first screening indicator of the behavior of a material in the blow molding process. There is a strong correlation between low MFR values (high viscosity) and high sag length values in blow molding. Hence, the blow molding evaluation was not done for all cases, especially at the early stages and for the materials which did not seem promising based on the MFR value.
[0049] Additional criteria were used to qualify the blow molding behavior of the resins. In particular the parison and the finished part were visually observed to detect the presence of melt fracture (shark skin) or of inhomogeneities, undispersed material, gel-like particles or lumps. Emission of smoke or volatile compounds leading to objectionable odors were also monitored during the blow molding process.
Description of Ingredients
[0050] Materials used in the Examples set forth below are as follows, identified by the respective trademarks and trade designations:
[0051] TEEE 1: HYTREL 5556, a thermoplastic polyester elastomer from E.I. du Pont de Nemours having a Shore D Hardness of 55 and a melt flow rate of 7.5 dg/min at 220° C. under 2.16 kg load.
[0052] TEEE 2: HYTREL 5586, a thermoplastic polyester elastomer from E.I. du Pont de Nemours having a Shore D Hardness of 55 and a melt flow rate of 4.5 dg/min at 220° C. under 2.16 kg load.
[0053] TEEE 3: HYTREL 3078, a thermoplastic polyester elastomer from E.I. du Pont de Nemours having a Shore D Hardness of 30 and a melt flow rate of 5 dg/min at 190° C. under 2.16 kg load.
[0054] TEEE 4: HYTREL HTR4275 BK316, a thermoplastic polyester elastomer from E.I. du Pont de Nemours having a Shore D Hardness of 55 and a melt flow rate of 1.5 dg/min at 230° C. under 5 kg load. This particular resin grade is widely used and considered as a benchmark in the blow molding of technical components in thermoplastic polyester elastomers.
[0055] Terpolymer 1: a terpolymer of ethylene/28% n-butyl acrylate/5.2% glycidyl methacrylate having a melt flow rate of 12 dg/min at 190° C. under 2.16 kg load, commercially available as ELVALOY AM from E.I. du Pont de Nemours.
[0056] Terpolymer 2: a terpolymer of ethylene/25% methyl acrylate/6.5% glycidyl methacrylate having a melt flow rate of 6 dg/min at 190° C. under 2.16 kg load, commercially available as LOTADER AX8900 from Atofina.
[0057] Terpolymer 3: a terpolymer of ethylene/30% ethyl acrylate/2% maleic anhydride methacrylate having a melt flow rate of 7 dg/min at 190° C. under 2.16 kg load, commercially available as LOTADER 4700 from Atofina.
[0058] Rubber 1: an acrylate terpolymer having a Shore A hardness of 53, commercially available as SUNIGUM P7395 from Goodyear Chemical.
[0059] Rubber 2: a butyl acrylate/PMMA core-shell modifier, commercially available as PARALOID) EXL 2314 from Rohm & Haas Co.
[0060] Black masterbatch: a masterbatch of carbon black in polyether ester elastomer, commercially available as HYTREL 41CB from E.I. du Pont de Nemours.
Screening Experiments
[0061] Compositions were prepared using eight different epoxy compounds incorporated one by one in TEEE1 (A1), in presence of calcium oxide and zinc stearate. It appeared clearly that the Terpolymers 1 and 2 were most efficient to increase the viscosity of the composition, resulting in MFR values as low as 0.1 dg/min at 230° C. under 2.16 kg load. In contrast, epoxy bisphenol condensation products, such as EPON 1004F from Shell, yielded compositions with a viscosity equal or close to the viscosity of the initial TEEE 1 (above 20 dg/min at 230° C./2.16 kg). Intermediate results were obtained with a polyglycidyl ether of ortho-cresol novolac, commercially available as EPON 164 from Shell Chemicals, and with a mixture of 70-82% terephthalic acid diglycidylester and 18-30% trimellitic acid triglycidylester, commercially available as ARALDITE PT910 from Ciba Specialty Chemicals.
[0062] A second series of screening experiments was done, where the variables were the concentrations of Terpolymer 2 (4-15%), Terpolymer 3 (0-15%), calcium oxide (0-1%), black masterbatch (3-10%), and TEEE 2 (59-93%, adjusted to a total of 100% for each composition). It was found that the dominant factor controlling viscosity is the concentration of the Terpolymer 2: addition of 15% Terpolymer 2 increases the viscosity so much that it becomes essentially impossible to process the resulting material, whereas addition of 4% Terpolymer 2 increases the viscosity to MFR values comprised between 0.8 and 5.3 dg/min at 230° C. under 5 kg load. These experiments also demonstrated clearly that, all other parameters being equal, the presence of calcium oxide increases the viscosity, whereas the amount of black masterbatch has no significant influence on viscosity.
COMPARATIVE EXAMPLES 1 TO 5
[0063] The compositions of Comparative Examples 2 to 5 in Table 1 were prepared by extrusion as described above; in addition to the ingredients listed there, they each also contained 1% calcium oxide (component E), 2% black masterbatch and 1.9% stabilisers. Blow molding evaluation of Comparative Examples 1 to 5 was done on the Battenfeld Fischer machine using the above procedure, and the sag length was measured by reading directly from the raw data.
[0064] It is found that the sag length is more sensitive to the concentration of Terpolymer 2 than to that of Terpolymer 3. Furthermore, melt fracture is clearly visible when the concentration of Terpolymer 2 is 10%. Compared to the behaviour of the benchmark material TEEE 4, the Comparative Examples 2 to 4 show some improvement of sag length, whereas Comparative Example 5 which has much longer sag length is hampered by a severe melt fracture, leading to unacceptable aspect of finished parts.
TABLE 1 Component Ingredients CE 1 CE 2 CE 3 CE 4 CE 5 Al TEEE 2 [%] 87.1 85.1 85.1 85.1 TEEE 4 [%] 100 B Terpolymer 2 [%] — 6 6 8 10 C Terpolymer 3 [%] — 2 4 2 Ratio B/A [%] 6.9 7.1 9.4 11.8 Sag length [dm] 4.5 5 6 7 10.5 Parison aspect Good Good Good Good Melt fracture
EXAMPLES 1 TO 6 AND COMPARATIVE EXAMPLES 6 AND 7
[0065] The compositions of Examples 1 to 6 and Comparative Examples 6 and 7 in Table 2 were prepared by extrusion as described above; in addition to the ingredients listed there, they also each contained 1% calcium oxide (component E), 2% black masterbatch, 0.4% zinc stearate and 1.4% stabilizers. Blow molding evaluation was done on the Battenfeld Fischer machine, and the sag length was calculated from the equation fitted through the raw data.
TABLE 2 Component Ingredient Ex 1 Ex 2 Ex 3 Ex 4 Ex 5 Ex 6 CE 6 CE 7 A1 TEEE 1 [%] 49.2 49.2 57.2 65.2 A1 TEEE 2 [%] 57.2 57.2 75.2 65.2 A2 TEEE 3 [%] 10 10 10 10 10 10 10 20 B Terpolymer 2 [%] 8 8 8 10 8 8 10 10 C Terpolymer 3 [%] 8 8 10 D Rubber 1 [%] 20 20 20 D Rubber 2 [%] 20 20 Ratio B/A [%] 13.5 13.5 11.9 13.3 11.9 11.9 11.7 11.7 Sag length [dm] 42 21 19 12 22 33 (a) (a)
[0066] No melt fracture was observed in any of the Examples 1 to 6. This shows that presence of the softer components TEEE 3 and/or rubber strongly reduces the tendency for the parison to show melt fracture. Very high sag length values are found with a fair parison aspect; some lumps or gel-like particles were observed with all examples, and some smoke was evolved with examples 1, 2, 3 and 5, but these defects are minor and cosmetic rather than functional.
[0067] Comparative Examples 6 and 7 show that although Terpolymer 3 and rubber are each optional, there must be at least one of these in the composition.
EXAMPLES 7 TO 25 AND COMPARATIVE EXAMPLE 8
[0068] A design of experiments was done, where the compositions are as described in Table 3. All compositions in this Table also contained 2% black masterbatch, 1% calcium oxide (component E), 0.4% zinc stearate and 1.4% stabilizers.
[0069] All examples in Table 3 have high viscosity, as shown by the MFR values measured at 230° C. under 21.6 kg load. Comparative Example 8 shows that when the amount of Terolymer 2 is higher than 15% of the amount of blend A, then the composition becomes too viscous to be extruded. This finding is in agreement, and indeed more strict, than the observation done with the second series of screening experiments, where compositions using Terpolymer 2 at 15% of the total composition (i.e. 18 to 25% relative to TEEE 2) were too viscous to be processed. It can also be seen that all Examples comply with this upper limit of 15% component B relative to the blend A.
[0070] The Examples 7 to 25 also all show much improved sag length relative to the benchmark TEEE 4 (Comparative Example 1, Table 1). Indeed some compositions of Table 3 have extremely high melt strength, with essentially no sagging over the measurement height of 1.2 m (almost no curvature of the parison length versus time graph, sag length calculated as high as 50 dm).
[0071] The surface aspect of the parts was estimated globally, based on presence of melt fracture, lumps, pits/craters and other aspect defects. The best surface aspect with no visible surface defects, which was obtained with the benchmark material TEEE 4 (Comparative Example 1), reached the score of 10 on this scale. Materials within Examples 7 to 25 exhibit surface aspect of parison and finished parts ranging from rather poor (e.g. Ex. 19) to very good (e.g. Ex. 7).
[0072] The Examples have been given to illustrate but not to limit the invention. Depending on the desired pattern of characteristics, persons skilled in the art will be able to select from the range of possible compositions exemplified here the optimal combination between processing behavior and aspect of the parison and finished parts.
TABLE 3 Com- ponent Ingredient Ex 7 Ex 8 Ex 9 Ex 10 Ex 11 Ex 12 Ex 13 Ex 14 Ex 15 Ex 16 Ex 17 A1 TEEE 1 [%] 74.2 59.2 76.2 72.2 69.2 65.2 65.2 69.2 63.2 67.2 75.2 A2 TEEE 3 [%] 4 10 7 7 4 4 10 10 8 8 4 B Terpolymer 2 [%] 6 8 6 8 6 8 10 8 8 8 8 C Terpolymer 3 [%] 6 8 6 8 6 8 10 8 8 8 8 D Rubber 1 [%] 10 10 8 D Rubber 2 [%] 5 10 4 Ratio B/A [%] 7.7 11.6 7.2 10.1 8.2 11.6 13.3 10.1 11.2 10.6 10.1 Sag length [dm] 8 16 10 26 11 50 31 19 17 30 28 Aspect (a) 9 8 8 6 7 7 7 7 8 4 5 MFR (b) [dg/mm] 12.1 3.3 6.1 1.2 4.6 1.9 0.3 0.9 2.1 0.4 0.8 Com- ponent Ingredient Ex 18 Ex 19 Ex 20 Ex 21 Ex 22 Ex 23 Ex 24 Ex 25 CE 8 A1 TEEE 1 [%] 65.6 73.2 69.1 79.2 63.2 71.2 76 68.2 61.2 A2 TEEE 3 [%] 5.6 10 3.6 4 10 7 3.2 9 4 B Terpolymer 2 [%] 8 6 9 6 6 6 8 9 10 C Terpolymer 3 [%] 8 6 9 6 6 6 8 9 10 D Rubber 1 [%] 4.5 5 10 D Rubber 2 [%] 8 10 Ratio B/A [%] 11.2 7.2 12.4 7.2 8.2 7.7 10.1 11.7 15.3 Sag length [dm] 41 10 34 11 22 11 25 20 (c) Aspect (a) 6 1 7 5 7 8 7 2 MFR (b) [dg/mm] 0.3 5.5 0.3 4.8 1.9 6.3 0.8 0.5 | Blow-moldable resin compositions based on polyether ester elastomers or block copolymers n which rubber-like polyether soft segments and plastic-like hard segments are alternately linked to one another. | 2 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention pertains to the field of aircraft ground maneuvering devices. More particularly, this invention pertains to hand-held portable aircraft towing devices powered by electricity as opposed to manual devices such as tow bars and the like.
2. DESCRIPTION OF THE PRIOR ART
Aircraft come in a variety of sizes, shapes and weights from huge multi-engine military and commercial airplanes weighing many tons to single and twin engine private and light commercial airplanes weighing a few thousand pounds. While aircraft seem to slip through the air with the greatest of ease, on the ground they are cumbersome vehicles, with relatively few handholds and wide soft tires, that are difficult and awkward to maneuver by hand. Whether in a hangar or out on the tarmac, pushing or pulling an airplane from one location to another is often the most physically difficult portion of the flight.
Female flyers have an even more difficult time. While both males and females are fully capable of flying an airplane, and while man can usually use his body weight to aid him in pushing a heavy aircraft, women being generally light-weight and of small frame often find it extremely difficult, if not impossible, to move the airplane on the ground. This has led some people to leave the sport of flying that they might otherwise enjoy.
A few attempts have been made to make the chore of moving aircraft easier. Virtually every airport has one or more manual tow bars that are nothing more than an elongated metal shaft having a handle at one end and a pair of ears or hooks at the other end for temporarily attaching to an aircraft to pull or push it. These are of little use for heavy aircraft, not recommended for female pilots because of the low mechanical advantage, and not good for any aircraft where the movement is to be up an inclined surface, such as is often encountered in aircraft parking areas.
Some airports have power-tow devices. They come in a variety of sizes and shapes, all with their own individual problems. One type comprises a gasoline engine powered dolly weighing over one hundred pounds; another type is an electrically-powered tow that weighs sixty pounds and requires an extension cord weighing an additional ten pounds. The gasoline-powered unit is generally too much for the female pilot and because of its weight cannot be carried in the aircraft. The electric device is limited in range to the length of the extension cord and also is too heavy to carry in the aircraft. Accordingly, these prior art devices are confined to one location which is exactly one-half or less of the number of locations to be visited by the pilot.
SUMMARY OF THE INVENTION
This invention is a truly portable, very lightweight and relatively inexpensive aircraft moving device. It utilizes a cordless electric drill. It's operation involves the simple steps of attaching it temporarily to the aircraft and pulling the trigger-switch on the drill while at the same time pushing downward on the drill handle to bring the drive wheel into contact with the front wheel of the aircraft. Simply raising and lowering the device against the aircraft's front tire provides very efficient and accurate one-hand control of the airplane. With a cordless electric drill, the device may be used anywhere. One embodiment of the invention includes an a.c. powered drill and an extension cord generally useful where the device is going to be kept around a hangar or other covered storage. The device is so light and compact as to be easily carried in the aircraft for use anywhere. In addition, one embodiment of the battery for powering the electric drill may be placed in a charging device in the airplane while in flight to bring it back to full charge so that its full capacity may be realized at the next ensuing landing place of the aircraft. In another embodiment, the device utilizes the aircraft's own battery to power the drill.
The invention comprises a hand-held electric drill that is attached to one end of an elongated support tube where the other end of the tube is attached to a power diverter and speed reducer adapted to be pivotally attached by a releasable connection to the aircraft adjacent its front wheel. A drive shaft is interconnected between the drill output shaft and the power diverter for rotation with the drill in response to a squeeze of the trigger switch. The power diverter and reducer redirects rotation of the incoming drive shaft along an output axle whose axis is substantially parallel to the aircraft's front wheel. A drive wheel attached to the output axle, rotating at a slower speed than the drill, is pressed into tangential contact with the upper front of the aircraft's front wheel by downward pressure exerted on the drill handle. This allows a one-hand operation to start, stop, engage the drive wheel and to change the direction of the moving aircraft solely at the handle of the drill.
Additional features include using a drill that has a variable speed, through variable movement of the drill trigger to vary the speed of movement of the aircraft. Further, one may incorporate a reversible drill to provide forward and reverse motion of the aircraft. By locating the relatively heavy hand drill at the far end of the device, adjacent the handle and actuation switch, the weight of the drill is used effectively to help bring drive wheel pressure against the front wheel of the airplane thereby providing substantial mechanical advantage to the overall design and bring the act of moving the aircraft fully within the capability of both men and women. By this means, complex, and other substantially heavy components found in prior art towing devices have been eliminated. There is thus produced a mechanism whereby men and women, large and small, may easily move an aircraft without need to start and stop gasoline engines, work with heavy and cumbersome electrical extension cords and most importantly, without having to leave the device behind when they proceed to the next place of landing.
Accordingly, the main object of this invention is a lightweight, portable aircraft moving device that may be carried in the aircraft and used wherever the pilot lands. Other objects include a device that is compact and contains relatively few parts; a device where the battery that powers the drill may be recharged during flight for use at other points of landing, a device light enough to be transportable without a large weight penalty and that is useful in moving a wide variety of aircraft.
These and other objects of the invention will appear more clear when reading the following description of the preferred embodiments when taken together with the drawings that are appended hereto. The scope of protection desired by the inventor may be gleaned from a fair reading of the claims which conclude this specification.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a top plan view of one embodiment of this invention;
FIG. 2 is a bottom plan view of the embodiment shown in FIG. 1;
FIG. 3 is a close-up bottom plan view of another embodiment of the drill showing the use of an electric extension cord to provide electrical energy to the drill motor;
FIG. 4 is a side elevational, partially sectional, view of one embodiment of connection between the drive shaft and the drill output shaft;
FIG. 5 is a side elevational, partially fragmented, view showing one embodiment of the universal joint attached to the drive shaft;
FIG. 6 is a bottom plan view of one embodiment of the power diverter and aircraft wheel drive means;
FIG. 7 is a top view of the embodiment shown in FIG. 6 and shows in greater detail the pivotal means for attaching the device to the aircraft;
FIG. 8 is a side elevational view of the embodiment shown in FIGS. 6 and 7 showing one particular embodiment of the pivotal attachment means;
FIG. 9 is a side elevational view showing the device temporarily attached to an aircraft and ready for use; and,
FIG. 10 is an illustrative view showing a person utilizing the invention to move an aircraft.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Turning now to the drawings wherein like elements are identified with like numerals throughout the nine drawings, this inventive device is generally shown and identified by the numeral "1". In the Figures device 1 is shown to comprise a hand-held portable electric drill 3 that includes a rotating output shaft 5 having a forward extending shaft end 7 (see FIG. 4) powered by an electric motor indicated generally at 9 that are all operably mounted in a drill body 11 that is set atop and forward of a pistol-grip shaped handle 13. Handle 13 contains a palm-grasping portion 15, extending generally downward and to the rear of motor 9, and a finger-actuated electric switch 17, generally located in front of portion 15, for squeezing with the fore-finger to activate drill motor 9.
A first means 19 is provided for energizing electric drill 3. In FIGS. 1 and 2 means 19 is shown to comprise a battery 21 attached to and made part of palm-grasping handle portion 15. Such batteries are generally either received in handle portion 15, removable for replacement or recharging, or are made in the shape of palm-grasping portion 15 and attached thereto to form said handle 13. Preferred in this embodiment of the invention is a battery 21 that is separable from drill handle 13 and insertable into a separate receptacle (not shown) for recharging. Such batteries are already known in the art as is the receptacle. Said receptacle contains a means to make the incoming voltage compatible with the battery, where needed, as well as means for monitoring and controlling the flow of current into the battery so that it does not become damaged by overcharging. Such a receptacle may be easily and conveniently mounted somewhere in the interior of the aircraft and attached to the aircraft's electrical system for use in flight to charge the battery after take-off and before landing to insure a full charge at the next landing point. An example of a portable electric drill of the type just described and usable herein is a Model 2735 Cordless Drill, manufactured by Skil Tools, Inc. Chicago, Ill.
As shown in FIG. 3, means 19 may comprise a remote source 23 of electric current, such as a.c. current, that is connectable to drill 3 by an elongated electric extension cord 25, having male and female end plugs 27 and 92, for attachment respectively to a female receptacle 31 on remote source 23 and male plug 33 that extends from a short wire 35 emanating from the bottom of palm-grasping portion 15. This latter embodiment is especially useful where device 1 will remain at a single location, such as an aircraft hangar, and be continually used to move the aircraft in and out of that hangar as opposed to taking it on extensive trips. An example of a portable electric drill of the type just described and usable herein is a Model 4700 Portable Drill, 110 volts, a.c. powered, manufactured by Makita Electric Works Ltd., Japan. In another embodiment of this invention, remote electrical source 23 may be the aircraft's own battery carried internally within the aircraft. Extension cord 25 would then connect said battery to drill 3 through the aforesaid male and female receptacles to provide the requisite power to move the aircraft.
As shown in FIGS. 1, 2 and 3, drill body 11 is placed in a saddle 37 comprised of a pair of mutually spaced apart, elongated plates 39a and 39b that are welded or otherwise attached near the first end 41 of an elongated tube 43, the second end 45 of tube 43 being attached to a second means 47 as will be hereinafter more fully explained. A strap 49 may extend around drill body 11, that encloses electric motor 9, and over plates 39a and 39b, and tightened at clamp screw 51 to hold drill 3 in rigid position at tube end 41. On some models of electric drills there is a threaded aperture at the side of the motor housing for insertion of a side handle to steady the drill during usage. As shown in FIGS. 1-4, an aperture 53 is formed in plate 39a in registration with the threaded receptacle on drill 3 so that the side handle may be replaced with a short threaded bolt 55 that is tightened therein to aid in holding drill 3 rigidly against first tube end 41.
An elongated drive shaft 57 having spaced-apart first and second ends 59 and 61 respectively is set parallel to and preferably received inside of elongated tube 43 and attached at said first end 59 to drill output shaft forward end 7. Elongated tube 43 and drive shaft 57 may be set in side-by-side arrangement, however, it is preferred that drive shaft 57 be placed inside tube 43 for compactness and safety. Further, while tube 43 and shaft 57 may be made solid throughout, it is preferred that they both be made hollow, from strong material such as aluminum or steel and be thin-walled for light weight. Examples of tubing that may be utilized as elongated tube 43 and drive shaft 57 are 6061-T6 aluminum tubing having a wall thickness ranging from 0.058-0.065 inches and 1020 mild steel tubing having a wall thickness of 0.065 inches.
As shown in FIG. 4, first drive shaft end 59 is preferably connected to drill output shaft end 7 through a rigid coupling connection. A typical type of connection is shown to comprise a washer-shaped insert 63 having a threaded circumference 65 for mutual engagement with like threads 67 cut or formed on the inside wall 69 of drive shaft end 59. Said insert 63 has formed therein a smooth-bore central aperture 71 for receipt therethrough of the threaded shaft 73 of a bolt 75 whose bolt head 77 is positioned on the opposite side of insert 63 from drill forward shaft end 7. The threads of bolt shaft 73 are opposite in direction from the threads of threaded insert circumference 65 and drive shaft end threads 67. Matching threads 79 are formed about drill forward shaft end 7 for receipt thereover of the threaded portion of drive shaft end 59. Depending upon the relative diameters of shaft end 7 and inside tube wall 69, a separate thread reinforcing coil 81, such as a Helicoil (tm), manufactured by Heli-Coil Products, Division of Mite-Corporation, Danbury, Conn., may be inserted therebetween to assist in obtaining a rigid connection. A central bore 83 is formed forward shaft end 7 and threaded in the same direction and diameter as bolt shaft 73 for threaded receipt therein to lock drive shaft end 59 into rigid connection with output shaft 5 and to compensate for any drive shaft length variation. Adhesive, such as Locktite 290 (tm) may be added to the mating surfaces of the aforesaid components to retain them in position notwithstanding coil 81 established between insert 63 and forward shaft end 7.
As an alternate embodiment, elongated drive shaft 57 may be connected to electric drill output shaft end 7 by the use of the drill's chuck (not shown) being open to receive first drive shaft end 59 in clasping relationship therein, said drive shaft end 59 formed with circumferential lands or other grasping geometry, and thereafter tightened. While this latter embodiment is not preferred it is possible thereby allowing drill 3 to be temporarily and conveniently separated from device 1 and used for other purposes.
A universal joint 85 is interposed shaft 57 to compensate for shaft bending during use of device 1. As shown in FIG. 5, joint 85 is comprised of a pair of sleeves 87a and 87b axially aligned with their adjacent ends 89a and 89b formed into pairs of mutually spaced-apart ears 91a and 91b and 93a and 93b interconnected by a pivot pin 95 as is generally known in the art. Sleeve 87a is slipped over second drive shaft end 61 and sleeve 87b is slipped over second means input shaft stub 97; both are held fast to their respective inserted shafts by keyways (not shown) or by roll pins 99a and 99b received in bores formed through the respective sleeve and shaft.
As shown in FIGS. 5 and 6, second means 47 is provided and connected to drive shaft 57 through universal joint 85 for reducing the input rotation speed from drill 3 and divert it to a slower output rotation about an output shaft stub 101 whose central axis W--W is aligned substantially parallel to the axis of rotation X--X of the front wheel of the aircraft when device 1 is pivotally attached to the aircraft. As shown in FIG. 6, one embodiment of second means 47 comprises a worm-gear type reducer 103 connected through input shaft stub 97 and universal joint 85 to drive shaft second end 61. An internal worm gear and meshed drive gear (not shown) are arranged to reduce the incoming rotation speed of input shaft stub 97 to a lower speed and correspondingly higher torque and divert the output shaft rotation to output shaft stub 101. While the angle between drive input shaft stub 97 and output shaft stub 101 may vary with different situations, it is preferred that it be maintained at approximately 90°. An example of second means 47 of the type just described and usable herein is a Model 710-10-J Worm Gear Reducer manufactured by Boston Gear, Incom International Inc. of Boston, Mass.
Examples of other means 47 for reducing the incoming speed of drive shaft 57 and for changing the direction of rotation from a direction aligned with drive shaft 57 to an output shaft stub 101 whose axis of rotation is parallel to the axis of rotation of the aircraft's front wheel exist such as separate planetary rotary speed reducing devices for implantation along drive shaft 57 or along the axle axis as well as diverters such as universal joints that change the direction of rotation without reducing speed. All of these different types of means are fully contemplated in this invention.
A bracket 109, defined by a base plate 111, an upstanding side wall 113, an upstanding rear wall 115 and front edge 117, is provided on which is mounted second means 47. Second means 47 is shown in FIGS. 6 and 8 to be mounted to base plate 111 with bolts 107 received in threaded apertures formed therein (not shown). An aperture 119 is formed in rear wall 115 through which passes input stub 97. Another aperture 121 is formed in bracket side wall 113 opposite output shaft stub 101 and is adapted to receive a bearing 123 therein. An axle 125 is attached and keyed to output shaft stub 101 and is supported in bearing 123 for turning therein with output shaft stub 101. A flange 127 is welded or otherwise attached to elongated tube second end 45 and bolted to bracket rear wall 115 with bolts 129 and nuts 131. By this means drill 3, elongated tube 43, drive shaft 57, second means 47 and bracket 109 are all maintained in fixed geometry.
As shown in FIGS. 6 and 8, a drive roller or wheel 133 is fixedly mounted on axle 125 for rotation with second means output shaft stub 101 in response to rotation of drill motor 9 turning drive shaft 57. Drive wheel 133 is made of frictional material and shaped for tangential contact against the front tire of the aircraft to be moved. While a wide variety of materials and shapes are usable herein, it is preferred to have drive wheel 133 made of hard wood, such as oak, and be made in the shape of a pair of face-together contiguous frustums 135a and 135b where their smaller diameters 137a and 137b lie in a common plane Y--Y and are jointed together at said plane. Wheel 133 is conveniently attached to axle 125 by adhesive bonding, pins or other known means.
Attached to the underside of bracket base plate 111 and extending forward of bracket front edge 117 is pivotal means 139 for temporarily attaching device 1 to the aircraft such that drive wheel 133 is able to be brought into tangential contact wherein plane Y--Y is co-planar with the plane Z--Z of the front wheel of the aircraft as shown in FIG. 7.
One embodiment of pivot means 139 comprises a pair of spaced-apart elongated fingers 141 and 143, arranged mutually parallel and attached to the underside of base plate 111 at an angle "A" by welding or otherwise through a pair of small, triangular shaped brackets 145 and 147 that are attached between base plate 111 and fingers 141 and 143. Said fingers 141 and 143 extend in the same direction beyond base plate front edge 117 and terminate in distal ends 149 and 151. Preferably, fingers 141 and 143 are formed in square or rectangular hollow cross-section for weight advantage having mutually parallel, facing, spaced-apart walls 153 and 155. The distance between said walls 153 and 155 is shown in FIG. 7 as "B" and is slightly larger than the aircraft attachment points or strut 157 (shown in phantom) for the front wheel 159 (shown in phantom) of the aircraft on which device 1 is to be used. A pair of spaced-apart yet facing apertures 161 and 163, preferably lined with steel sleeves 165 and 167, are formed in walls 153 and 155 near distal ends 149 and 151 for receipt therein of the ends 169 and 171 of a cross-pin 173 that is normally found in tubular strut 157 above front aircraft wheel 159.
The phantomed strut and wheel assembly shown in FIG. 7 is that found in a Beech model aircraft. Other configurations of pivotal means 139 may be needed for other designs of aircraft, such as for instance the Cessna model aircraft where the cross-pin is found rearward of that found in the Beech, or such as in the Piper aircraft where the cross-pin is replaced by a flat member having rounded ends but containing an aperture adjacent each end of the pin. In this latter situation, fingers 141 and 143 would be narrowed and curved to temporarily fit through these apertures to operably connect device 1 to the front of the aircraft. All of these means are fully contemplated herein.
In the particular embodiment shown in FIG. 7, finger 141 is made in two parts: a first larger part 175 that is welded or otherwise attached through bracket 145 to base plate 111 and extending a short distance beyond front edge 117 and a second, smaller cross-sectional element 177 that is partially received in first larger part 175 at its opened end 179 and is adapted to pivotally rotate by a hinge-pin 181 passing therethrough. A cross-bore 183 is formed through parts 175 and 177 outboard of hinge pin 181 and is adapted to receive therein a lock pin 185 when apertures 161 and 163 are placed over the cross-pin ends 169 and 171 to pivotally attach device 1 on aircraft front strut 157. A cutout portion 187 is formed in finger 175, opposite finger wall 153 to allow smaller finger part 177 to pivot off of its centerline into the opposite direction to allow apertures 161 and 163 to be placed about cross-pin 173 as shown in dotted lines in FIG. 7.
In operation, fingers 141 and 143 and apertures 161 and 163 are placed over exposed cross-pin ends 169 and 171. Lock-pin 185 is then inserted into cross-bore 183 to lock fingers 141 and 143 in position about strut 157 and temporarily pivotally attach device 1 to the aircraft above its wheel 159. As shown in FIG. 9, tube 43 supports drill 3 out in front of aircraft front wheel 159 and at an angle "C" of approximately 40° above the surface over which the aircraft is to be moved. As shown in FIG. 10, the user merely grasps drill handle 13 and pushes downward to swing drive wheel 133 down against aircraft front wheel 159. By squeezing finger-actuated switch 17, drill motor 9 is caused to turn drive wheel 133 against aircraft wheel 159 to move the airplane. Swinging drill 3 to the left or to the right will cause the moving airplane to veer toward that particular direction. Angle "C" will vary depending upon the type of aircraft, size of the aircraft's wheel and tire and size of drive wheel 133. | A portable aircraft moving device comprising a portable electric drill containing a drive shaft extending from the drill output shaft to a worm gear reducer having an output shaft connected to a drive wheel that is mounted temporarily to the front wheel of an airplane above the airplane wheel, the drive shaft located inside a straight hollow support tube attached between the drill and the gear reducer, so that by actuating the trigger on the drill, causes the drive shaft to be turned and produce, through the gear reducer, rotation of the drive wheel on an axis parallel to the axis of the airplane's wheel. Pivotal means are employed to allow the drive wheel to be rotated into contact with the airplane wheel, by lowering the drill, to impart rotation to the airplane's wheel and movement to the airplane. | 1 |
BACKGROUND OF THE INVENTION
[0001] The present invention, in general, relates to a shredder for shredding semi-solid or particulate matter entrained in a non-homogenous liquid-solid flow. The shredder disclosed herein finds an application in process industries, for example in the ore, paper, pulp, food and fiber industries for macerating particulate or solid material in an incoming liquid-solid feed.
[0002] An example of the application of the shredder disclosed herein is in marine and recreational vehicle toilets. These toilets are designed to accept waste, such as human waste and toilet paper which can be easily flushed down the toilet. But if products such as feminine hygiene and diapers are discarded in the toilet, the toilet often clogs. Repeated attempts to flush such products down the toilet may eventually be successful but it results in excessive usage of fresh water. In one embodiment of the invention disclosed herein, the shredder is located downstream of the toilet bowl discharge line of a marine or recreational vehicle toilet to prevent clogging of toilets, especially when products such as feminine hygiene products and baby diapers are discarded in the toilet bowl.
[0003] In general, there is an unsatisfied market need for shredding solid matter in an incoming liquid-solid feed without clogging the line transporting such flow.
BRIEF DESCRIPTION OF THE DRAWINGS
[0004] FIG. 1A illustrates the exploded view of the shredder.
[0005] FIG. 1B illustrates the impeller assembly.
[0006] FIG. 1C illustrates the plan view of the impeller assembly.
[0007] FIG. 1D , FIG. 1E and FIG. 1F illustrate different isometric views of another embodiment of the impeller.
[0008] FIG. 1G illustrates the sectional view of the impeller taken along section line A-B of FIG. 1E .
[0009] FIG. 1H illustrates the side elevation view of the impeller assembly.
[0010] FIG. 1I illustrates the isometric view of the cup.
[0011] FIG. 1J illustrates another isometric view of the cup.
[0012] FIG. 1K illustrates the plan view of the cup.
[0013] FIG. 1L illustrates the side elevation view of the cup.
[0014] FIG. 1M illustrates an isometric view of the impeller assembly abutting the cup with the cutting blade projecting through the circular opening in the cup.
[0015] FIG. 2A illustrates the perspective view of the self-contained toilet system.
[0016] FIG. 2B illustrates the exploded view of the self-contained toilet system with the built-in shredder.
[0017] FIG. 2C is a cross-sectional rear view of the self-contained toilet system with built-in shredder.
DETAILED DESCRIPTION OF THE INVENTION
[0018] The method and apparatus of this invention, including all its embodiments are herein referred to as a shredder.
[0019] FIG. 1A illustrates the exploded view of the shredder 100 . The shredder 100 housing comprises an inlet line 109 through which the liquid-solid feed enters the reservoir 116 located in the front section of the shredder housing 110 , a generally cylindrical cup 106 that is open at the upstream end with respect to the incoming liquid-solid flow and capped at the other end by a circular end-cap 114 with an axial opening 107 through which the cutting blade 112 projects into the cup 106 , an impeller assembly 103 mounted on a shaft 115 , and a motor 101 that drives the shaft 115 . The cup 106 including the end-cap 114 is stationary and does not rotate.
[0020] An O-ring 105 on the discharge side of the shredder 100 provides a seal between the front section of the housing 110 and the rear section of the housing 102 .
[0021] FIG. 1B illustrates one embodiment of the impeller assembly 103 . The impeller assembly 103 consists of impellers 104 rigidly affixed to the impeller plate 116 and extending radially from the center of the impeller plate 116 towards the circumference of the impeller plate 116 and perpendicular to the upstream face of the impeller plate 116 with the cutting blade 112 located at the center of the impeller 104 . In one embodiment of the invention shown in FIG. 1B , the impeller assembly 103 consists of two impellers 104 positioned at right angle to each other with an integrally machined or cast cutting blade 112 . In another embodiment of the invention, the cutting blade 112 may be cast separately from the impeller 104 and thereafter rigidly affixed to the impeller 104 . In the assembled position, the impeller assembly 103 is positioned with the impeller 104 adjacent to and abutting the downstream surface of the end-cap 114 with the cutting blade 112 projecting through and upstream of the axial opening 107 in the end-cap 106 . With the shedder in operation, the cutting surface 118 of the cutting blade 112 shreds solid matter in the liquid-solid feed as the feed approaches the opening 107 in cup 106 . The surface 117 of the impeller 104 rotates adjacent to and immediately downstream of the end-cap 114 . The relative motion of the surface 117 of impeller 104 over the downstream surface of the end-cap 114 shreds the solid matter in the liquid-solid feed at the downstream surface of the opening 107 , and in one embodiment of the invention where the opening has a plurality of recesses 113 , also at the downstream surface of the recesses 113 . The impeller assembly 103 is located in the housing 110 of the shredder 100 . The shaft 115 is connected at one end to the center of the impeller plate 116 and to the variable speed motor 101 at the other end. In one embodiment of the invention, impellers 104 shown in FIG. 1D through 1F are axially mounted at one end of the shaft 115 , with the other end of the shaft 115 connected to the motor 101 . In one embodiment of the invention, the speed of the motor 101 is adjustable. For example, the motor 101 speed may be adjusted to provide a cutting blade 112 rotational speed of approximately 2600 revolutions per minute.
[0022] FIG. 1C illustrates the plan view of the impeller assembly 103 showing the impeller 104 and the cutting blade 112 at the center of the impellers 104 .
[0023] FIG. 1D , FIG. 1E and FIG. 1F illustrates another embodiment of the invention where the impeller assembly comprises only the impeller 104 and the cutting blade 112 .
[0024] FIG. 1G illustrates the sectional view of the impeller assembly 103 showing the impeller 104 , cutting blade 112 , cutting surface 118 and impeller surface 117 that abuts the downstream surface of opening 107 and recesses 113 .
[0025] FIG. 1H illustrates the side elevation view of the impeller assembly 103 , the impeller 104 , cutting blade 112 and impeller plate 116 as shown in FIG. 1B .
[0026] FIG. 1I illustrates an isometric view of the generally cylindrical cup 106 that is open at one end and has a circular end-cap 114 at the other end. The end-cap 114 has an axial opening 107 opening that provides a conduit for transfer of the feed through the end-cap 114 . In one embodiment of the shredder, cutting teeth 111 are located along the circumference of the opening 107 . The axial opening 107 may be of any generally circular shape. In another embodiment of the invention, the opening 107 is in the shape of a circle with a plurality of recesses 113 . In another embodiment of the invention, cutting teeth 111 are located on the periphery of the opening 107 . In yet another embodiment of the invention, the cutting teeth 111 and recesses 113 are located alternately on the periphery of the opening. The relative motion of the section of the impeller blade 112 that projects through opening 107 with respect the stationary cutting teeth 111 , shreds the solid material in the incoming liquid-solid feed as the feed moves through the opening 107 . The recesses 113 also provide a conduit for transfer of the incoming feed through the end-cap 114 .
[0027] FIG. 1J illustrates another isometric view of the cup 106 showing the axial opening 107 , cutting teeth 111 and recesses 113 located along the periphery of the opening 107 .
[0028] FIG. 1K illustrates the plan view of the cup 106 with the axial opening 107 , and the recesses 113 and cutting teeth 111 located along the periphery of the axial opening 107 .
[0029] FIG. 1L and FIG. 1M illustrates the impeller assembly 103 in the assembled position with the impeller assembly 103 adjacent to and abutting the end-cap 114 of cup 106 with the cutting blade 112 projecting through the opening 107 in cup 106 .
[0030] FIG. 2A illustrates the perspective view of the self-contained toilet system, with the built-in shredder 100 . The toilet consists of a seat cover 201 , a hand lever 203 and a toilet bowl 202 .
[0031] FIG. 2B illustrates an example of the exploded view of a self-contained toilet system with the built in shredder 100 . A seat cover 201 is positioned above the toilet bowl 202 . The shredder 100 is positioned below the toilet bowl 202 . An inlet port 109 accepts the contents of the toilet bowl 202 when the flush is actuated. The shredded waste is discharged through the outlet 108 of the shredder 100 . The flush can be either manually operated using a hand lever 203 control or electronically activated using an electronic timer control circuit 206 powered off a wall switch. A solenoid valve (not shown) regulates water consumption during each flush by controlling the inlet water pressure. The hand lever 203 operates a crank (not shown) that is connected to a crank lever. Micro-switches are placed in various locations with respect to crank lever positions. Multi-functional operation of the crank lever is achieved using these micro switches. The hand lever 203 also activates the flush. The electronic timer control circuit 206 sequences the flush by first bringing water in through the intake hose 207 , emptying the toilet bowl 202 and re-filling the water in the toilet bowl. A discharge connector 204 is connected to the inlet port 109 of the front section of the shredder housing 110 . The outlet 205 of the toilet bowl 202 is connected to the discharge connector 204 .
[0032] FIG. 2C is a cross-sectional rear view of the self-contained toilet system with a built-in shredder 100 showing the outlet of the toilet bowl 205 , cutting edge 112 , the semi-circular recesses 113 , and the shredder outlet 108 .
[0033] When the motor 101 is turned on, the rotation of the impeller over the downstream surface 114 of the cup 106 creates suction to effect the transfer of the incoming liquid-solid feed from the reservoir 100 located in the front section of the housing 110 through the opening 107 . As the feed moves towards and through the opening 107 , the solid material in the feed is shredded by the following: the cutting edge 118 of the rotating cutting blade 112 , the cutting surface 117 of the rotating impeller 104 as the solid material in the feed moves to a point immediately downstream of the opening 107 and the recesses 113 , and by the rotation of the impeller 104 with respect to the stationary cutting teeth 111 located on the periphery of the opening 107 . The centrifugal action of the impeller 104 throws the shredded feed to the rear section of the housing 102 from where the shredded waste is discharged through outlet nozzle 108 located at the upper part of the rear section of the housing 102 .
[0034] In one embodiment of this invention, the apparatus comprises a toilet bowl 202 , a discharge opening at the bottom of said toilet bowl 205 and the shredder 100 positioned at the bottom of the toilet bowl 202 . When a flush hand lever 203 is actuated, the waste from the toilet bowl feeds through the shredder inlet line 109 to the upstream reservoir 116 located in the front section of the housing 110 . The outlet 108 of the shredder 100 is coupled to and in fluid communication with the exterior discharge opening of the toilet bowl 202 .
[0035] When the flush hand lever 203 is actuated, motor 101 is turned on and waste from the toilet enters the shredder 100 through the inlet line 109 . The cutting blade 112 rotates along the upstream surface of the stationary circular end-cap 114 to shred the incoming particulate matter in the liquid-sold feed. The feed containing the shredded particulate matter passes through the opening 107 ; and, in one embodiment of the invention, through the opening 107 and recesses 113 located on the periphery of the opening 107 . The rotation of the impeller blades 104 creates suction to transfer the waste from the upstream reservoir 116 of the shredder to the outlet 108 of the shredder 100 . The shredder 100 shreds solid wastes such as feminine hygiene and baby diaper products in addition to human sewage and toilet paper. The shredded feed is discharged through the discharge nozzle 208 .
[0036] The following example illustrates the working of the shredder 100 in a toilet application. Ms. Jenny goes to a restroom to use the toilet facilities, and needs to dispose off a soiled sanitary napkin. She wraps the soiled sanitary napkin and puts it into the waste basket. Even though quite simple and cost-effective, this conventional method poses a threat of infection to other toilet users through atmospheric dispersal of microbial germs and such disposal also emits an unpleasant odor. If the restroom is equipped with the shredder, Ms. Jenny need not dispose it off in the wastebasket. She can flush the soiled sanitary napkin down the toilet bowl 202 . When the flush hand lever 203 is activated, a shredder 100 mounted inside the toilet bowl 202 is also activated. The rotation of the cutting blade 112 and the impeller 104 , and the rotation of the impeller 104 with respect to the cutting teeth 111 on the opening 107 shreds the soiled sanitary napkin inside the toilet bowl 202 , and the shredded waste is flushed out without clogging the toilet system. | Disclosed herein is a non-clog shredder that is used to shred solid matter entrained in a non-homogenous liquid-solid feed. In one embodiment of the invention, the shredder is located at the bottom of a toilet bowl and is used to shred solid disposable products such as napkins and diapers that are discarded in the toilet bowl. The shredder comprises a generally cylindrical cup that is open at one end, with a circular end-cap at the other end. The end-cap has an axial opening that allows the feed to pass through the cup. In one embodiment of the invention, the opening has recesses and/or teeth on the periphery of the opening. An impeller disposed against the circular end plate creates suction for transfer of the waste through the shredder. A cutting blade on the impeller assembly projects axially through the opening in the end-cap. | 4 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] The invention claims priority under 35 U.S.C. §119 to provisional application serial No. 60/450,042, filed Feb. 26, 2003, the disclosure of which is incorporated herein by reference in its entirety.
FIELD OF THE INVENTION
[0002] This invention relates to containers.
[0003] More particularly, the present invention relates to storage and transport bins.
BACKGROUND
[0004] In the art of storage and shipping bins, especially those used in retail markets, safety and durability are very important. Conventional bins used for transport and storage are formed of corrugated paper formed in an octagonal shape and carried on a rectangular pallet. These bins typically have an open top and are used to hold a variety of bulk items, such as watermelons and pumpkins in grocery stores, stuffed animals, balls, etc. in toy stores, and the like. While simple, inexpensive and effective at holding items, the octagonal shape solves some problems, but creates more. Specifically, the shape provides greater structural rigidity than rectangular bins. However, the shape also leaves the corners of the rectangular pallets, upon which they sit, uncovered. These exposed corners can and have resulted in injuries and lawsuits. It would be highly advantageous, therefore, to remedy the foregoing and other deficiencies inherent in the prior art.
[0005] Accordingly, it is an object of the present invention to provide a new and improved bin.
[0006] Another object of the invention is to provide a bin having structural rigidity and having outer walls matching a supporting pallet.
[0007] And another object of the invention is to provide a rectangular bin having an octagonal inner wall.
[0008] Still another object of the present invention is to provide a unitary sheet folded into a double walled bin.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] The foregoing and further and more specific objects and advantages of the instant invention will become readily apparent to those skilled in the art from the following detailed description of a preferred embodiment thereof taken in conjunction with the drawings, in which:
[0010] [0010]FIG. 1 is a perspective view illustrating a bin according to the present invention.
[0011] [0011]FIG. 2 is a top plan of an unfolded bin sheet;
[0012] [0012]FIG. 3 is a perspective view of a glued and collapsed bin;
[0013] [0013]FIG. 4 is a side view of the collapsed bin of FIG. 2;
[0014] [0014]FIG. 5 is a perspective view illustrating folding the bin sheet into a bin; and
[0015] [0015]FIG. 6 is a perspective view illustrating the final folds forming the bin.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0016] Turning now to the drawings in which like reference characters indicate corresponding elements throughout the several views, attention is first directed to FIG. 1 which illustrates a bin generally designated 10 supported upon and substantially covering a pallet 12 . As can be seen, the footprint of bin 10 substantially matches the surface of pallet 12 . Bin 10 includes outer walls 13 and bottom 14 defining a substantially rectangular volume and inner walls 15 define an octagonal volume within outer walls 13 . It will be understood that while a rectangular bin is illustrated, outer walls 13 can also define other shapes such as a square.
[0017] Referring now to FIG. 2, a bin blank 16 is shown to illustrate the various scores and cuts used to create bin 10 from a single integral sheet of material. Blank 16 is preferably formed of multiple walled corrugated paper well known in the art. Single, double, triple or more layers of corrugated paper can be employed as desired. Blank 16 is then processed to create the scores, perforated scores and cuts as shown, in any manner or method, but preferably by die cutting. Through cuts are designated A, standard scores are designated B, perforated scores are designated C. Blank 16 is divided into longitudinal rows 17 , 18 and 19 . Row 17 is separated from row 18 by scores B. Row 18 is separated from row 19 by a combination of scores B and cuts A.
[0018] With additional reference to FIG. 2, bottom flaps 21 , 22 , 23 and 24 are formed in row 17 of blank separated by through cuts A. Flaps 21 and 23 each include a pair of slots 26 formed in the score separation from row 18 and are shaped to include tabs 27 . Flaps 22 and 24 include a pair of slots 28 formed in the score separation from row 18 and include slots 29 formed therein for receiving tabs 27 . Flaps 22 and 24 each additionally include a pair of slots 30 formed diagonally therein, for purposes which will be described presently and slots 31 . Tabs 27 are received within slots 29 to form flaps 21 , 22 , 23 , and 24 into bottom 14 . It should be understood that other types of bottom configurations can be employed.
[0019] Still referring to FIG. 2, row 18 is separated into panels 35 , 36 , 37 and 38 by standard scores B, and a glue tab 40 extending from panel 38 for attachment to panel 35 to create a collapsed bin 10 as illustrated in FIG. 3. Row 19 is separated into two 3-wall panels 43 , and 44 , and two end walls 45 and 46 by through cuts A. 3-wall panels 43 , and 44 , and end walls 45 and 46 each include a pair of tabs 47 along their cut edge which correspond to and are received within slots 26 and 28 . End walls 45 and 46 include additional slots 50 formed in the separation from row 18 . 3-wall panels 43 and 44 each include a central portion 52 and opposing end portions 54 and 55 separated from central portion 52 by perforated scores C. Each end portion is further divided by a perforated score C to form an angle wall 58 and an end flap 59 . Angle walls 58 include a tab 61 extending from the cut edge and end flaps 59 include a tab 62 extending from the cut edge.
[0020] Due to processing constraints, 3-wall portion 44 is completed in the gluing process which creates collapsed bin 10 . Thus, end portion 55 of 3-wall portion 44 is created by providing end flap 59 thereof with a glue tab 65 . Glue tab 65 is adhered to angle wall 58 to create the correct 3-wall panel. While this is the preferred process, one skilled in the art will understand that 3-walled panel 44 can be formed without end portion 55 . It will also be seen that additional scores 70 are formed in 3-wall panels 43 and 44 . This is to facilitate proper folding into collapsed bin 10 for use on existing machinery.
[0021] Turning now to FIGS. 1, 5 and 6 , bin 10 is created from collapsed bin 10 by first folding bottom flaps 21 , 22 , 23 and 24 to form bottom 14 and outer walls 13 . Referring to FIG. 5, 3-wall panels 43 and 44 are then folded over in the direction of the arrowed lines to create six of the sides of octagonal inner walls 15 . Tabs 47 of 3-wall panels 43 and 44 are received within slots 28 formed in bottom 14 to position and retain 3-wall panels 43 and 44 in position. Tabs 61 are received in slots 30 of bottom 14 , and tabs 62 are received in slots 31 of bottom 14 . With reference to FIG. 6, end walls 45 and 46 are folded over in the directed of the arrowed lines with tabs 47 being received within slots 26 formed in bottom 14 to position and retain end walls 45 and 46 . Additionally, end walls 45 and 46 overlie end flap 59 , further securing them. Tabs 70 of end flaps 59 are received within slots 50 to further retain end flaps 59 . The interconnections provide a secure and rigid bin.
[0022] Various changes and modifications to the embodiments herein chosen for purposes of illustration will readily occur to those skilled in the art. To the extent that such modifications and variations do not depart from the spirit of the invention, they are intended to be included within the scope thereof. | An improved corrugated paper bin blank, collapsed bin, and bin for holding bulk goods are disclosed. According to an embodiment, the bin blank comprises three longitudinal sections, one for a bottom section, another for rectangular outer walls, and a third for octagonal inner walls. Various cut and/or scored portions of the longitudinal sections fold and overlap each other to create the final bin, and can be secured with matching tabs and slots. | 1 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates generally to an apparatus and method for loading a medical device onto a minimally invasive delivery system, such as a delivery catheter, and deploying the device in situ.
[0003] 2. Description of the Related Art
[0004] Percutaneous aortic valve replacement (PAVR) technology is emerging that provides an extremely effective and safe alternative to therapies for aortic stenosis specifically, and aortic disease generally. Historically, aortic valve replacement necessitated surgery with its attendant risks and costs. The replacement of a deficient cardiac valve performed surgically requires first opening the thorax, placing the patient under extracorporeal circulation or peripheral aorto-venous heart assistance, temporarily stopping the heart, exposing and excising the deficient valve, and then implanting a prosthetic valve in its place. This procedure has the disadvantage of requiring prolonged patient hospitalization, as well as extensive and often painful recovery. Although safe and effective, surgical replacement presents advanced complexities and significant costs. For some patients, however, surgery is not an option for one or many possible reasons. As such, a large percentage of patients suffering from aortic disease go untreated.
[0005] To address the risks associated with open-heart implantation, devices and methods for replacing a cardiac valve by less invasive means have been developed. For example, CoreValve, Inc. of Irvine, Calif. has developed a prosthetic valve fixed to a collapsible and expandable support frame that can be loaded into a delivery catheter. Such a prosthesis may be deployed minimally invasively through the vasculature at significantly less patient risk and trauma. A description of the CoreValve bioprosthesis and various embodiments appears in U.S. Pat. Nos. 7,018,406 and 7,329,278, and published Application Nos. 2004/0210304 and 2007/0043435. By using a minimally invasive replacement cardiac valve, patient recovery is greatly accelerated over surgical techniques. In the case of the CoreValve device, the support frame is made from shape memory material such as Nitinol. Other catheter-delivery valve replacement systems use stainless steel, or do not rely upon a rigid frame.
[0006] As demonstrated successfully to date, using a transcatheter procedure, percutaneous aortic valve replacement proceeds by delivering a prosthetic valve to the diseased valve site for deployment, either using a balloon to expand the valve support against the native lumen or exposing a self-expanding support in situ and allowing it to expand into place. With the latter, the self-expanding frame remains sheathed during delivery until the target site is reached. Advantageously, the frame may be secured to the catheter to avoid premature deployment as the sheath is withdrawn. In the CoreValve valve prosthesis, a hub is employed with two lateral buttons around each of which a frame zig may reside during delivery. The internal radial force of the sheath keeps the frame compressed against the catheter, including the frame zigs in place around the lateral buttons. The catheter generally comprises at least two tubes, an inner tube that carries the prosthesis and an outer tube that carries the sheath, permitting the sheath to move relative to the prosthesis.
[0007] As with traditional cardiovascular interventional therapies, transcatheter device deployment may proceed retrograde against normal blood flow, or antegrade, with blood flow. For aortic valve replacement, entry through the femoral arteries proceeds in a retrograde format through the iliac, descending aorta, over the arch and to the native annulus. In some cases, entry has been made closer to the arch; for example through the left subclavian artery. Antegrade procedures have been performed whether delivery takes place through the venous system transeptally to the native aortic annulus. More recently, transapical procedures have been performed whereby a cardiac surgeon delivers a catheter through the left ventricle apex to the target site.
[0008] With retrograde deployment, it is generally desired that the catheter be advanced within the vasculature so that the device is positioned where desired at the annulus site. With some embodiments under development, the desired site is the annulus itself. With the CoreValve device, the desired site extends from the annulus to the ascending aorta, given its relative length. In the transfemoral approach, when the CoreValve device is positioned at the desired site, the sheath is withdrawn to the point where the inflow end of the device (preferably positioned at the native annulus) expands to engage and push radially outwardly the native valve leaflets. The sheath continues to be withdrawn proximally as the prosthesis continues to expand as it is exposed until the sheath covers just the outflow portion of the prosthesis still secured to the hub ears. Any readjustment of the axial position of the device in situ can be made during this process based upon electronic visual feedback during the procedure. Once well positioned, the sheath is fully withdrawn, the device fully expands in place, and the catheter is withdrawn through the center of the device and out through the vasculature. While it would be possible to deploy the prosthetic device such that the sheath could be withdrawn distally so that the outflow end of the prosthesis deploys first, such an arrangement would require advancing distally the outer tube of the catheter connected to the sheath distally. In the case of transfemoral retrograde delivery, that would cause the outer tube to project well into the left ventricle, which is not desirable. In a antegrade approach, for example transapical delivery, the reverse situation exists. There it is more desirable to advance the sheath distally to expose the inflow end of the prosthesis at the native annulus first. The native anatomy can accommodate this distal deployment because the outer tube carrying the sheath is advanced up the ascending aorta towards the arch. Like the retrograde approach, once the valve prosthesis is fully deployed, the catheter may be withdrawn through the center of the prosthesis and removed through the apex of the heart.
[0009] With minimally invasive cardiac valve replacement, as may be appreciated, loading of a self-expanding valved frame into a sheath (or capsule) can be difficult because of the frictional forces that inhibit movement of the frame into and out of the sheath. The radial forces attendant in a self-expanding frame are pushing the frame against the inner wall of the sheath during the axial movement of the frame relative to the sheath. The friction translates into a greater axial force that must be applied to smooth and reliably load and deploy the frame from within the distal sheath. Where precision is demanded, such friction requiring greater axial force to be applied makes accurate deployment more difficult. Accordingly, a need exists for a suitable system and method of loading and deploying a self-expanding valved frame using a delivery catheter that reduces the inhibiting nature of the frictional forces during loading and deployment.
SUMMARY OF THE INVENTION
[0010] The invention provided comprises embodiments for minimally invasively delivering a medical device to a patient. The apparatus comprises a sheath that is connected at opposing ends to concentric tubes that move relative to each other in a manner that alternatively covers and exposes the medical device. A portion of the sheath is arranged so as to invert upon itself causing an inversion point. It is contemplated that axial movement of one tube relative to the other simultaneously moves the inversion point over or away from the medical device. In such a manner, there is little frictional engagement between the inversion point and the device (e.g., self-expanding frame). As contemplated, there are several different embodiments that can be made to employ the invention claimed herein, including some with more than one inversion point. These and other features, aspects and advantages of embodiments of the present invention are described in greater detail below in connection with drawings of the apparatus and method, which is intended to illustrate, but not to limit, the embodiments of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] FIGS. 1A-C are cross-sectional views of one embodiment of a device delivery system showing sequential axial movement of an internal tube relative to an outer tube.
[0012] FIGS. 2A-C are cross-sectional views of a second embodiment of a device delivery system showing sequential axial movement of an internal tube relative to an outer tube.
[0013] FIGS. 3A and 3B are cross-sectional views of another embodiment of a device delivery system showing sequential axial movement of an outer tube relative to an outer tube.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0014] Referring to FIGS. 1A-C , one exemplary embodiment of an improved delivery system 10 for a medical device 12 comprises a catheter 14 having a distal end 16 and a proximal end 18 . In the figures shown, and by way of example, the medical device 12 is a self-expanding frame.
[0015] The catheter 14 further comprises a first inner tube 22 and an outer tube 24 . At the distal end of the outer tube 24 is a cap 26 affixed to the outer tube 24 . The cap 26 is preferably configured to have a smooth rounded surface at its distal most-end. By way of simplifying the description herein, FIG. 1A shows the system 10 such that the distal end of inner tube 22 is positioned proximal the distal end of outer tube 24 , whereas FIG. 1B shows the inner tube 22 pulled in a proximal direction, with FIG. 1C showing it pulled further in the proximal direction.
[0016] The catheter 14 further comprises a sheath 30 preferably made of resilient pliable material, such as those used in the industry. The sheath may comprise in whole or in part a braided, woven, or stitched structure, a polymer, or may comprise an inflatable balloon. A first end 32 of the sheath 30 is affixed to an outer surface of the cap 26 affixed to the distal end of the outer tube 24 . A second end 34 of the sheath 30 is affixed to the outer surface of the distal end of the inner tube 22 . As shown in FIG. 1A , the sheath 30 is configured to constrain the medical device 12 in a collapsed position for delivery to a target site.
[0017] The sheath 30 is configured so that it overlaps itself on an external surface of the catheter 14 to form an inversion point 36 proximal of the distal end. The sheath 30 is further configured to conform to the smooth rounded distal surface of the cap 26 such that, as the inner tube is pulled in a proximal direction, the sheath smoothly slides over the cap causing the inversion point 36 to move distally. FIGS. 1A through 1C show that progression. As the sheath 30 is pulled so that the inversion point 36 moves distally, the medical device 12 is progressively exposed, permitting it to expand as desired.
[0018] With the embodiment shown in FIGS. 1A-1C , the inner tube 22 does not need to advance distally beyond the distal cap 26 of the outer tube 24 . Indeed, the catheter 14 need not be placed much more distal than the target site of the medical device 12 . Thus, deployment of a medical device using this embodiment may be made translumenally through the vasculature in one of many possible directions. For example, with respect to an aortic valve replacement, where the medical device 12 is an expandable valved frame, the catheter 14 may be directed transfemorally, transapically or through the sub-clavian artery conveniently. The device 12 may be delivered antegrade or retrograde through the arterial or venous system. Once the medical device 12 is deployed, the entire catheter 14 may be withdrawn proximally from the target site.
[0019] It should be appreciated that loading of the medical device 12 onto the outer tube 24 of catheter 14 would entail collapsing the medical device over the outside surface of the outer tube 24 and then moving the inner tube 22 distally relative to the outer tube 24 so as to cause the inversion point 36 to move proximally over the medical device 12 . When the inversion point has reach its proximal-most point, as shown in FIG. 1A , then catheter 14 may then be used to deliver the medical device 12 . For a self-expanding frame, collapse may be induced by, for example, reducing its temperature. For a balloon expandable frame, the device 12 can be crimped onto the outer tube 24 in one of many known ways. In that case, outer tube 24 would comprise a dilation balloon for in-situ deployment.
[0020] A variation on the embodiment of FIGS. 1A-1C is shown in FIGS. 2A through 2C , where the components are the same. With this embodiment of catheter 114 , the second end 34 of the sheath is attached to the inner tube 22 so as to permit effective advancement of the inner tube 22 in the distal direction, rather than the proximal direction. As the inner tube 22 is directed distally, the inversion point 36 also advances distally, exposing the medical device 12 . While the embodiment of FIGS. 2A-2C may be used in a variety of delivery directions, as discussed above with the embodiment of FIGS. 1A-1C , it is preferred that the target site for the medical device 12 using this catheter embodiment 14 be such that there is sufficient room distal of the target site for effective advancement of the inner tube 22 .
[0021] Referring to FIGS. 3A and 3B , a third exemplary embodiment is shown. There, a medical device 212 is shown sheathed within catheter 214 , which has similar components to catheters 14 and 114 discussed above, but with a somewhat different arrangement. Catheter 214 has a proximal end 216 and a distal end 218 , and comprises an inner tube 222 and an outer tube 224 , where the outer tube and inner tube are movable relative to each other. A collar 226 is affixed to the outside of inner tube 222 . A sheath 230 , covering medical device 212 , has a first end 232 affixed to collar 226 and a second end 234 affixed to the outside distal end of outer tube 224 . The sheath 230 is arranged so as to create an inversion point 236 at a distal location. As the outer tube 224 is retracted proximally, the inversion point 236 likewise moves proximally, exposing the medical device 212 in the same way as explained with the other embodiments.
[0022] It should be understood that with any of these exemplary embodiments, or any variation on these configurations, the clinician may manipulate the alternative of the inner or outer tubes to expose the medical device, although this would result in the medical device moving toward a target site during its deployment, rather than remaining stationary during deployment. For example, in the first embodiment, instead of pulling the inner tube 22 proximally, the medical device 12 may be exposed by advancing the outer tube 24 distally. The result is the same; the inversion point 36 is advanced distally. Likewise, the outer tube 24 of embodiment 2 A- 2 C could be pulled proximally rather than the other tube advanced distally and the inner tube 222 of embodiment 3 A- 3 B could be pulled distally, rather than the other tube being advanced proximally.
[0023] One advantage of using an inverting sheath to load and deploy a medical device is that the sheath alternatively covers and exposes the medical device by predominantly a rolling motion rather than a sliding motion, which results in less friction between the medical device and the sheath. This reduces the force required to retract the sheath, which enables more control over the deployment position by, for example, reducing the compression and elongation of the delivery catheter. In addition, where the medical device comprises a prosthetic tissue-based heart valve sutured to a self-expandable frame, the patient's body heat can cause the frame to want to revert to its natural expanded configuration, thereby exerting an outward force against the sheath. During deployment, friction between the sheath and medical device can damage the tissue-based heart valve and sutures. Accordingly, reducing the friction between the sheath and medical device by using a rolling motion rather than a sliding motion can help reduce damage to the medical device and help maintain the condition of the medical device. In other cases, the medical device may be coated with a drug or bioactive material, and the friction caused by sliding the coated stent out of the sheath can result in removal of some of the drug or bioactive material.
[0024] In some embodiments, the surface of the sheath that contacts the medical device may be tacky, which enables the tacky surface to frictionally engage the medical device and reduce sliding between the medical device and sheath. The surface can be made tacky by, for example, application of a polymeric material such as polyurethane or another thermoplastic elastomer to the surface or by fabricating the surface from the tacky material.
[0025] It is contemplated that the surface of the sheath that contacts itself when inverted may be provided with a lubricious coating or can be made of a lubricious material. The lubricious coating or material can be made of, for example, PTFE, ePTFE, a hydrophilic material, or any other substance that reduces the friction as the inverted sheath slides over itself. Where desired, the sheath may be reinforced to minimize elongation of the sheath as tension is applied. For example, axially-oriented tension bands (not shown) having high tensile modulus material such as ultra high weight polyethylene, Kevlar, carbon, steel, titanium, in the form of a monofilament or fiber may be incorporated within or on the sheath.
[0026] In operation, the catheters described are particularly suited for delivery of a heart valve, where precise placement is important. Other critical and less-critical target sites are also contemplated. In the case of a self-expanding aortic valve replacement, the catheter may be delivered transfemorally, transeptally, transapically or through the sub-clavian, among other possible entry ways. In one procedure, the catheter is deployed so that the valved frame is positioned entirely aligned with the target site; e.g., aortic annulus up to ascending aorta. The frame may then be exposed from one end to the other, depending upon the direction of delivery, by either advancing the inner tube relative to the outer tube (for the embodiment of FIG. 2 ) or vice versa (for the embodiment of FIG. 1 ), or retraction of the outer shaft (for the embodiment of FIG. 3 ). As the frame is exposed, it expands outwardly to engage the native intimal lining so placement accuracy is maximized. When the sheath is fully removed and the frame fully expanded, the catheter may then be withdrawn though the functioning prosthetic valve and removed from the patient.
[0027] Although embodiments of this invention have been disclosed in the context of certain preferred embodiments and examples, it will be understood by those skilled in the art that the embodiments of the present invention extend beyond the specifically disclosed embodiments to other alternative embodiments and/or uses of the invention and obvious modifications and equivalents thereof. In particular, while the present loading system and method has been described in the context of particularly preferred embodiments, the skilled artisan will appreciate, in view of the disclosure, that certain advantages, features, and aspects of the system may be realized in a variety of other applications, many of which have been noted above. Additionally, it is contemplated that various aspects and features of the invention described can be practiced separately, combined together, or substituted for one another, and that a variety of combination and subcombinations of the features and aspects can be made and still fall within the scope of the invention. Thus, it is intended that the scope of the present invention herein disclosed should not be limited by the particular disclosed embodiments described above, but should be determined only by a fair reading of the claims. | A catheter that comprises a sheath that is connected at opposing ends to concentric tubes that move relative to each other in a manner that alternatively covers and exposes a medical device loaded onto the catheter. A portion of the sheath is arranged so as to invert upon itself so that axial movement of one tube relative to the other simultaneously moves the inversion point over or away from the device, alternatively covering or exposing the device. | 0 |
BACKGROUND OF THE INVENTION
[0001] The field of the present invention relates to building materials and particularly to “green” building blocks made from culm such as residual rice straw, a by-product of the rice growing industry.
[0002] Providing affordable housing while decreasing air pollution is an ideal worth fighting for. Housing is typically considered by most not to be affordable due, in part, to the high cost of the building materials. Conventional building materials, such as lumber, are costly because they are becoming more and more scarce as the demand for more and more housing increases to meet the needs of the world's burgeoning population. In addition, when the trees are cut down to make the lumber to build the house, the result is an adverse effect on our air quality as these natural resources are no longer able to turn carbon dioxide into oxygen.
[0003] In an effort to find alternative building materials, people have been turning to recycled goods and/or the by-products of an industry. One such source has been culm, commonly referred to as straw, which is what is left over when grains, such as wheat, rice, barley, oats, and rye, are harvested. Straw is a viable building material because it is plentiful and inexpensive. Buildings built with straw bales have well-insulated walls, simple construction, and low costs. Moreover, in many areas, straw is still burned in fields, producing significant air pollution. For example, in California more than one million tons of rice straw were burned each fall in the early 1990's, generating an estimated 56,000 tons of carbon monoxide annually, which is approximately twice that produced from all of the state's power plants. By converting an agricultural by-product into a valued building material, another benefit to the community is therefore a reduction in air pollution.
[0004] A number of drawbacks exist to the use of straw as a building material. Straw does not have the same structural integrity as wood, cement, or other conventional building materials. As a consequence, straw does not have the load bearing capacity that so many architects, engineers, and contractors require. Straw is also highly susceptible to moisture and can and will rot if there is too much exposure to moisture over time. Moreover, straw bales are of an inconsistent quality. They are also not sized to building industry standards.
[0005] [0005]FIG. 5 is illustrative of some of these points. Shown there are two differently sized conventional straw bales, namely, a 3-tie straw bale on the left and a 2-tie straw bale on the right. The denomination of “3-tie” or “2-tie” is due to the number of ties T being wrapped about the straw stalks S, as seen in FIG. 5. The larger 3-tie bale is typically 32″ to 47″ long by 23″ to 24″ wide by 14″ to 17″ high. The dimensions of a 2-tie bale are similarly varied and are typically in the range of 35″ to 40″ long by 18″ wide by 14″ high. A conventional concrete or cinder building block, however, is typically 24″ long by 12″ wide by 12″ high. The weight of a 3-tie bale can be anywhere between 75 to 100 lbs., whereas a 2-tie bale is typically 50 lbs. OSHA product weight requirements, however, require less than 50 lbs. per block, with 40 lbs. typically being an acceptable weight that can be handled by one person.
[0006] [0006]FIG. 5 illustrates that the straw stalks S of a conventional straw bale appear to be aligned parallel to a single axis of alignment, A w . The appearance of alignment occurs because of the cut, rake, and bale process of making the bale. There are no machines or modifications of machines that intentionally align the straw to make specific straw-aligned bales. The general alignment A w of the straw S can be described as “horizontally aligned”, i.e., horizontal or parallel to the ground G when the bale is laid flat. The general alignment A w can also be described as running parallel to the width W axis and perpendicular to the length L and height H axes or, alternatively, parallel to the plane defined by the top or bottom walls (the intersection of the L and W axes).
[0007] It is the inventors' understanding that those skilled in the art prefer “horizontal alignment” to increase the load bearing capacity of each bale. Gleaned from compression tests of individual bales, the prior art teaches that flat bales can carry far more load than bales stacked on edge. Flat bales failed at an average load of 10,000 lb/ft 2 (48,800 kg/m2); on edge, bales failed at an average of 2,770 lb/ft 2 (13,500 kg/m 2 ). To further increase the load bearing capacity of the bale other than laying it flat, the prior art also teaches the use of threaded rods that may be inserted through each bale or framed around each bale and then bolted through a wide top plate and tightened down after the roof is installed. Pre-compressing the walls in this manner minimizes further settling after the roof is installed.
[0008] [0008]FIG. 5 also illustrates how conventional prior art straw bales do not have a smooth cut surface and the corners are rounded, i.e., the edges are not crisp and the corners are not square. What FIG. 5 does not illustrate is the high level of susceptibility to moisture damage that straw has or the inconsistent and often poor quality of the traditional straw bale itself.
[0009] A “green” building material such as a culm or straw block that has an increased load bearing capacity over traditional straw bales, is of a consistent quality, is sized for building industry standards, and has an increased resistance to water damage is therefore desired.
SUMMARY OF THE INVENTION
[0010] Having recognized these conditions, the present invention is directed to a culm block comprising a plurality of straw stalks that are “vertically aligned”, i.e., perpendicular to the ground when the block is laid flat. Vertically alignment, the inventors surprisingly discovered, advantageously provides for at least 25% greater load bearing capacity compared to conventional horizontally aligned bales. Vertical alignment also advantageously provides for increased insulating values, as well as a smooth cut surface. By vertically aligning the straw, the culm block of the present invention also advantageously has a consistent shape, with square corners and crisp edges.
[0011] Another related aspect of the invention is to provide a culm block that is properly sized for building industry standards.
[0012] The culm block may also be treated with a binder and a moisture inhibitor to further increase the block's quality, structural integrity, and resistance to moisture damage.
[0013] The culm block may optionally include a pair of throughholes drilled through the top and bottom walls. The holes may be used to tie the blocks to the foundation and thereby ultimately increase the shear integrity of the wall system.
[0014] In a similar manner, the culm block may include a lath or external strapping sleeve for added structural support. Prior to the addition of the lath, the culm block may be mill finished to further increase its quality and consistency.
[0015] Another aspect of the present invention is a method for forming the novel culm block that may include sorting the stalks according to length, checking the stalks for moisture content, and drying the stalks depending upon their moisture content prior to compression and formation. Other and further objects and advantages will appear hereinafter.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] [0016]FIG. 1 is a perspective view of a culm block according to a preferred embodiment;
[0017] [0017]FIG. 2 is another perspective view of the culm block shown in FIG. 1;
[0018] [0018]FIG. 3 is a cross-sectional view taken along line 3 - 3 shown in FIG. 1;
[0019] [0019]FIG. 4 is a flow chart illustrating a preferred method of manufacturing the culm block shown in FIG. 1; and
[0020] [0020]FIG. 5 illustrates the prior art.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0021] Preferred embodiments will now be described with reference to the drawings. For clarity of description, any element numeral in one figure will represent the same element if used in any other figure.
[0022] FIGS. 1 - 3 illustrate a culm block 10 comprised of a plurality of adjacent stalks 12 substantially aligned parallel to one another and formed to define the building block 10 . The stalks 12 may be wheat, rice, barley, oats, or rye straw. Rice straw is preferred due to its extremely high silica content and therefore inherent fire retardant properties. Moreover, rice straw is typically weed and pest free.
[0023] The block 10 has a top wall 14 and an opposing bottom wall 16 , a front wall 18 and an opposing rear wall 20 , and first and second opposed sidewalls 22 . A lath 24 is seen disposed about the front and rear walls 18 , 20 and sidewalls 22 . The lath 24 may be described as a sleeve that is wrapped about the block 10 .
[0024] The lath 24 provides increased structural support to the block 10 . Such a feature is particularly advantageous when one considers that a traditional bale typically only has two or three ties usually made of twine for support, such as the ties T illustrated in FIG. 5. Because of such a lack of support, conventional bales can easily fall apart or bulge under their own weight. The lath or wire mesh banding 24 around block 10 girdles it and advantageously provides resistance to the straw stalks 12 from bulging. In addition, the lath 24 also provides an additional option for an anchoring system. In particular, the lath 24 acts as stucco wire and will make the construction process with the block 10 faster than conventional bales. Conventional bales require the stapling of stucco wire on the side of the straw bale wall in order to provide an adequate structural matrix for the stucco. This process is eliminated with the novel block 10 .
[0025] The lath 24 may be comprised of completely recycled material such as recycled steel or plastic. If steel is used, it is preferably galvanized and more preferably galvanized and coated.
[0026] Turning to FIGS. 1 and 2, the top wall 14 and bottom wall 16 define a pair of holes 25 therethrough. Tubing 26 , which may be made from recycled plastic, may be inserted into each hole 25 . The holes 25 , either with or without tubing 26 , may be included in block 10 to offer an optional alignment and anchoring system. If employed, the holes 25 are preferably 2½″ in diameter. Structural steel reinforcing may be inserted through each hole 25 and set with a concrete grout, for example. The pre-drilled holes 25 , when filled with concrete and steel, help to tie the blocks to the foundation, ultimately increasing the shear integrity of the wall system.
[0027] [0027]FIGS. 1 and 2 illustrate a block 10 that is sized to a building industry standard, namely, 24″ long by 12″ wide by 12″ high. Accordingly, the block 10 illustrated in FIGS. 1 and 2 is rectangular in shape. Other dimensions may also be employed as long as they are standardized building sizes. Unlike traditional bales that are odd-sized, such as a 3-tie bale that may be 40″ long by 22″ wide by 16″ high, the block 10 is a size that a builder can utilize consistent with existing building techniques developed for concrete blocks. Consequently, block 10 is easily adapted to current construction techniques; it easily integrates with traditional 4′ by 8′ construction modules; and it requires less space in the floor plan when compared to the larger footprint of a traditional straw bale wall.
[0028] As shown in FIGS. 1 and 2, the block 10 preferably weighs under 40 lbs. With this light weight, one person can handle the block 10 . This weight is also within the OSHA product weight requirements, unlike traditional bales that may weigh up to 75 to 100 lbs., which weight requires two or more persons for moving and constructing.
[0029] As best seen in FIG. 3, the stalks 12 of the culm block 10 are “vertically aligned”, i.e., they are perpendicular to the ground G when the block 10 is laid flat. The axis of alignment A H of the straws 12 is therefore preferably orthogonal to the plane defined by the top and bottom walls 14 , 16 (the intersection of the L and W axes). As seen in FIG. 3, the axis of alignment AH runs orthogonal to the width W and length L axes and parallel to the height H axis or, alternatively, orthogonal to the plane defined by the ground G.
[0030] Contrary to the teachings of the prior art, vertically alignment provides for at least 25% greater load bearing capacity compared to conventional non-aligned or potentially “horizontally aligned” bales. Vertical alignment also advantageously provides for increased insulating values, possibly R-28 or higher, because horizontally placed straw of traditional bales acts like a wick, thus increasing the conductance (U-value) of the material and undesirably allowing for greater thermal transmission. Vertical alignment also provides for a smooth cut surface. By vertically aligning the stalks 12 , the culm block 10 of the present invention has a consistent shape, with square corners and crisp edges. This makes the construction of buildings much more efficient when compared to traditional rounded corner straw bales.
[0031] Turning to FIG. 4, a method of forming the novel block illustrated in FIGS. 1 - 3 is disclosed. As shown there, the first step is “Harvest straw from field” at step 28 . After harvesting, the straw then needs to be transported to the processing facility as shown at step 30 . Once at the processing facility, the straw is unloaded at step 32 , preferably via a hydraulic squeeze lift, and then loaded into an apparatus to remove the ties T (as shown in FIG. 5). The apparatus is preferably a Hunterwood 3-tie de-stacker. Once loaded into the de-stacker, the straw is moved down a conveying system to a twine saw. When the twine hits the twine saw, the bale ties are removed at step 34 . The next step, step 36 , is entitled “Treat straw with a non-toxic moisture inhibitor and/or binder.”
[0032] At step 36 , a moisture inhibitor and/or a binder is disposed on or integrated into the straw 12 . Step 36 ensures that the block 10 , when delivered, has a consistent quality. Current bales, such as those illustrated in FIG. 5, have high fluctuations in sizes, typically up to five inches, and a wide range in moisture content, typically between 10 to 25%. High moisture is the weakness and largest concern for builders interested in integrating straw building materials into their work. Straw will not rot at a moisture content of 14% or less. For this reason, the block 10 preferably has a predetermined moisture content not to exceed 14%. To ensure this, a drier system is part of the manufacturing process, as illustrated in FIG. 4 at step 42 .
[0033] The binder and moisture inhibitor are both preferably environmentally friendly and non-toxic. When treated with the binder, the structural integrity of the block 10 should be increased without decreasing the insulating properties of the block 10 . In a similar manner, when the stalks 12 are treated with the moisture inhibitor, the block's resistance to moisture is increased without decreasing the insulating properties of the block 10 . Accordingly, the binder may be selected from the group consisting of aluminum hydroxide, magnesium hydroxide, clay, kaolin, bitumen, and most preferably borax (a natural product composed of hydrated sodium borate, sometimes referred to as or including sodium borate decahydrate, sodium diborate, tincal, tincalconite, tincar, hydrated sodium boration, sodium tetraborate, rasorite, or Sporax®). The moisture inhibitor may be selected from the group consisting of paraffin wax, silica gel (a non-toxic, non-corrosive form of silicon dioxide synthesized from sodium silicate and sulfuric acid and processed into granular or beaded form), molecular sieve (a uniform network of crystalline pores and empty adsorption cavities derived from sodium, potassium or calcium crystalline hydrated aluminosilicates), activated clay (a layered structure of activated (bentonite) clay that is a naturally occurring, non-hazardous and salt-free substance), bitumen, and most preferably borax.
[0034] Referring again to FIG. 4, the next step in the process is step 38 entitled “Align and sort straw.” Here, the stalks 12 are intentionally aligned substantially parallel and most preferably parallel to one another. The stalks 12 are also preferably sorted according to length, wherein stalks 12 of substantially identical length are grouped together. After the stalks 12 are aligned and sorted together and step 38 , the moisture content of the stalks 12 is then checked at step 40 . The stalks 12 are dried via a drier system dependent upon the moisture content at step 42 . The stalks 12 are preferably dried to a moisture content not to exceed 14%, as straw will not rot at a moisture content of 14% or less.
[0035] After the stalks 12 are dried to the preferred moisture content of 14% or less, the stalks 12 are compressed and formed into standardized building blocks wherein the stalks 12 are vertically aligned or, stated otherwise, perpendicular to the ground when the block is laid flat, as shown in FIG. 4 at step 44 and, regarding the vertical alignment, as best seen in FIG. 3. For compressing and forming the stalks 12 into the block shape, the stalks 12 are preferably fed into a Hunter Wood fc8310 series forage compactor. Once compacted, the block 10 exits the compression chamber and is sleeved with a lath, preferably comprised of recyclable galvanized steel and coated at step 46 . The block 10 then exits the conveyor, is palletized, stretch-wrapped, pallet bar coded, and ready for shipping or storage.
[0036] Prior to the addition of the lath, such as lath 24 illustrated in FIGS. 1 and 2, the culm block 10 may be mill finished to further increase its quality and consistency. Where the optional throughholes, such as holes 25 illustrated in FIGS. 1 and 2, are desired, the holes may be drilled before or after step 46 , but are preferably drilled before step 46 . Tubing 26 may also be inserted into each hole 25 at this time. The pre-drilled holes 25 , when filled with concrete and steel, help to tie the blocks 10 to the foundation, ultimately increasing the shear integrity of the wall system.
[0037] Thus, while embodiments and applications of the novel culm block and method for making the culm block have been shown and described, it would be apparent to one skilled in the art that other modifications are possible without departing from the inventive concepts herein. The invention, therefore, is not to be restricted except in the spirit of the claims that follow. | A culm block and a method of manufacture are disclosed. The culm block comprises a plurality of straw stalks that are “vertically aligned”, i.e., perpendicular to the ground when the block is laid flat. The straw is treated with a moisture inhibitor and/or a binder. Throughholes, which may have tubes associated therewith, are formed into the top and bottom walls of the culm block. A lath or external strapping sleeve is wrapped about the front, rear, and side walls of the block for added structural support. The method of manufacture may include sorting the stalks according to length, checking the stalks for moisture content, and drying the stalks depending upon their moisture content prior to compression and formation. | 4 |
BACKGROUND OF THE INVENTION
The present invention relates to a mechanical fancy seam sewing machine with a cam set for controlling needle and feeding movements.
For sewing complicated fancy seams, such sewing machines are provided with arrangements for automatic control of stitch width, stitch field and feeding. For setting the initial position of the stitch and the stitch field, the sewing machine is equipped with a manual control unit which possibly is a combination control (e.g., a double knob) used for setting of several fancy seams. As to the setting of the stitch width and the zigzag pattern, this is preferably made by a separate control. Such a mechanism for controlling positions and movements in respect to several different units in the machine required that all the interior space in the machine be occupied. Such a machine is described in detail, for example, in Swedish Patent Spec. SE-P-212 970. In more recent sewing machine production, the requirements for lightness and compact performance of the machine have been raised, and therefore the adjustable zigzag mechanism is now built together with the ordinary fancy seam mechanism. This earlier construction described in SE-P-7303690-7 is known for its cam set, gear head and cam follower, which by way of link arms produce and transmit lateral movements to the needle. The lateral movement performed by only a cam disk and links is proportionally simple to effect, but when adjustment and proportionality of such a simply effected movement are also required, the problem with the needle control becomes more complicated. However, it is possible to make the construction somewhat simpler if the stitch field positions only need to be used when sewing straight seams in those positions. As to zigzag sewing machines in general, there is a tendency for an impaired feeding exactness in the middle of the stitch field as the tooth rows of the feed dog are situated widely apart on these machines. A possibility for obtaining better feeding exactness is to locate the stitch formation to some of the outer positions in the stitch field, where at least one tooth row is situated.
SUMMARY OF THE INVENTION
According to the present invention, a fancy seam sewing machine has a cam disk unit rotatable with a driving shaft in the machine, and includes a cam selecting unit which is adjustable by a pattern selection control device relative to the cam disk unit. A movable guide is journalled for oscillatory movement by one of the cam disks and a sensor in the form of a slide in the control device is mounted for oscillatory and sliding movement in the plane of the oscillatory movement of the guide. The slide has a longitudinal slot or groove within which is mounted a pin carried on a bar connected to the needle bar unit. A zigzag control is continuously adjustable to move the slide longitudinally in the direction of the slot and in the plane of oscillatory movement relative to the guide to vary the amplitude of oscillatory movement of the slide, and hence the needle bar unit.
Another feature of the invention is the provision of a mechanism for adjusting the position of the guide during straight stitch sewing so that the guide remains stationary, and adjustable movement of the zigzag control and the resulting longitudinal movement of the slide will then move the pin and bar together with the needle bar unit to move the needle position laterally with respect to the center line.
An embodiment of the sewing machine with the fancy seam mechanism according to the invention is discussed in the following with reference to the attached drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an elevational view of a sewing machine with the back removed;
FIG. 2 is a perspective view of a fancy seam mechanism;
FIG. 3 is a vertical projection, partially in section, of the fancy seam mechanism;
FIG. 4 is a detailed view on line IV--IV of FIG. 3, showing the mechanism in straight seam position;
FIG. 5 is a view similar to FIG. 4, but in the zigzag position; and
FIGS. 6-8 show different seam patterns.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
With reference to FIG. 1. the sewing machine presented contains parts which are known in conventional sewing machines. Consequently, a presser bar and needle bar unit 10, a thread tension unit 11, an upper shaft 12, a stitch length unit 13, a zigzag control 14, as well as lower shafts and the shuttle mechanism, can be recognized. On the front side of the machine, there are control knobs with bearings in the front wall of the machine body. These knobs include control cams, cog wheels, pins, etc. to be found at the inside of the front wall. The zigzag control 14 is located in a pillar 15 of the body and attached with two firm shafts 16,17 included in the unit, whose upper ends are formed as pins and entered into holes in the top side of the body and having their lower ends attached with clamps 18,19 at the body.
With reference to FIGS. and 3, the setting of the zigzag control on different seams is effected with a control knob 20, which, by means of an angular gear train 21,22, is connected to a circular axial cam 23 which thus can be rotated around the shaft 16 by means of the knob. The cam is kept in firm position by a latch 24 which engages with recesses 25 in a co-rotating disk 26. The latch contains an arm 27 journalled in bearings and provided with a wedge-shaped tooth 28 going automatically into and out of the recesses during the rotation of the disk, due to the action of a spring 29 on the arm. On the shaft 16, there is also a cam disk unit 30, journalled and displaceable, and driven by an angular gear train 31, 32 that is driven by the upper shaft 12. The cam disks are scanned by a cam follower 33 which is journalled in bearings on the shaft 17 and tensioned against the cam disks by a plate spring 34 (see FIG. 1) of the needle bar unit. The vertical position of the cam disk unit on the shaft 16 is determined by the axial cam 23, which is funnel-shaped and scanned by a cam follower 35 which has at the bottom a bracket whose end is fit into a groove 37 lowest down in the cam disk unit and holding the unit at the height set. In order to make a vertical adjustment of the cam disk unit possible, a lifting of the cam follower out from the cam disks is necessary, however, and this movement is made by the arm 27, which, by way of a setscrew 38, influences a clamp 39 on which the cam follower is located. When the disk 26 rotates, the arm 27 is forced outward by the tooth 28 and the recess 25, so that the clamp and the cam follower move outward, after which the cam follower 35, with the bracket 30 and a downward acting spring 40, produce a vertical movement according to the shape of the axial cam, upward (by the curve) and downward (by the spring). At the top of the cam disk unit there is a cam disk 41 on a level with a second cam follower 42, which are used for control of the stitch length unit 13 (see FIG. 1) of the machine via a control arm 43. Furthermore, the shaft 17 supports a small clamp 44 which is revolving and has an outgoing arm 45 which supports a bar 46 whose outer end is fixed to the needle bar unit 10. The connection between the arm 45 and the cam follower 33 will now be described in more detail with reference to FIGS. 3-5.
As evident from FIG. 3, the mechanism as shown therein contains a number of flat link elements between the knob 20 and the shaft 17. Inside the knob 20 there is a further knob 47 having an axial cam 48 which is scanned by a cam follower 49 journalled on a supporting plate 50. This cam follower is mechanically connected to a slide 51 which straddles with a fork 52 (also see FIG. 2) over the shaft 17 and has in the middle a groove 53 (see FIG. 4). In this groove there is a bearing pin 54 which, moreover, also unites the arm 45 and the bar 46. The slide can be moved in its longitudinal direction between two end positions which are illustrated in FIG. 4 and FIG. 5. The pin 54 is then at the one and at the other end, respectively, of the groove 53. The one end 55 of the slide is kept in contact with a sliding surface 56 of the cam follower, due to a screw spring 57 which is tensioned between points on the slide as well as on te supporting plate. Between those two, there is a space for a guide 58 journalled on a pin 59 (also see FIG. 3) projecting from the supporting plate. It has the shape of a short angle piece whose one flange 60 is extended over the slide, which then, via a projection 61 on the same, is in a direct connection with the guide. This one has, in its turn, connection by means of a toggle joint 62 with an arm 63 emanating from the clamp 39 by way of a bearing on the shaft 17. The spring 57 is tensioned from a point at the side of the slide, which always causes the projection 61 to be pressed against the flange 60. To the supporting plate there is also fixed a stop pin 64 preventing the end 55 of the slide from moving off the sliding surface 56 (FIG. 5) when being mounted or assembled, as well as during a possible blocking, for instance, from the needle bar.
The axial curve 48 has such a shape that the slide 51 is moved from the position in FIG. 4 to the position in FIG. 5 when the curve is rotated about one revolution. If the guide is situated as in FIG. 5 (solid-line position), the slide end 55 will slide on the surface 56 from the center to one of the borders close to the pin 64. Then the pin 54 is moved closer to the shaft 16, causing the needle to be moved to the left in FIG. 1. This needle position can then be used for straight stitches or constitute a width limit for the zigzag stitches of the machine.
The zigzag seam sewn by the machine when set as in FIG. 5 is symmetrical around a center line in the stitch field and is obtained from a cam disk 65 (see FIG. 2) in the unit. This disk has cams all around which lift the cam follower 33 so that the guide, every second revolution of the machine, is in the solid-line position as to FIG. 5 and, in other revolutions, in the dashed-line position. The pin 54 will then swing between the outer positions, i.e., make an oscillatory movement in FIG. 5, which movement is passed on to the needle bar by the bar 46. By means of the knob 47 and the curve 48, the amplitude of the movement can be set on an arbitrary value so that a picture according to FIG. 6 is obtained when the knob is rotated from the maximum value of zigzag to zero. During this setting movement of the knob 47, the slide 51 is moved from the position in FIG. 5 to that in FIG. 4 and the said oscillatory movement of the pin 54 is decreased successively.
When sewing a zigzag seam, the guide must be free to operate as indicated in the foregoing. When making firm stitch positions in the stitch field, however, the guide should be fixed to the dashed-line or the solid-line position of FIG. 5. When sewing those stitches, the cam follower 33 is put on a cam disk 66 (see FIG. 2) with a low, smooth profile which does not guide the needle bar. The setting of the guide takes place by means of the latch 24, the disk 26, and the spring 34. As to the position according to FIG. 4 (dashed lines in FIG. 5), the spring 34 determines that the needle bar is positioned to the right of the center line according to FIG. 8. The stitches shown there are obtained when the slide 51 is pushed from one of its end positions to the other. The solid-line position shown in FIG. 5 can be fixed by means of the latch 24, whose arm 27 is swung out when the curve 23 is rotated and prevents, by way of the screw 38, the clamp 39 from being drawn against the shaft 16. The tooth 28 located in a lower recess 67 (see FIG. 5) thus constitutes the setting of the needle in the left end position of the stitch field. The stitches which can be sewn in this position are shown in FIG. 7, which thus indicates a continuously variable distance from the center line, which distance is set, as in the foregoing, by means of the knob 47 and the curve 48, the slide 51 thus sliding along the immobile guide. In order to make the stitches in FIG. 7 instead of the stitches in FIG. 8, it is thus necessary to make a separate setting of the knob 20 so that the recess 25 is moved from the tooth 28 and the recess 67 takes that position instead. The basic setting of the knob 47 and the curve 48 is that shown in FIG. 5, as the guide then can freely transfer the movements effected by the cam follower to the slide, and consequently to the needle bar. The knob, however, has a scale which can be used for recommended settings of all controls on the machine. Each control has an indicator showing the value recommended, and as far as the knob 47 is concerned, the indicator consists of, for example, a tape with figures fed by the fancy seam selector 20 and read through a window in the panel. However, such an indicator system is not described in this specification but is more closely explained in another Swedish patent Spec. SE-A-8702191-1. | A fancy seam sewing machine has an infinitely variable zigzag module (47,51,58) which also includes a continuous setting of stitch positions in a stitch field between two outer positions of the needle. The arrangement includes a slide (51) in cooperation with a guide (58) and a setting device (48,49) for the slide as well as a driving unit (33,62) for an oscillatory movement of the guide. The slide has direct contact with the needle bar, which then carries out through the slide an arbitrarily set proportion of the said oscillatory movement. | 3 |
BACKGROUND OF INVENTION
Apparatuses used for melt spinning of synthetic threads are known from German Patent Application 195 40 907 A1, for example.
To this end, a polymer melt is fed to a spin beam from a melt source, for example an extruder or a polymerization unit. Inside the spin beam the melt is fed to usually one, or, by use of a distributor, multiple, metering pumps, which distribute the melt at a defined volumetric flow rate to spin cans in which the filaments are formed. The elements of the spin beam, that is, the distributor, metering pumps, piping, and spin cans, are all heated together and are enclosed by insulation.
Occasionally the physical characteristics of the polymers used for the melt spinning are altered under the influence of temperature and time. Polyamide 6.6, for example, tends to undergo post-polycondensation, resulting in an unmeltable hardening of the material and thus to deposits, or, in extreme cases, to plugging, in the lines. For this reason, in the design of spin beam special attention is given to a uniform, short residence time of the melt in the spin beam, and to a very uniform temperature. The residence time of the melt can be made uniform by mechanically optimizing the flow in the lines. Uniform temperature of the spin beam is achieved by heating, using a heat transfer medium contained as a liquid/gas mixture in the spin beam. Heat is transferred to the cold locations by condensation of the gaseous portion of the fluid on same, so that a very uniform temperature corresponding to the boiling point of the heat transfer medium is achieved within the spin beam. It is also known to use oil as heat transfer medium, or electrical heating.
Despite the above-described constructive measures, spinning of polyamide 6.6 is not regarded favorably by manufacturers of synthetic fibers. If post-polycondensed polymer forms, resulting in plugging of the lines, the spin beam must be completely disassembled and the plugged elements regenerated in an external furnace, i.e.; pyrolytically cleaned at temperatures of 450 to 550° C. This situation may occur in particular upon unit shutdowns, or when there is insufficient polymer throughput. However, even without the occurrence of an unexpected operating state it may be necessary to regenerate the spin beam at certain time intervals.
The cost of regeneration deters small, inexperienced synthetic fiber manufacturers from processing critical polymers such as polyamide 6.6.
The design of a spin beam must take into account ease of disassembly and the ability to dismantle into small units. Appropriate flanges on piping, using sealants, must be provided.
BRIEF SUMMARY OF INVENTION
The object of the present invention, therefore, is to further refine an apparatus for spinning according to the prior art, thus allowing the spin beam to be regenerated without costly disassembly.
This object is achieved by the invention by providing the spin beam with regeneration heating, either permanently installed or temporarily attachable to the spin beam, which heats the spin beam to the required pyrolysis temperature as needed. The advantage of the invention lies in the fact that the regeneration process can thus take place without costly disassembly of the spin beam. The spin beam may be constructed as a single unit so that removable flanges and other leak hazards are not necessary, resulting in a spin beam with a more economical and simple design.
In the case of a spin beam heated by a heat transfer medium, it is usually not possible with this heating principle to achieve the pyrolysis temperature required for the regeneration process. For this reason separate regeneration heating is provided for the regeneration process in the form of electrical resistance heating, a hot air blower, or the like.
To carry out the regeneration process, the regeneration heating is able to heat the melt-conducting components to temperatures above the operating temperature. This temperature is preferably in the range of 450 to 550° C., which thermally destroys the organic deposits.
If the spin beam is heated by an electrical heating unit, the unit can simultaneously be put to practical use as regeneration heating, and is capable of heating the spin beam to the regeneration temperature.
The thermal destruction of the organic deposits generates gases and vapors in the spin beam. For this reason, in one preferred refinement of the invention means are provided for exhausting the generated gases and vapors. In one particularly preferred refinement the exhausted gases and vapors are filtered.
For the case in which the spin beam is heated using a heat transfer medium, in one advantageous refinement of the invention means are provided to drain off the heat transfer medium for the duration of the regeneration process, and to store it outside the spin beam which is heated to regeneration temperature. In one particularly advantageous refinement of the invention, means are provided to remove the vapors produced by evaporation of the heat transfer medium during the regeneration process.
One exemplary embodiment is described in greater detail below, with reference to the accompanying drawings.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 shows a section through an apparatus for spinning melt-spun filament yarns according to the present invention;
FIG. 2 shows a section through a variant of an apparatus for spinning melt-spun filament yarns according to the present invention; and
FIG. 3 shows a section through another variant of an apparatus for spinning melt-spun filament yarns according to the present invention.
DETAILED DESCRIPTION
FIG. 1 illustrates in sectional view an inventive apparatus for spinning. A polymer melt is fed from an extruder 1 via a melt feed line 2 to spin beam 3 . Instead of extruder 1 , a direct polycondensation reactor may be used here as the source for the polymer melt. Inside spin beam 3 , melt feed line 2 is apportioned to two spinning pumps 4 . Spinning pumps 4 distribute the polymer melt, metered via distribution lines 5 , to the individual spinning cans, not shown, which are accommodated in spinning can receivers 6 . The filaments for forming the thread are extruded from the polymer melt in these spinning cans. The number of spinning can receivers 6 as well as the number of spinning pumps 4 are chosen here by way of example.
Inside spin beam 3 , a cavity 7 is formed so that it may be filled with a heat transfer medium. This heat transfer medium circulates through an operational heating means 8 . 3 via an inlet 8 . 1 and an outlet 8 . 2 . Spin beam 3 is thus heated to operating temperature by operational heating means 8 . 3 , an operating temperature of 250 to 330° C. being common.
The use of oil or Diphyl as heat transfer medium is known. Diphyl is a trademark of Lanxess Deutschland GmbH, and is used in association with a family of heat transfer fluids. Diphyl is advantageous here since it is present in spin beam 3 in the liquid and the gaseous phase, so that cold components of spin beam 3 are heated in a targeted manner by the heat of condensation produced by condensation of the gaseous Diphyl heat transfer fluid. For the sake of brevity the operational heating of melt feed line 2 , which cooperates with operational heating 8 . 3 or is operated separately, is not illustrated here.
Although the length of divided feed line 2 , as well as the length of each distribution line 5 to the particular spinning can receiver 6 , is the same for every branch, and therefore the residence time of the melt in the melt-conducting parts of spin beam 3 is equal for each spinning can receiver 6 , degradation of the polymer can occur in spite of the uniform temperature in spin beam 3 .
For this reason, in FIG. 1 spin beam 3 is provided with regeneration heating by which spin beam 3 can be heated to a regeneration temperature above the operating temperature.
In this case the regeneration heating is a hot air blower comprising hot air exhaust 10 , filter 12 , blower 13 , regeneration heating means 14 , and hot air feed 9 .
To carry out the regeneration heating process, the heat transfer medium contained in cavity 7 can be transferred into a collection reservoir 8 . 4 . The regeneration heating causes hot air to flow through cavity 7 , which is now filled only with air, long enough to heat the components inside spin beam 3 to the regeneration temperature. To this end, blower 13 directs the air through regeneration heating means 14 which heats the air flowing through. The hot air is led via hot air feed 9 through spin beam 3 , and is returned via hot air exhaust 10 . Any vapors formed from the residues of the heat transfer medium are collected by filter 12 . Parallel to the above-described path of the hot air through spin beam 3 , in the example in FIG. 1 a second hot air duct 11 is provided which heats melt feed line 2 , likewise to the regeneration temperature.
Control means 15 detect the temperature in spin beam 3 by use of a temperature sensor 19 , and, based on a comparison of set point and actual values, controls blower 13 and regeneration heating means 14 .
During the regeneration process the spinning cans, not shown here, are removed from spinning can receivers 6 so that the openings in distribution lines 5 are open. An opening 2 . 1 is provided in melt feed line 2 through which compressed air can be blown into the melt feed line system. Alternatively, melt feed line 2 is connected via opening 2 . 1 to an exhaust device 2 . 2 by which the gases generated during the regeneration process are exhausted and filtered.
Residues in melt feed line 2 and distribution lines 5 which could not be completely removed by the regeneration process, i.e.; the polymer chains of which were not fully broken up to the gaseous form, are discharged by flushing the lines with polymer—not including the spinning packets used—following the regeneration process.
The regeneration heating may be permanently connected to the spin beam 3 . However, it is also possible and practical for economic reasons to design filter 12 , blower 13 , regeneration heating means 14 , and control means 15 to be removable so that they can be attached as needed to hot air feed 9 and hot air exhaust 10 of the spin beam 3 to be regenerated. Thus, a manufacturer of chemical fibers need have only one regeneration heating system on hand for a plurality of spin beams.
Although heating with heat transfer medium is illustrated in FIG. 1 as the operational heating system, the spin beam according to the invention also encompasses other embodiment forms of the operational heating system, such as (electrical) trace heating of the melt-conducting components, for example. These are known in the art. The same also applies to the figure which follows.
FIG. 2 shows a variant of spin beam 3 illustrated in FIG. 1 . In this case, regeneration heating means 16 are based on additional electrical heating of spin beam 3 . Although hot air does not flow through the cavity in the spin beam here, a collection reservoir 8 . 4 for the heat transfer medium is nevertheless provided, since as a rule the heat transfer media used are not heat-resistant in the regeneration temperature range. Residues of the heat transfer medium remaining in spin beam 3 evaporate during the regeneration process and are discharged by an exhaust means 20 .
The spin beam is typically well insulated from the outside, whereas the interior components conduct heat relatively well. In this manner, and by the heat radiation inside spin beam 3 , a sufficiently uniform heat distribution is achieved, the requirements for uniformity of temperature being less stringent for the regeneration process than for the spinning operation. The number of regeneration heating means 16 and their particular location are deduced from the design of spin beam 3 , and can be appropriately designed by one skilled in the art. Regeneration heating means 16 are designed as heating coils, heating rods, etc., and transfer the heat by means of heat conduction or heat radiation. Here as well, regeneration heating means 16 may be either permanently installed in spin beam 3 or designed to be interchangeable. With regard to heating rods in particular, it is possible to use these in openings in spin beam 3 which are provided specifically for this purpose and which are closed by stoppers during normal operation.
FIG. 3 shows a further variant of the apparatus according to the invention for spinning 3 . In contrast to the examples illustrated in the previous figures, heating of spin beam 3 during normal spinning operations (operational heating) is provided not by a heat transfer medium, but rather by heating means 17 to the individual melt-conducting parts, the heating means being designed here as trace heating. This may be electrical resistance heating, for example. Heating means 17 are controlled by control means 18 which include temperature regulation, for example. Control means 18 are provided with a separate operating mode in which the heating means can be operated at a higher regeneration temperature, so that the regeneration process can be simultaneously carried out using the operational heating means.
LIST OF REFERENCE NUMBERS
1 . Extruder
2 . Melt feed line
2 . 1 Opening
2 . 2 Exhaust means
3 . Spin beam
4 . Spinning pump
5 . Distribution line
6 . Spinning can receiver
7 . Cavity
8 . 1 Heat transfer medium inlet
8 . 2 Heat transfer medium outlet
8 . 3 Operational heating means
8 . 4 Collection reservoir
9 . Hot air feed
10 . Hot air exhaust
11 . Second hot air duct
12 . Filter
13 . Blower
14 . Regeneration heating means
15 . Control means
16 . Regeneration heating means
17 . Heating means
18 . Control means
19 . Temperature sensor
20 . Exhaust means
The disclosure in German Patent Application 102 58 261.0 of Dec. 13, 2002 is incorporated herein by reference. This German Patent Application describes the invention described hereinabove and claimed in the claims appended hereinbelow and provides the basis for a claim of priority for the instant invention under 35 U.S.C. 119.
While the invention has been illustrated and described as embodied in a spin beam, it is not intended to be limited to the details shown, since various modifications and changes may be made without departing in any way from the spirit of the present invention.
Without further analysis, the foregoing will so fully reveal the gist of the present invention that others can, by applying current knowledge, readily adapt it for various applications without omitting features that, from the standpoint of prior art, fairly constitute essential characteristics of the generic or specific aspects of this invention. | An apparatus for spinning melt-spun filament yarns including a spin beam is disclosed. A polymer melt fed to a spin beam is distributed within the spin beam to a plurality of spinning cans mounted on the spin beam. To reduce costs to the manufacturer for ensuring ease of disassembly of the spin beam, as well as to avoid the need for disassembling the spin beam and having a furnace on hand, the spin beam is provided with an integrated or removably attachable regenerative heater by which the melt-conducting components of the spin beam can be heated to a regeneration temperature of between about 450 to 550° C. to pyrolytically remove the deposits. | 3 |
CROSS-REFERENCE TO RELATED APPLICATIONS
The present application is a continuation-in-part of U.S. patent application Ser. No. 11/439,831 filed on May 23, 2006, the disclosure of which is incorporated by reference.
BACKGROUND OF THE INVENTION
This application relates to the field of compressed paper and woven goods.
Products made in a compressed state are small, for example, the size of a coin or a button. When such products are put into a liquid, for example, water, they expand, become larger, and are then suitable for their intended purpose. For example, buttons of compressed paper can be hydrated to be used as wipes. In other examples, compressed fabrics are hydrated to make towels, face cloths, tee shirts, and other clothing. Compressed sponges that expand upon contact with water are another example.
Compressed goods are useful because their light weight and small size make shipping and handling them easier than otherwise. There is a need to provide compressed goods with enhanced features, for example, ones that provide medicinal or comfort therapies.
SUMMARY OF THE INVENTION
In one aspect of the invention, microencapsulated materials are added to compressed products. Generally, the materials are added to the products before the products are compressed. The microencapsulated products can also be added to the products after they have been compressed.
Microencapsulation permits a wide range of products to be incorporated into these dehydrated compressed products while maintaining the dry, compressed nature of the products. The coatings of microencapsulated beads of material can be soluble in various types of liquid, for example, water. Moreover, in some examples, it may be desirable that the coatings only release material upon mechanical force, e.g., friction.
Methods of making an article are provided, the methods comprising forming the article, that comprises paper or fabric, in a size of intended use; attaching a plurality of microencapsulated beads containing a material therein to the paper or fabric; and compressing the article to a compressed size that is smaller than the size of intended use. In one embodiment, the step of compressing the article comprises dehydrating the article. In another embodiment, the step of compressing the article comprises exposing the article to vacuum pressure. In yet another embodiment, the method further comprises contacting the article with a liquid to expand the article to approximately the size of intended use.
In another aspect of the invention, the articles comprise a liquid-expandable paper or fabric, and a plurality of microencapsulated beads containing a material therein attached to the paper or fabric. Generally, the paper or fabric material is in a compressed state and the material remains compressed until a liquid contacts the material. This application may refer to the compressed paper or cloth as a compressed coin. In some examples, the microencapsulated beads are attached to the surface of the paper or fabric. In other examples, the beads are embedded within the fabric or paper.
In one embodiment, the material is released from the beads upon expansion of the paper or fabric in the liquid. In some examples, the material comprises therapeutic compounds such as antibiotics or alcohols, to be used, for example, for cleaning wounds or other medicinal purposes. Articles having such materials can be useful in military or third world environments. In other examples, the material comprises comforting compounds such as a fragrance, an oil, salt, a vitamin, a skin-moisturizer, or combinations thereof. Articles having such materials can be used as compresses for aromatherapy or other relaxation therapies. In another embodiment, the materials can be in the form of a hardening facial mask. These materials can be in the form of clay, resin, or other material that is pliable when wet but hardens upon drying.
In some embodiments, articles in accordance with the present invention comprise a towel, a face cloth, or a wiping cloth. If the article is used as a facial mask, it is supplied with cut-outs for the eyes, nose and mouth.
There are many uses for the micro encapsulated products in accordance with various aspects of the present invention. One use is combining the compressed coins with coated alcohol or antibiotic. When they are expanded, they then have the ability to be able to be used to clean wounds and other medical uses. This might be of particular value in third world areas or military situations.
Another use is to microencapsulate fragrances and/or oils with these compressed coins. In this application, these coins would be placed in warm water. As they are expanded they can be used as compresses for aromatherapy or other relaxation therapies.
It is believed that there are substantial uses and a substantial business for combining these two technologies. Without the dryness of the microencapsulation it would cause the coins to expand and/or the ingredients to be dissipated.
The articles can be packaged and sold individually, or in groups. In one embodiment, a plurality of similar articles are packaged in a strip, with each coin individually sealed in the strip. Thus, a single coin could be cut off of the strip without affecting the seal of the others, so that they are not exposed to air when removing a single coin. The strip could be formed from a plastic material that can be colored or printed to indicate the contents of the strip. The strip could have perforations along the seam to make separation easier. The strip could also have a weakening line extending to the area enclosing each coin to allow tearing of the packaging along the weakening line.
BRIEF DESCRIPTION OF THE DRAWINGS
Other objects and features of the present invention will become apparent from the following detailed description considered in connection with the accompanying drawings. It is to be understood, however, that the drawings are designed as an illustration only and not as a definition of the limits of the invention.
In the drawings, wherein similar reference characters denote similar elements throughout the several views:
FIGS. 1 and 2 illustrate a compressed cloth having microencapsulated beads in accordance with various aspects of the present invention.
FIG. 3 illustrates a method in accordance with one aspect of the present invention.
FIG. 4 illustrates the article in the form of a facial mask.
FIG. 5 illustrates several of the compressed articles in a strip of packaging.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now in detail to the drawings and, in particular, FIG. FIG. 1 illustrates one aspect of the present invention. Article 10 is paper, a woven good or cloth. The article 10 can, for example, be made of rayon, but any compressible material can be used.
Microencapsulated beads or materials 16 are added to the article 10 by known techniques to form a new article 12 . The microencapsulated beads 16 can be formed to be soluble in a liquid, such as water. In this case, the microencapsulated beads 16 will dissolve upon contact with the liquid and, upon being dissolved, will release the encapsulated material in the beads 16 . The microencapsulated beads 16 can also be formed to break upon a pressure or friction being asserted on the beads 16 . In this case, the beads 16 will break and release their contents upon the exertion of the pressure.
The article 12 having the microencapsulated beads can be compressed to a smaller size, such as the size of article 14 , using any known technique, the techniques including but not limited to dehydration or submitting the article 14 to vacuum pressure. The size of the article 12 is usually small, such as the size of a coin or a button. Other sizes, however, can be used.
The materials in the microencapsulated beads 16 can include an antibiotic, a pharmaceutical, an alcohol, a fragrance, an oil, vitamin, a salt, a skin conditioner, a skin moisturizer, or combinations thereof. Other materials can include cleansers, polishes, anti itch materials and anti-inflammatory materials.
Any number of fragrances can be used. For example, aromatherapy fragrances thought to help calm people can be used. A bubble gum fragrance can also be used to provide a unique bubble bath for children.
FIG. 2 illustrates the article 14 being exposed to a liquid 20 . The liquid 20 can be any liquid that will de-compress the article 14 . By way of example, the liquid could be water. The liquid 20 , in this case, also preferably dissolves the microencapsulated beads 16 to release the contents of the beads.
The result of the application of liquid 20 is that the article 14 expands to the size of the article 22 . The microencapsulated beads 16 have dissolved, releasing the contents 24 and 26 . Generally, if the contents of the beads 16 were in liquid form, the contents 24 will stay on the article 22 . If the contents of the beads 16 included fragrances, the contents 26 may leave the article 22 .
In the case where the microencapsulated beads 16 are broken by friction, the application of the liquid 20 would not dissolve the beads 16 . Instead, when the article 22 is rubbed on another article, such as a person's skin, the beads 16 are broken and the contents 24 and 26 are released.
The article 10 can be any compressible material that can be expanded.
FIG. 3 illustrates a method in accordance with one aspect of the present invention. In step 30 , microencapsulated beads are added to an article. As stated before, the article can be cloth, a woven material, paper or any compressible material. In step 32 , the article is compressed. The order of these two steps can be reversed.
In step 34 , the article is expanded. In step 36 , the contents of the microencapsulated beads 16 are released either as a result of contact with a liquid or as a result of friction or pressure.
The articles of the present invention can be used, by way of example only, to treat wounds, to provide therapy, such as aroma therapy or relaxation therapy, for bubble baths, for cleaning—both personal and for objects.
In accordance with another aspect of the present invention, the article 10 that is compressed can also be shaped. The article 10 can also have printed material on it. The shape of the article 10 and the printed material preferably have a relation to the article 10 and the material released by the microencapsulated beads 16 . For example, if the article 10 is a wash cloth and the microencapsulated material is a bubble gum fragrance so that a child might enjoy a bath, the article 10 can be shaped like a cartoon character and a picture of the carton character can be printed on the article 10 . For example, the article 10 could be shaped like Mickey Mouse and a picture of Mickey Mouse could be placed on the article 10 .
FIG. 4 shows another embodiment of the invention, in which article 100 is configured as a facial mask. Article 100 is compressed into a coin via vacuum compression, and expands into a facial mask shape, with cutouts 101 , 102 , 103 for the face, when contacted by liquid 180 . Embedded into article 100 is a microencapsulated facial mask material 150 that is beneficial to the skin and hardens upon drying. Any suitable mask material could be used, such as clay, resin or other synthetic or organic materials. Application of article 100 to a face 190 allows article 100 to mold to the shape of the face and dry thereon, thus providing beneficial treatment to the skin.
FIG. 5 shows a strip 200 of compressed articles 10 , which have been compressed into coin shape and are individually sealed in strip 200 in between sealed seams 215 . Strip 200 can be decorated or colored to match the type of material embedded within article 10 . In order to use an article 10 , the portion of strip 200 adjacent article 10 is cut or ripped away from the rest of strip 200 . Since each article 10 is individually sealed along seams 210 , the remaining articles 10 stay sealed. Perforations 216 can be placed along seams 215 to make separation of each article 100 easier. A weakening line 218 can extend into the space between seams 215 to make tearing of the packaging easier when accessing article 100 .
While there have been shown, described and pointed out fundamental novel features of the invention as applied to preferred embodiments thereof, it will be understood that various omissions and substitutions and changes in the form and details of the device illustrated and in its operation may be made by those skilled in the art without departing from the spirit of the invention. It is the intention, therefore, to be limited only as indicated by the scope of the claims appended hereto. | A compressed article of hygiene is formed by a compressed cloth that has been compressed by dehydration or vacuum pressure into a coin shape and that is expandable upon contact with a liquid, and a plurality of microencapsulated beads containing a material. The microencapsulated beads are attached and embedded in the compressed cloth. Upon contact with water, expansion of the compressed cloth is unconstrained, and the compressed cloth when expanded has a shape of a facial mask with openings for eye, nose and mouth. The material is a facial treatment material that hardens upon drying. | 0 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an improvement in the structure and method of assembling a sleeping bag.
2. The Prior Art
A sleeping bag structure is known, wherein the outside material and the lining form a space therebetween to be filled with a large quantity of feathers. Certainly, such a feather-filled sleeping bag is advantageous in certain aspects such as its ideal heat insulating effect and portability. However, it also has serious disadvantages such as its high cost and the fact that the feathers tend to bunch up within the sleeping bag structure, often adversely affecting the heat insulating effect.
Feathers are generally high in their moisture absorption characteristics and thus have their volume reduced as they absorb moisture. Such tendency causes a mass of feathers to become further bunched up in the sleeping bag structure and even after dried and redistributed within the sleeping bag, feathers can never be restored to their initial uniform distribution within the sleeping bag structure. This also adversely affects the heat insulating effect.
It has also been known that, after the space between the outside material and the lining has been filled with a layer of feathers, the sleeping bag may be subjected to a quilting operation performed through the outside material, the feather layer and the lining so as to clamp the feather layer against displacement thereof within the bag structure. However, such quilting disadvantageously prevents the feather layer from conforming to the configuration of a human body and deteriorates the heat insulating effect at least in the region of quilting. Thus, the most preferred characteristics of the high cost feather filler material cannot be adequately enjoyed.
Attempts have been made to solve the above-described problems. In one proposed solution, the structure of a sleeping bag is formed so that a layer of synthetic fiber or cotton and a thin layer of feathers are formed between the outside material and the lining and directly sewn together therewith. Such an improvement permits the ideal characteristics of feathers to be satisfactorily enjoyed by the user. The layer of feathers can be held to some degree against being bunched up against the layer of synthetic fibre cotton during use of the sleeping bag and the sleeping bag can be provided at a relatively low cost. However, even in this improved structure, the layer of feathers still bunches up to some extent and the problem of heat insulation remains unsolved.
In another proposed solution, the sleeping bag structure comprises an outside material, a lining and partition sheets interposed between the outside material and the lining in such a manner that the individual partition sheets are sewn along their upper and lower edges to the outside material and the lining material, respectively, to form a plurality of tubular spaces defined by the outside material, the lining and an associated pair of partition sheets, to be filled with respective portions of a feather layer together with respective portions of another heat insulating layer. In this prior art structure, however, it has been extremely difficult to fill the tubular spaces with the feather layer together with the other heat insulating layer. Consequently, the assembly of such sleeping bags has been extremely time consuming and cumbersome.
OBJECTS AND SUMMARY OF THE PRESENT INVENTION
An object of the present invention is to provide a sleeping bag structure comprising an outside material, a lining and a relatively small quantity of feathers inserted in a space defined between said outside material and the lining in such a manner that the feathers are prevented from becoming bunched up, thus avoiding heat loss, while maintaining the preferred characteristics peculiar to feathers, such as their excellent heat insulating effect, light weight and portability and at the same time retaining 100 percent of their inherent restorative capability in spite of being placed over a layer of different material; thus enabling an ideal sleeping bag, incorporating such structure, to be assembled at a relatively low cost.
Another object of the present invention is to provide a mass-producible sleeping bag basic structural component, which not only permits the feathers and the other heat insulating material to be easily and rapidly inserted into the component, but also enables a readily portable sleeping bag of extremely high heat insulating characteristics to be assembled therefrom, and in which the layer of feathers can slidably move within a limited range, when assembled into a sleeping bag with the layer of feathers being disposed along the inner side of the sleeping bag, thereby conforming to and completely covering the user's body with a resulting improved heat insulating effect.
Still another object of the present invention is to provide structural elements for a sleeping bag which can be smoothly sewn together so as to clamp the non-feather heat insulating layer rapidly and reliably.
According to the present invention, these objects are achieved by providing a sleeping bag structure comprising an outside material, a lining material, a heat insulating layer interposed within an internal space defined between the outside material and the lining material and closely adjacent the inner side of the outside material so as to form a space between the inner side of the heat insulating layer and the lining material, and partition sheets adapted to divide the last mentioned space into a plurality of compartments to be filled with feathers.
Another embodiment of the present invention comprises an outside sheet, an intermediate sheet of flexible and slippery material, a heat insulating layer of natural cotton, synthetic fiber or the like interposed between the outside sheet and the intermediate sheet, a lining sheet and a plurality of partition sheets arranged so that each of the partition sheets is fixed along one edge by a sewing thread running through said edge, the intermediate sheet and the outside sheet for clamping the cotton layer to said intermediate sheet while each of said partition sheets is fixed along the other edge by sewing, adhesion or other means to the lining sheet to form a tubular space defined by the intermediate sheet, the lining sheet and an associated pair of partition sheets, which is adapted to be filled with feathers and then to be sealed.
Other features and advantages of the present invention will be apparent from the following description with reference to the several embodiments shown in the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1 and 2 are perspective views of a sleeping bag assembled from structural components according to the present invention, in a complete condition and an incomplete condition, respectively;
FIG. 3 is a longitudinal section of a first embodiment of the present invention;
FIG. 4 is a section similar to FIG. 3 showing a second embodiment of the present invention;
FIG. 5 is a section similar to FIG. 3 showing a third embodiment of the present invention;
FIGS. 6 through 8 illustrate a fourth embodiment of the present invention in a perspective view, in a partial longitudinal section and in a partial enlarged longitudinal section; respectively; and
FIG. 9 is a schematic diagram illustrating a functional effect of the sleeping bag structural component according to the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to the drawings wherein like reference numerals designate like parts throughout the several views thereof, FIG. 1 illustrates an example of a sleeping bag consisting of structural members formed according to the present invention and FIG. 2 illustrates the same sleeping bag prior to hemming, along its lowermost edge. The basic structural component of the sleeping bag, generally designated by reference numeral 1, is shown in more detail in the embodiments of FIGS. 3 to 5. Interposed between the outside material 2 and lining material 3 is a layer 4 of heat insulating material such as natural or synthetic cotton or nonwoven cloth, immediately adjacent the inner side of the outside material 2 or the lining material 3. Partition sheets 6 of cloth or the like are longitudinally disposed on the inner side, as shown, of the heat insulating layer 4, one end of each partition sheet 6 being sewn to the heat insulating layer 4 and the other end of each partition sheet 6 being sewn to the lining material 3, so that there are formed spaces between the upper side 9 of the heat insulating layer 4 and the lining material 3. FIG. 3 illustrates an embodiment in which the partition sheets are vertically disposed; FIG. 4 illustrates another embodiment in which the partition sheets are disposed on a slant and FIG. 5 illustrates still another embodiment in which the partition sheets are disposed in a zig-zag manner. It should be noted that, although the partition sheets 6 have been shown in FIGS. 3 to 5 as each being sewn along one edge on the lining material 3 and along the other edge on the heat insulating layer 4 with threads 5 running therethrough, said one edge may be sewn on the rear side of the lining material 3 while said other edge may be sewn on the heat insulating material 4 as well as on the outside material 2. In such a case, it is preferred that a layer of a gauzy material be fixed to the upper side of the heat insulating layer 4. Attachment of the partition sheets may also be effected by other means, such as adhesive bonding.
Reference numeral 7 designates openings through which a small quantity of feathers 8 is introduced into respective compartments defined by each pair of adjacent partition sheets 6,6. Then, the respective openings 7 are sealed by sewing, adhesion or other means. The structural members thus formed may be assembled into a sleeping bag, for example, as illustrated in FIG. 1.
When the structural members are assembled into the sleeping bag, respective layers of feathers do not move beyond the associated partition sheets and these layers as a whole do not bunch up in the sleeping bag, since an extremely small quantity of feathers suffices to fill each compartment in view of the presence of the associated heat insulating layer 4. The layers of feathers 8 are accommodated within the respective compartments defined at their upper part by the outside material 2 or the lining material 3, laterally by the partition sheets 6,6 and at their lower part by the heat insulating layer 4.
As will be understood from the foregoing description, the present invention provides structural components for a sleeping bag, which can provide an ideal sleeping bag at low cost. More specifically, the small quantity of feathers filling the space between the outside material and the lining material is substantially prevented from being bunched up. Moreover, when the structural components are assembled into a sleeping bag, no loss of the heat insulating effect results from any bunching up of the feather layer. Thus, the layer of feathers incorporated therein can be advantageously put to use as to such characteristics as heat insulation, lightness, portability, compactness and sleeping comfort. Furthermore, the space between the outside material and the lining material is divided into a plurality of compartments in accordance with the present invention so that the individual layers of feathers can be uniformly distributed within the respective compartments and contribute to a high degree of restoration of the sleeping bag.
Referring to FIGS. 6 through 8 which illustrate another embodiment of the present invention, reference numeral 10 designates a sheet of material which is usually used for the outside of a sleeping bag, as for example, water-proof cloth of synthetic resin fibers or the like. A heat insulating layer 12 of synthetic cotton is placed thereon and an intermediate sheet 17 is placed upon the heat insulating layer. The intermediate sheet 17 is made of flexible and slippery material such as nylon or silk cloth and disposed on the upper side thereof are a plurality of partition sheets 14 transversely extending and being spaced longitudinally one from another. Sewing threads 13 extending through lower edges 15, the intermediate sheet 17, the layer 12 of synthetic fiber cotton and the outside sheet 10 serve to clamp layer 12 of synthetic fiber or cotton so that it is prevented from being disadvantageously moved or bunched up. Upper edges 16 of partition sheets 14 and lining sheet 11 are sewn or adhered together at 20 so that a plurality of tubular spaces 19 are defined by intermediate sheet 17, lining sheet 11 and partition sheets 14. One opening of each such space is sealed by sewing, adhesion or other means and a quantity of feathers 18 is inserted through an opposite opening into the space 19 to form the desired structural component for the sleeping bag. These members are assembled, with the respective lining sheets 11 inwardly facing, into a sleeping bag.
The construction concept described above can thus provide a structural component for a sleeping bag comprising two layers, i.e., a layer of feathers and a heat insulating layer other than feathers in an easy, rapid, economical and mass-producible manner employing an extremely simple technique in which the edges of the respective partition sheets can be sewn to the intermediate sheet and the heat insulating layer of synthetic fiber, cotton or the like can be fixed in place by sewing.
According to the present invention, the intermediate sheet 17 of flexible and slippery material is employed, so that the needle of a sewing machine can smoothly run through the edge of each partition sheet, the intermediate sheet, the heat insulating layer of synthetic fiber, cotton or the like and the outside sheet, permitting the sewing of various components together and the anchoring of the heat insulating layer with a high degree of efficiency and reliability. It is also a feature of the present invention that the intermediate sheet of flexible and slippery material employed, as mentioned above, permits the feather layer inserted in the tubular space 19 defined by the intermediate sheet, the outside sheet and the associated partition sheets to freely, slidably move within the tubular space. When assembled into a sleeping bag, therefore, the layer of feathers properly moves within the respective tubular spaces 19 substantially in conformity with the configuration of a human body 21 (FIG. 9) so as to cover the latter closely and comfortably. Thus, the present invention provides a structural component for a sleeping bag having a heat insulating effect substantially higher than is conventionally achieved.
It should be understood that the structural component according to the present invention may be used to assemble items of clothing similar to sleeping bags and it is intended that such use for the structural component is included within the scope of the present invention. | A structural component for forming sleeping bags or insulated items of wearing apparel is formed of an outer layer of waterproof or the like material and a laterally spaced inner lining material. Attached to the inner surface of the outer material is a layer of heat insulating material such as cotton, the upper surface of which is laterally spaced from the inner surface of the lining material. Extending transversely between the upper surface of the cotton material and the inner surface of the lining material are a plurality of spaced partition sheets forming tubular cavities therebetween. These cavities are filled with feathers and sealed at their outer ends. | 0 |
BACKGROUND OF THE INVENTION
[0001] The present invention relates to a scroll fluid machine for compressing, expanding, or pressure feeding fluid and an assembling method thereof.
DESCRIPTION OF THE RELATED ART
[0002] In a scroll fluid machine, three sets of mechanism for preventing rotation of the revolving scroll comprising auxiliary crank are placed near the periphery of the scrolls at equal circumferential spacing in order to prevent rotation of the revolving scroll and allow it to revolve.
[0003] It is necessary that the mirror-surfaces of both of the revolving and stationary scrolls are parallel to each other, since if they are not parallel to each other, hermeticity of the closed compression pocket formed by the wraps of the scrolls as the revolving scroll revolves is damaged due to the deflection of the mirror-surfaces. Therefore, each scroll should be supported by means of the auxiliary cranks of the rotation preventing mechanisms so that both of the mirror-surfaces are parallel.
[0004] In Japanese Patent No. 2562581 is disclosed a scroll compressor which has three sets of mechanism for preventing rotation of the revolving scroll capable of adjusting the gap between the top surface of wrap and the mating mirror-surface by rotating the double nuts which determine the position of the auxiliary crank of each of the rotation preventing mechanisms relative to the bearing provided in the bearing housing of the stationary scroll.
[0005] Therefore, the gap between the top surface of wrap and the mating mirror surface is adjusted after the stationary scroll and revolving scroll are assembled, and the adjusting must be performed for three auxiliary cranks. which means the adjusting is intricate and time-consuming.
[0006] If each of the auxiliary cranks is divided into two parts, a stationary scroll side crank member and a revolving scroll side crank member, one of the crank members being able to be pressed into the other crank member to connect them to be compose a one-piece auxiliary crank, and both of the crank members installed respectively in the both of the scrolls are pressed into one-piece when both of the scrolls are assembled, said adjustment procedure of the gap after assembling both of the scrolls is eliminated. In this case, if both of the crank members are so configured that the distance between the mirror-surfaces of both of the scrolls can be adjusted by press-in depth of one of the crank member into the other crank member, dimensional deviation of component parts can be cancelled by the press-in depth.
[0007] When the dimensions of the component parts are accurate, the scrolls are assembled without undue deflection of the scroll plate by preparing a standard auxiliary crank having the length corresponding to the distance between the mirror-surfaces of both of the scrolls. But, when there is dimensional deviation of the component parts, the scroll plates may be deflected when both of the scrolls are assembled if said length of the standard auxiliary crank does not correspond to the distance between the mirror-surfaces at all of the rotation prevention mechanisms.
[0008] The dimensional deviation varies depending on production lots, so that many auxiliary cranks of different size (tolerance) must be prepared, resulting in complicated production control.
SUMMARY OF THE INVENTION
[0009] The present invention was made in light of the problem mentioned above, and an object of the invention is to provide an auxiliary crank composed of a pair of crank members capable of being connected by pressing-in one of the crank members to the other crank member to compose a one-piece auxiliary crank and a scroll fluid machine having said auxiliary crank.
[0010] Another object of the present invention is to provide a scroll fluid machine which does not need the adjustment of the distance between the mirror-surfaces after the revolving scroll and stationary scroll are assembled.
[0011] The present invention proposes a scroll fluid machine having a revolving scroll side connected to a stationary scroll side by means of auxiliary cranks for regulating the motion of the revolving scroll, wherein each of said auxiliary crank comprises a revolving scroll side crank member and a stationary scroll side crank member, and both of the crank members are connected by pressing one of the crank members into the other crank member to compose a one-piece auxiliary crank.
[0012] Here, “revolving scroll side” and “stationary scroll side” refer not only to the revolving scroll and stationary scroll respectively. Referring to FIG. 1, said revolving scroll side includes, for example, the scroll 12 having a revolving scroll wrap 12 a and a mirror-surface 12 c , and moving components attached to and revolving together with the revolving scroll 12 .
[0013] Said stationary scroll side includes, for example, the stationary scroll 11 having a stationary scroll wrap 11 a and a mirror-surface 11 c, and the scroll housing 13 surrounding the revolving scroll 12 and fixed to the stationary scroll 11 .
[0014] According to the present invention, the auxiliary crank is divided into two crank members of the revolving scroll side and stationary scroll side, and both of the crank members are connected to compose a one-piece crank by pressing one of the crank members into the other crank member.
[0015] Therefore, even if there is dimensional deviation of component parts, the length of the auxiliary crank can be adjusted by adjusting the press-in depth of one of the crank members into the other crank member in accordance with the distance between the mirror-surfaces of both of the scrolls, that is, in accordance with the scroll wrap height.
[0016] To be more specific, when auxiliary cranks having different length are needed for maintaining the even distance between the mirror-surfaces of both of the scrolls at all of the three rotation preventing mechanisms, if the auxiliary cranks having the same length is used, deflection occurs in the scroll plates.
[0017] By adjusting the press-in depth of one of the crank members to connect both of the crank members, dimensional deviation of the component part can be absorbed or cancelled. Therefore, it is not necessary to prepare auxiliary cranks of different dimension (tolerance), and dimensional deviation of component parts can be circumvented by adjusting the press-in depth.
[0018] In this way, auxiliary cranks each having the length capable of canceling dimensional deviation of component parts which differ depending on rotation preventing mechanisms and production lots are composed, resulting in a reduction of costs.
[0019] When scrolls with another scroll wrap height is to be assembled, the auxiliary cranks having the length corresponding to the wrap height are needed. This is also acieved by adjusting press-in depth of one of the crank member into the other crank member to compose a one-piece auxiliary crank.
[0020] It is an effective means of the present invention that pairs of crank members are selected in accordance with scroll wrap height and one of each pair of crank members is pressed into the other crank member to compose an auxiliary crank corresponding to the wrap height.
[0021] With the technical means like this, by preparing one or both of the crank members of various length and selecting the crank members, an auxiliary crank having the length corresponding to scroll wrap height can be composed.
[0022] It is also an effective means of the present invention that both of the crank members are pressed into both side of a connector piece(spacer) to compose a one-piece auxiliary crank having the length corresponding with scroll wrap height.
[0023] With the technical art like this, the length of the auxiliary crank can be changed largely by changing the thickness of the spacer.
[0024] It is also an effective means of the present invention that press-in depth of at least one of the crank members into said connector piece(spacer) is varied to compose a one-piece auxiliary crank having the length corresponding with scroll wrap height.
[0025] With the technical art like this, it is not necessary to prepare a variety of pair of crank members. It is enough to prepare at least one of the crank members of various lengths and change said one of the crank members to correspond to scroll wrap height.
[0026] It is also an effective means of the present invention that a bolt for fixing one of the crank members with the other crank member is provided, and both of the crank members are fixed by said bolt to compose auxiliary crank having the length corresponding with scroll wrap height.
[0027] With the technical art like this, by preparing one of the crank members of various length and selecting the one which corresponds to the height of the scroll wrap, it becomes unnecessary to prepare many auxiliary cranks of various length and cost reduction is achieved.
[0028] The auxiliary crank according to the present invention is characterized in that it is composed of a pair of crank members capable of being connected by pressing in one of the pair of crank members, and a plurality of at least one of the crank members of different height are prepared so that said one of the crank members can be selected.
[0029] By preparing a plurality of one of the crank members of different length and selecting one of the crank members in order to correspond to the height of the scroll wrap, it is not necessary to prepare many auxiliary crank of different length, resulting in a reduction of costs.
[0030] Further, the method of assembling a scroll fluid machine is characterized in that each of the auxiliary cranks is divided in two crank members, each crank member is mounted on the revolving side and stationary scroll side respectively, and both of the scrolls are assembled by shifting one of the scroll side in the direction of the axis of the crank member so that one of the crank members is pressed into the other crank member to be connected to compose a one-piece auxiliary crank.
[0031] According to the invention, each of the auxiliary cranks is divided into a revolving scroll side crank member and a stationary scroll side crank member, and both of the crank members are connected in the assembling process of the scroll machine by shifting the revolving or stationary scroll side in the direction of the axis of the crank members. Thus a one-piece auxiliary crank is composed in the scroll machine when both of the scrolls are assembled. Therefore, it is not necessary to adjust the gap between the tip of the scroll wrap and mirror-surface after both of the scrolls are assembled. Said gap is already adjusted when both of the scrolls are assembled, as the press-in depth is adjusted in the process of assembling. In this way, a plurality(three)of auxiliary crank are composed in the scroll machine by pressing one of the crank members into the other crank member in the process of assembling the scroll machine.
[0032] Therefore, according to the present invention, as the auxiliary crank is divided into a revolving scroll side crank member and a stationary scroll side crank member and both of the crank members are connected by press fitting, dimensional deviation of components parts can be cancelled by the adjustment of the depth of insertion when assembling the revolving and stationary scroll side. As a result, preparation of auxiliary cranks of various dimension is not necessary, auxiliary cranks can be composed in assembling process in accordance with dimensional deviation of component parts which differs according to production lots, and cost reduction is achieved.
BRIEF DESCRIPTION OF THE DRAWINGS
[0033] [0033]FIG. 1 is a sectional view of an embodiment of the scroll fluid machine of the present invention.
[0034] [0034]FIG. 2 is an illustration for explaining the method of assembling the revolving scroll side with stationary scroll side mounted with revolving scroll side crank members and stationary scroll side crank members respectively.
[0035] [0035]FIG. 3 is another illustration for explaining the method of assembling the revolving scroll side with stationary scroll side mounted with revolving scroll side crank members and stationary scroll side crank members respectively.
[0036] [0036]FIG. 4 is a side view of an embodiment of the auxiliary crank consisting of three component parts to be connected to compose an auxiliary crank including a partially sectional view.
[0037] [0037]FIG. 5 shows sectional views of two embodiments of the auxiliary crank consisting of a pair of crank members to be connected to compose an auxiliary crank.
[0038] [0038]FIG. 6 shows sectional views of another three embodiments of the auxiliary crank consisting of a pair of crank members to be connected to compose an auxiliary crank.
[0039] [0039]FIG. 7 shows sectional views of still another three embodiments of the auxiliary crank consisting of a pair of crank members to be connected to compose an auxiliary crank.
[0040] [0040]FIG. 8 shows an embodiment of the auxiliary crank consisting of a pair of crank members provided with a tightening bolt.
[0041] [0041]FIG. 9 shows another embodiment of the auxiliary crank consisting of a pair of crank members provided with a tightening bolt.
[0042] [0042]FIG. 10 shows still another embodiment of the auxiliary crank consisting of a pair of crank members provided with a tightening bolt.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0043] A preferred embodiment of the present invention will now be detailed with reference to the accompanying drawings. It is intended, however, that unless particularly specified, dimensions, materials, relative positions and so forth of the constituent parts in the embodiments shall be interpreted as illustrative only not as limitative of the scope of the present invention.
[0044] [0044]FIG. 1 is a sectional view of an embodiment of the scroll fluid machine of the present invention. In the drawing, a scroll fluid machine 1 is composed of a revolving scroll 12 having a wrap 12 a , a stationary scroll 11 having a wrap 11 a meshing with said wrap 12 a , a scroll housing 13 surrounding said revolving scroll 12 and fixed to said stationary scroll 11 , and a motor housing 14 incorporating a motor 2 to drive said revolving scroll 12 .
[0045] The circular stationary scroll 11 is provided with a discharge hole 11 d in the center of the mirror-surface 11 c thereof, the hole 11 d communicating with a outlet port 16 . The stationary scroll 11 have a stationary scroll wrap 11 a extending spirally outwardly from the vicinity of said discharge hole 11 d . A tip seal 34 made of fluorine contained resin having self-lubricating property is received in the groove defined in the tip of the wrap 11 a.
[0046] Three bearing housing bosses 11 b are formed equally spaced with a central angle of 120° near the periphery of the stationary scroll. Each bearing housing boss 11 b has an opening 11 g, in which ball bearings 8 , 9 are received. The lower part 22 a of a crank member 22 is fit in the inner races of the bearing 8 and 9 and a bolt 38 is screwed in the female screw 22 b of the crank member 22 to fix the inner races thereto via a washer 20 .
[0047] The revolving scroll 12 has a revolving scroll wrap 12 a extending spirally to mesh with the stationary scroll wrap 11 a. A tip seal 35 made of fluorine contained resin having self-lubricating property is received in the groove defined in the tip of the wrap 12 a.
[0048] Three bearing housing bosses 12 b are formed near the periphery of the revolving scroll corresponding to those of the stationary scroll. Each bearing housing bosses 12 b has an opening 12 g, in which ball bearings 6 , 7 are received.
[0049] The upper part 21 a of a crank member 21 is fit in the inner races of the bearing 6 and 7 and a bolt 37 is screwed in the female screw 21 b of the crank member 21 to fix the inner races thereto via a washer 19 .
[0050] The end part 21 c of the crank member 21 of the revolving scroll 12 side is pressed into the hole 22 c of the crank member 22 of the stationary scroll 11 side to form an auxiliary crank with the center axis of the crank member 22 and that of the crank member 21 offset to compose a rotation preventing mechanism 10 .
[0051] The revolving scroll 11 has a wall surrounding the stationary scroll wrap 11 a and a dust seal 36 is received in the groove defined in the tip of the wall, the tip surface facing the mirror-surface 11 a of the stationary scroll.
[0052] A bearing housing boss 12 d is formed on the other side of the mirror-surface 12 c of the revolving scroll 12 in the housing hole of which is fitted a ball bearing 25 .
[0053] The scroll housing 13 having a inlet port of fluid is provided with a bearing housing boss 13 d which is fitted a ball bearing 15 . In side the scroll housing 13 and the motor housing 14 is mounted a rotation shaft 3 having a rotor 18 , and a stator 17 surrounding the rotor 18 is attached to the motor housing 14 which is fixed to the scroll housing 13 by means of bolts 23 . The stationary scroll 11 is fixed to the scroll housing 13 by means of bolts 24 .
[0054] An end side of the rotation shaft 3 is supported for rotation by the motor housing 14 via a ball bearing 26 and the other end side 3 a is supported for rotation by a ball bearing 5 in the housing hole 13 d of the scroll housing 13 .
[0055] An offset crank member part projecting from the end surface of said end side 3 a of the rotation shaft 3 is fit in the inner race of the ball bearing 25 .
[0056] In the scroll fluid machine 1 composed as described above, the revolving scroll 12 revolves as the rotation shaft 3 rotates, fluid is sucked from the inlet port 15 of the scroll housing 13 to be taken into the closed pocket formed by the wraps of the revolving and stationary scrolls. The closed pocket is transferred toward center reducing in its volume as the revolving scroll revolves and the fluid in the pocket is compressed to be discharged from the discharge hole 11 d and then let out from the outlet port 16 .
[0057] Next, the method of pressing the revolving scroll side crank member 21 into the stationary scroll side crank member 22 will be explained with reference to FIG. 2.
[0058] Referring to FIG. 2, three bearing housing bosses 12 b are provided near the periphery of the revolving scroll 12 equally spaced with center angle of 120° as mentioned before. Similarly, the stationary scroll is provided with three bearing housing bosses 11 b corresponding to the three bearing housing bosses 12 b of the revolving scroll 12 .
[0059] Marks 11 e are inscribed on the stationary scroll to show the position of the openings of the bearing housing bosses 11 b. One of the marks 11 e is on the straight line passing the centers of the stationary scroll and the opening of one of the nearing housing bosses 11 b, other two marks are on the lines parallel to said straight line passing the centers of the openings of the other bearing housing bosses 11 b.
[0060] The stationary scroll side crank member 22 has on its top the hole 22 c , the center axis of which is offset from the center axis of the lower part 22 a . A mark 22 e is inscribed on the stationary scroll side crank member 22 on the straight line extending from the center of the lower part 22 a (see FIG. 1) passing the center of the hole 22 c . The stationary scroll side crank members 22 are rotated so that the marks 22 e coincide with the marks 11 e respectively. In this state, the revolving scroll is positioned so that the end part 21 c (see FIG. 1) of each crank member 21 matches to the opening 22 c of the crank member 22 , then the revolving scroll 11 is pressed down so that the lower end part of each crank member 21 is pressed into the opening 22 c of each crank member 22 .
[0061] The existence of the hole 21 d in the crank member 22 favors the pressing-in of lower end part of the crank member 21 into the opening 22 c of the crank member 22 .
[0062] Next, the method of pressing the revolving scroll side crank member 21 into the stationary scroll side crank member 22 will be explained with reference to FIG. 3. The point of difference from FIG. 2 is that assembling is performed with the motor 2 accommodated in the motor housing 14 and scroll housing 13 , and with the revolving scroll attached to the rotation shaft 3 of the motor.
[0063] In this case also each of the marks 22 e are brought to coincide with each of the marks 11 e respectively. Then the rotation shaft 3 is set to its maximum offset position toward right in the drawing.
[0064] The revolving scroll is positioned so that the lower end part 21 c of each crank member 21 matches to the opening 22 c of each crank member 22 , then pressing force is applied on the motor housing 14 near the periphery so that the lower end part 21 c of each crank member 21 is pressed into the opening 22 c of each crank member 22 . The pressing force applied on the motor housing is transmitted to the scroll housing 13 , and the wall of the scroll housing deflects to contact the top of each bolt 37 which fixes the crank member 21 to the bearing 6 , 7 , and the revolving scroll side crank member 21 are pressed into the openings 22 c of the stationary scroll side crank member 22 .
[0065] The press-in depth of each of the crank members 21 into the hole 22 c of each of the crank members 22 can be determined by the push-down distance of the motor housing 14 . Since the distance between the mirror-surface of the revolving scroll and that of the stationary scroll can be adjusted by controlling said press-in depth, the adjusting is simple compared with the prior art of adjusting by means of the double nuts at three places, and accurate adjusting is possible.
[0066] It is preferable that the pressing force is applied on the top near the periphery 14 a immediately above the circumferential wall 14 b of the motor housing 14 , and that the bolt 37 are located immediately below the circumferential wall 13 b of the scroll housing 13 with a gap of about 0.5˜1 mm between the top of the bolt 37 and the inner upper surface 13 b of the scroll housing 13 . Further, it is preferable that the clearance between the top face 3 e of the rotation shaft 3 and the bottom surface 12 h of the bearing housing 12 d of the revolving scroll 12 is larger than the press-in depth of the crank member 21 into the opening 22 c of the crank member 22 .
[0067] As a result, the top face 3 e of the rotation shaft 3 does not contact with said bottom surface 12 h when pressing force is applied on the periphery part 14 a of the motor housing 14 . The pressing force is transmitted through the circumferential wall 14 b of the motor housing 14 to the circumferential wall 13 b of the scroll housing 13 , then to the bolt 37 of the crank member 21 , so that undue stress which induces damage of the motor does not act on the motor.
[0068] According to the embodiment, each of the auxiliary cranks is divided into a revolving scroll side crank member and a stationary scroll side crank member, and both of the scrolls can be assembled so that the mirror-surface of the revolving scroll is parallel to that of the stationary scroll without the necessity of adjusting the three auxiliary cranks by means of double nuts after the assembling of the scrolls by pressing the revolving scroll side crank member into the stationary side crank member with the press-in depth adjusted.
[0069] Another embodiment which is effective likewise will be explained hereunder.
[0070] [0070]FIG. 4 is a side view of an embodiment of the auxiliary crank consisting of three component parts to be connected to compose an auxiliary crank including a partially sectional view. A revolving scroll side crank member 31 and a stationary scroll side crank member 32 are pressed into a connecting ring 28 to be assembled into an auxiliary crank. The shaft part 31 a of the crank member 31 is inserted into the bearings of the revolving scroll and the shaft part 32 a of the crank member 32 is inserted into the bearing of the stationary scroll. The shaft part 31 c of the crank member 31 is pressed into the opening 28 c of the connecting ring 28 and the shaft part 32 d of the crank member 32 is pressed into the opening 28 d of the connecting ring 28 when both of the scrolls are assembled.
[0071] The length of the auxiliary crank cab be adjusted by preparing the connecting rings 28 of various height.
[0072] The opening 28 c and 28 d may be communicated to form a through hole and the press-in depth of the crank member 31 , 32 can be adjusted to adjust the length of the auxiliary crank.
[0073] A female screw thread may be provided in the center of each of the crank member 31 and crank member 32 for fastening bearings by means of a bolt.
[0074] The edge 28 a and 28 b of the opening 28 c and 28 d respectively of the connecting ring 28 are preferable to be rounded or taper-chamfered. The edge 31 b and 32 d of the shaft part 31 c and 32 d of the crank member 31 and 32 respectively are preferable to be tapered or rounded. By tapering or rounding like this, the crank members can be easily pressed-in even when the center axis of the shaft part to be pressed-in does not coincide accurately with that of the opening for receiving the shaft part.
[0075] [0075]FIG. 5 shows sectional views of two embodiments of the auxiliary crank consisting of a pair of crank members to be connected to compose an auxiliary crank. FIG. 5( a ) shows the case the top edge 39 Ad of the shaft part 39 Ac to be pressed-in of the revolving scroll side crank member 39 A is rounded so that the shaft part 39 Ac can be easily pressed into the opening 40 Ac of the stationary scroll side crank member 40 A. The shaft part 39 Aa of the crank member 39 A is inserted into the bearings of the revolving scroll, and the shaft part 40 Aa of the crank member 40 A is inserted into the bearings of the stationary scroll. Female screw thread 39 Ab and 40 Ab is cut in the center of the shaft part 39 Aa and 40 Aa respectively for fastening the bearings by means of a bolt.
[0076] [0076]FIG. 5( b ) shows the case the top edge 39 Bd of the shaft part 39 Bc to be pressed-in of the revolving scroll side crank member 39 B is taper-chamfered instead of being rounded as is the case with FIG. 5( a ).
[0077] By tapering or rounding the top edge of the shaft part of the revolving scroll side crank member like this, the crank member can be easily pressed into the opening 40 Ac of the stationary scroll side crank member even when the center axis of the shaft part 39 Bc does not coincide accurately with that of the opening 40 Ac.
[0078] [0078]FIG. 6 shows sectional views of another three embodiments of the auxiliary crank consisting of a pair of crank members to be connected to compose an auxiliary crank. In all of FIG. 6( a ), ( b ), ( c ), the edge of the opening 40 Bc of the stationary scroll side crank member 40 B is chamfered in a tapered shape ( 40 Bd), and the configuration of the crank member 40 B is the same as that of the crank member 40 A of FIG. 5 in other than that point.
[0079] Concerning the revolving scroll side crank member, the top edge of the shaft part 39 Cc to be pressed-in is not rounded or taper-chamfered in the case of FIG. 6( a ), but as the edge of the opening 40 Bc of the crank member 40 B is taper-chamfered, the shaft part 39 Cc can be pressed into the opening 40 Bc with relative ease. The configuration of the crank member 39 C is the same as that of the crank member 39 A of FIG. 5.
[0080] In the case of FIG. 6( b ), the crank member 39 B is used and the top edge 39 Bd of the shaft part 39 Bc to be pressed-in is taper-chamfered, so the shaft part 39 Bc can be easily pressed into the opening 40 Bc.
[0081] In the case of FIG. 6( c ), the crank member 39 B is used and the top edge 39 Ad of the shaft part 39 Ac to be pressed-in is rounded, so the shaft part 39 Ac can be easily pressed into the opening 40 Bc.
[0082] [0082]FIG. 7 shows sectional views of still another three embodiments of the auxiliary crank consisting of a pair of crank members to be connected to compose an auxiliary crank. In all of FIG. 7( a ), ( b ), ( c ), the edge of the opening 40 Cc of the stationary scroll side crank member 40 C is rounded( 40 Cd). and the configuration of the crank member 40 C is the same as that of the crank member 40 A of FIG. 5 in other than that point.
[0083] Concerning the revolving scroll side crank member, the crank member 39 C of FIG. 6 is used as revolving scroll side crank member and top edge of the shaft part 39 Cc to be pressed-in is not rounded or tapered in the case of FIG. 7( a ), but as the edge of the opening 40 Bc of the crank member 40 B is rounded ( 40 Cd), the shaft part 39 Cc can be easily pressed into the opening 40 Bc.
[0084] In the case of FIG. 7( b ), the crank member 39 B is used and the top edge 39 Bd of the shaft part 39 Bc to be pressed-in is taper-chamfered, so the shaft part 39 Bc can be easily pressed into the opening 40 Bc.
[0085] In the case of FIG. 7( c ), the crank member 39 A is used and the top edge 39 Ad of the shaft part 39 Ac to be pressed-in is rounded, so the shaft part 39 Ac can be easily pressed into the opening 40 Bc.
[0086] By taper-chamfering or rounding the top edge of the shaft part to be pressed-in or the edge of the opening to receive the shaft part as shown in FIGS. 5,6, and 7 , the shaft part to be pressed-in can be easily pressed into the opening to receive the shaft part even if the center axis of the shaft part does not coincide accurately with that of the opening.
[0087] [0087]FIG. 8 shows an embodiment of the auxiliary crank consisting of a pair of crank members provided with a tightening bolt. FIG. 8( a ) shows one of the crank member in a side view and the other crank member in a sectional view.
[0088] The stationary scroll side crank member having the shaft part 42 Aa to be inserted into the bearings of the stationary scroll is formed into a mushroom-like shape having a cap and a stem, a hole 42 Ac is formed in the cap, the center axis of the hole being offset from that of the stem. A slit 42 Ag is cut in the cap along the center line passing the centers of the stem 42 Aa and hole 42 Ac. A screw hole 42 Ae with spot facing 42 Af is provided perpendicular to the slit 42 Ag in order to firmly clasp the shaft part 41 Ac of the revolving scroll side crank member 41 A by tightening the bolt 33 after it is inserted into the hole 42 Ac.
[0089] [0089]FIG. 9 shows another embodiment of the auxiliary crank consisting of a pair of crank members provided with a tightening bolt.
[0090] The point different from FIG. 8 is that a slit 42 Bg is cut beyond the center axis of the shaft part 42 Ba through the cap and the stem(shaft part 42 Ba), although in the case of FIG. 8 the slit 42 Ag is cut only in the cap.
[0091] Therefore, when the material and geometry are the same as those of FIG. 8, weaker tightening of the bolt 33 than the case of FIG. 9 is allowed for firmly clasping the shaft part 41 Ac of the revolving scroll side crank member 41 A after it is inserted into the hole 42 Ac.
[0092] [0092]FIG. 10 shows still another embodiment of the auxiliary crank consisting of a pair of crank members provided with a tightening bolt.
[0093] In this case, a lateral slit 42 Ch reaching near the center axis of the stem(shaft part 42 Ca) is cut in the cap of the crank member 42 C in addition to a longitudinal slit 42 Cg.
[0094] Therefore, when the material and geometry are the same as those of FIG. 8 and FIG. 9, still weaker tightening of the bolt 33 than the case of FIG. 8 and FIG. 9 is allowed for firmly clasping the shaft part 41 Ac of the revolving scroll side crank member 41 A after it is inserted into the hole 42 Ac.
[0095] It is allowable that the revolving scroll side crank member is pressed into the hole of the stationary scroll side crank member with the bolt 33 tightened beforehand.
[0096] A female screw thread may be provided in both of the crank members in the center of the shaft part to be inserted into the bearings for fastening the bearings by means of a bolt.
[0097] It is possible in the embodiments of FIGS. 4 ˜ 10 that a spacer(connector piece) is provided between both of the crank members which are pressed into both side of the spacer and the length of the auxiliary crank can be adjusted in accordance with the distance between the mirror-surfaces of both of the scrolls.
[0098] It is also suitable to apply an adhesive agent at least to the shaft part to be pressed-in or to the hole to receive the shaft part in order to reinforce the connection between the crank members.
[0099] Although the bearing housings bosses 12 b are formed integral with the revolving scroll 12 as shown in FIG. 1, it is possible to prepare the bearing housing bosses separately and attach to the revolving scroll, for example, by means of bolts. In this specification, “revolving scroll side crank member” includes the crank member in both of the above cases.
[0100] Further, although the bearing housing bosses 11 b are formed integral with the stationary scroll as shown in FIG. 1, it is possible to form the bearing housing bosses in the scroll housing 13 which surrounds the revolving scroll and is fixed to the stationary scroll. In this specification, “stationary scroll side crank member” includes the crank member in both of the above cases. | The invention aims to provide a scroll fluid machine which has auxiliary cranks divided into two separate crank members connected by pressure fitting in the process of assembling of the scroll machine. Each of the auxiliary cranks for regulating the motion of the revolving scroll is divided into a revolving scroll side crank member and a stationary scroll side crank member, the crank members are configured such that one of the crank members can be pressed into the other crank member, and both of the crank members are connected to compose a one-piece auxiliary crank when both of the scrolls are assembled. | 5 |
RELATED APPLICATIONS
This application claims the priority of provisional patent application serial No. 60/245,488 filed Nov. 2, 2000.
BACKGROUND OF THE INVENTION
A turbogenerator electric power generation system is generally comprised of a compressor, a combustor including fuel injectors and an ignition source, a turbine, and an electrical generator. Often, the system includes a recuperator to preheat combustion air with waste heat from the turbine exhaust. A recuperator is most efficient if the mass flows through it are evenly distributed. A recuperator also reduces the expansion ratio of the turbine and thus the power extracted by the turbine. Therefore, what is needed is a turbine engine that promotes even mass distribution of the exhaust gas into the recuperator and maximizes the turbine expansion ratio.
SUMMARY OF THE INVENTION
In one aspect, the present invention provides a turbine engine comprising a turbine rotationally driven by hot gas to exhaust the gas, a compressor rotationally coupled to the turbine to generate compressed air, an annular combustor for combusting fuel and the compressed air to generate the hot gas, the combustor extending coaxially away from the turbine to form a passage for the turbine exhaust gas therethrough, an annular recuperator surrounding the turbine for transferring heat from the turbine exhaust gas to the compressed air, a surface spaced from the combustor to direct the exhaust gas exiting from the passage into the recuperator, and an elongated structure extending from the surface into the passage toward the turbine to direct the exhaust gas flowing through the exhaust passage.
In another aspect, the elongated structure is generally conical. In other aspects, the structure is spaced from the combustor to form an annular exhaust passage, wherein the exhaust passage may be configured to sustain diffusion of the exhaust gas flowing therethrough. The passage may also be configured for evenly distributing the exhaust gas entering the recuperator.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is perspective view, partially in section, of a turbogenerator system according to the present invention;
FIG. 2 is a simplified, partial sectional view of the turbogenerator system of FIG. 1 including a vortex disrupter according to the invention.
DETAILED DESCRIPTION OF THE INVENTION
Referring to FIG. 1, integrated turbogenerator system 12 generally includes generator 20 , power head 21 , combustor 22 , and recuperator (or heat exchanger) 23 . Power head 21 of turbogenerator 12 includes compressor 30 , turbine 31 , and common shaft 32 . Tie rod 33 to magnetic rotor 26 (which may be a permanent magnet) of generator 20 passes through common shaft 32 . Compressor 30 includes compressor impeller or wheel 34 that draws air flowing from an annular air flow passage in outer cylindrical sleeve 29 around stator 27 of the generator 20 . Turbine 31 includes turbine wheel or impeller 35 that receives hot exhaust flowing from combustor 22 . Combustor 22 receives preheated air from recuperator 23 and fuel through a plurality of fuel injectors 49 . Compressor wheel 34 and turbine wheel 35 are supported on rotor or common shaft 32 having radially extending air-flow bearing rotor thrust disk 36 . Common shaft 32 is rotatably supported by a single air-flow journal bearing within center bearing housing 37 while bearing rotor thrust disk 36 at the compressor end of common shaft 32 is rotatably supported by a bilateral air-flow thrust bearing.
Generator 20 includes magnetic rotor or sleeve 26 rotatably supported within generator stator 27 by a pair of spaced journal bearings. Both rotor 26 and stator 27 may include permanent magnets. Air is drawn by the rotation of rotor 26 and travels between rotor 26 and stator 27 and further through an annular space formed radially outward of the stator to cool generator 20 . Inner sleeve 25 serves to separate the air expelled by rotor 26 from the air being drawn in by compressor 30 , thereby preventing preheated air from being drawn in by the compressor and adversely affecting the performance of the compressor (due to the lower density of preheated air as opposed to ambient-temperature air).
In operation, air 110 is drawn through sleeve 29 by compressor 30 , compressed, and directed to flow into recuperator 23 . Recuperator 23 includes annular housing 40 with heat transfer section or core 41 , exhaust gas dome 42 , and combustor dome 43 . Heat from exhaust gas 110 exiting turbine 31 is used to preheat compressed air 100 flowing through recuperator 23 before it enters combustor 22 , where the preheated air is mixed with fuel and ignited such as by electrical spark, hot surface ignition, or catalyst. The fuel may also be premixed with all or a portion of the preheated air prior to injection into the combustor. The resulting combustion gas expands in turbine 31 to drive turbine impeller 35 and, through common shaft 32 , drive compressor 30 and rotor 26 of generator 20 . Expanded turbine exhaust gas 100 then exits turbine 31 and flows through recuperator 23 before being discharged from turbogenerator 12 .
Referring to FIG. 2, combustor dome 43 is formed in a annular configuration to creating turbine exhaust gas passage 50 . Exhaust passage 50 channels expanded turbine exhaust gas and directs it to flow towards exhaust dome 42 disposed at the end of combustor dome 43 distal of turbine 31 . Exhaust dome 42 is formed with a generally semi-spherical configuration that directs exhaust gas to flow radially outward and reverse direction towards recuperator core 41 . To maximize the diffusion of exhaust gas and thus maximize the expansion ratio across turbine 31 , exhaust passage 50 is formed with a generally conical configuration that allows the exhaust gas to diffuse as it flows towards exhaust dome 42 .
Exhaust gas exits turbine 31 at very high speed and with a rotational directional component due to the rotation of the turbine impeller 35 . Thus, the flow of exhaust gas resembles a vortex flow in which the primary or main flow travels along the outer annulus of passage 50 and the secondary flow travels in the center of passage 50 and is generally characterized as low energy or low velocity flow. In some cases the secondary flow can be in the reverse direction and travel back toward the turbine impeller. Most of the mass flow discharge from the turbine is contained in the primary flow. The primary flow in effect forms an acoustic cavity around the secondary flow. Due to the highly turbulent and unsteady nature of the flow, this acoustic cavity can be excited to thereby create an acoustic resonance within the secondary flow.
To facilitate the diffusion of the exhaust gas as it flows through passage 50 , one embodiment of the present invention provides exhaust vortex disrupter 200 disposed within exhaust passage 50 . Disrupter 200 is mounted to exhaust dome 42 and extends from the exhaust dome coaxially towards turbine 31 to terminate proximal to turbine impeller 35 . In the preferred embodiment illustrated, disrupter 200 is formed in a generally conical configuration that cooperates with combustor dome 43 to define passage 50 as an annular, generally conical passage for the exhaust gas. Disrupter 200 is configured and spaced from combustor dome 43 to displace the secondary core region of the flow in passage 50 and to promote a more even velocity distribution in the flow as well as sustained diffusion of the exhaust gas. A more even velocity distribution helps to reduce pressure losses created in passage 50 . By occupying the central volume of passage 50 , disrupter 200 guides the exhaust flow towards exhaust dome 42 with greater diffusion, lower pressure losses, and a consequent greater expansion ratio across the turbine and higher turbine power output.
Furthermore, disrupter 200 continues to direct exhaust gas as it arrives at exhaust dome 42 , encouraging the gas to flow radially outward. In conventional systems, the exhaust gas would impinge generally perpendicularly upon exhaust dome 42 before being forced radially outward by the upstream exhaust gas that is being discharged by the turbine impeller. Furthermore, in conventional systems the effective flow area increases rapidly as the gas passage turns radially. The rapid area increase causes flow separation which prevents further diffusion. Additionally, the momentum of the flow tends to pull the flow off the wall of combustor dome 43 as the flow turns radially outward. This flow separation increases the pressure losses in passage 50 and promotes uneven velocity distribution as the exhaust gas flows towards the recuperator inlet. Thus, the base of disrupter 200 at which the disrupter is mounted to the exhaust dome is contoured with a generally conical surface to direct oncoming exhaust gas 100 radially outward and thus allow the exhaust gas to continue diffusing after it exits passage 50 . The contours of combustor dome 43 and exhaust dome 42 are designed to guide the flow radially outward through a smoothly varying cross-sectional flow area and thus prevent flow separation and promote continued diffusion through the passage.
Disrupter 200 further acts to more evenly distribute exhaust gas as it exits passage 50 and is reversed by exhaust dome 42 to enter recuperator core 41 , thereby enhancing the heat transfer efficiency of the recuperator. Because exhaust dome 42 provides a stable platform onto which to mount disrupter 200 , there is no need for struts or similar structures to fasten and secure the disrupter. Avoiding the use of such struts is highly desirable because the struts cause pressure loss and noise. Noise is also reduced by the use of disrupter 200 because it displaces the potential acoustic cavity that may be created by the secondary flow downstream of the turbine and eliminates the noise associated with acoustic resonation of this cavity. An additional advantage of using disrupter 200 is that by enhancing the diffusion of exhaust gas 100 , passage 50 may be shortened and thus entire turbogenerator 12 may be constructed with a reduced footprint.
Having now described the invention in accordance with the requirements of the patent statutes, those skilled in the art will understand how to make changes and modifications to the present invention to meet their specific requirements or conditions. Such changes and modifications may be made without departing from the scope and spirit of the invention, as defined and limited solely by the following claims. | In a turbine engine with an annular recuperator surrounding the turbine, exhaust gas is directed from the turbine to the recuperator by a generally curved exhaust dome. A vortex disrupter structure extends from the exhaust dome to a point distal of the turbine to evenly distribute the exhaust gas entering the recuperator and sustain diffusion of the exhaust gas to increase the expansion ratio across the turbine. | 5 |
BACKGROUND AND SUMMARY OF THE INVENTION
This invention pertains to a system for recharging an aquifer for shallow wells and means for operating the system.
Aquifers of shallow or moderate depth are a common source of water used for irrigation and sometimes for municipal water systems. These aquifers are often found in broad flat flood plains of slow running rivers. It would be expected that the river would recharge the aquifer. However, the river beds of such rivers are frequently silted tightly so that the water does not seep into the aquifer. Then, the aquifer is recharged only when the river is at flood stage or by rain water or snow melt.
In order to provide for any other recharging of the aquifer it is necessary to remove or by-pass the siltation. The common means for recharging is to dig a large pit down to the level of the aquifer, then to fill the pit with gravel and filter sand and then to pump water from the river into the pit. However, the silt from the river water again soon fills the filter sand with silt which again blocks the water from flowing through the filter sand and the recharging pit is again ineffective. It is then necessary to dry the pit and replace the sand.
By my invention I provide a system of recharging the aquifer by use of wells or a trench dug into the aquifer. The opening is lined, preferably with a plastic membrane, and then filled with pea gravel and covered with filter sand.
I also provide novel means for lining the trench and cleaning the filter bed. By shaping the recharging area with a narrow trench into the aquifer and a broad filter bed it is possible to provide for lower siltation and easy cleaning of that bed by my novel means.
FIGURES
FIG. 1 is a sectional view of my recharging system as applied to a moderately deep aquifer,
FIG. 2 is a detailed, enlarged sectional view of the system of FIG. 1 taken on a plane 90 degrees to the section of FIG. 1,
FIG. 3 is a sectional view of the system as used in a shallow aquifer,
FIG. 4 is a front elevational view of my filter bed cleaning machine in place over the system shown in FIG. 2,
FIG. 5 is a side elevational view of the cleaning machine,
FIG. 6 is a pictorial detailed view of one type of agitator that could be used on the cleaning machine,
FIG. 7 is a pictorial view of the trench lining mechanism in place on a truck,
FIG. 8 is an enlarged pictorial view of the trench liner placing mechanism,
FIG. 9 is a rear pictorial view showing the discharge end of the liner placing mechanism,
FIG. 10 is an enlarged detail view of the lower end of a liner roll in place,
FIG. 11 is a detailed top sectional view of the wall lubricating means showing the lubricating parts and anti-plugging dirt covers,
FIG. 12 is an end sectional view of the lubricating means shown in FIG. 11,
FIG. 13 is a side elevational view of the tractor with a leveling rake attached,
FIG. 14 is a detailed enlarged view of the rake,
FIG. 15 is a detailed top view of the tractor showing a system for disposal of sand, water and silt pumped from the filter bed, and
FIG. 16 is an elevational view of the system of FIG. 15 with parts broken away to show underlying parts.
DESCRIPTION
Briefly my invention comprises a system for recharging a relatively shallow aquifer and the mechanism which makes the system operate. The system includes the provision of a trench or series of trenches dug into the aquifer, lined preferably with flexible membrane-like material and filled with pea gravel. A filter bed of fine sand is provided above the gravel, and a novel means is provided to clean the filter bed of silt and return the sand to the bed. Also, means may be used to provide a corrugated surface on the filter bed to provide more surface through which water may filter and gulleys in which silt will rest leaving the peaks of the corrugations free to receive the recharging water.
More specifically, and referring to the drawings, I envision that my system can be used either with very shallow or moderately deep aquifers. Referring first to FIGS. 1 and 2, I illustrate the use of my system in the relatively deep aquifer. In this system, a series of wells 19 is illustrated as reaching into the aquifer sand 18. A casing 20 is provided for the well, and terminates at its lower end in a screen 21. Around the screen I provide a gravel pack 17 of gravel large enough to provide for easy seepage of water to the aquifer sand. A grouted casing 22 is provided surrounding the casing 20 of the well at its lower part to prevent erosion of the walls of the well. Such erosion might well plug the aquifer sand with silt causing the well to become inoperative.
Above the grouted casings of the wells, I dig a trench lined with a membrane or film liner 10 preferably of a plastic material placed therein by my novel trench lining machine described hereafter. Within this trench I provide an extension 20' of the casing 20 having a cap 26 covering the upper end. A screen 23 connects the casing 20 and its extension 20'. This screen as best shown in FIG. 2 is of tubular shape having an axis running longitudinally of the trench. Caps 25 are provided at the ends of the screen tubes so that gravel and other foreign material will not get into the well.
At its upper part, the trench broadens out and is also lined by the plastic film 11 which may be integral with the liner 10 of the trench. Gravel 16 of the approximate size of pea gravel fills both the trench and a part of the flared trench 15. The pea gravel surrounds the extension 20' and the screen 23 at the top of each well. A layer 16' of gravel somewhat finer than the pea gravel 16 may be used in the flared trench above the coarser gravel 16 to support the filter sand 14.
Above the flared part 15 of the trench, I provide curbings 29 having an ell-shape with the foot 28 of the ell running inward toward the trench. As will be explained later, these curbings thus form a pair of tracks on which my novel device for cleaning the filter bed may run. Between the curbings and above the gravel layer 16' I provide a filter bed 14 of relatively fine sand. Preferably, this sand is filled to the approximate level of the top of the feet 28 of the curbing.
In order to operate this type of recharging system, water 13 is introduced from an outside source such as an adjacent stream, river, pond or the like into the space between the curbings. This water filters through the filter bed 14 into the gravel 16 and 16'. It then can seep rapidly through that gravel and through the screen 23 into the casing 20. From there it runs out of the lower screen 21 through the gravel 17 into the aquifer sand 18, thus recharging the aquifer. The relative sizes of the gravels and sands are of considerable importance. The gravel 16 should not be greatly different from that in the aquifer. More important, however, is the gradation between the filter sand 14, the support bed 16' and the pea gravel 16. The support bed must be fine enough to block any tendency of the filter sand to move into the coarser gravel 16.
For use with very shallow aquifers the system may be modified as shown in FIG. 3. In this system, the trench extends directly into the aquifer sand 18 and therefore can conduct the water 13 directly to the aquifer. In other respects the construction of the trench and filter bed are similar to that of the trench and bed used between the wells as shown in FIG. 1.
Unique means for cleaning the filter bed of my system is illustrated in FIGS. 4, 5 and 6. The device is shown above the shallow aquifer system in which the curbing feet 28 firmly based on the surrounding ground 12 provide tracks on which a tractor 27 can run. A hool 37 is suspended from beneath the tractor by chains 83 from arms 44. The arms 44 are adapted to raise the hood or lower it as may be desired. A rubber rim or flap 38 surrounding the hood 37 provides a seal by which water from the system can be pulled out of the hood. A pump 39 is provided for the purpose of pumping water from the hood which is discharged through a pipe 118 as at 41. If necessary, a constant prime pump 42 may be used to keep the pump 39 primed through the connection 43 between the pump 42 and the pump 39.
In order to be effective, in cleaning the filter bed, the silt which often clogs the bed must be removed from the filter sand and mixed in with the charging water 13. The water carrying the silt can then be pumped out by the pump 39. The agitation is accomplished by an agitator. This agitator takes at least two forms. My preferred form is shown in FIGS. 4 and 5. The agitator consists of a series of disks 30 mounted on a belt 82. The belt is driven in an oscillating manner by a belt 35 operating through pulleys 33 and 34. Power to the pulleys may come through a shaft 36 from the tractor 27 although independent power could also be used. For example an electric or a hydraulic motor could be used for that purpose. A gear box 84 may be used to convert the rotary motion of the shaft 36 to the oscillating motion required by the belt. The agitator is supported from the hood 37 by supports 81.
The alternate agitator shown in FIG. 6 is also driven from the shaft 36. In this case a gear box for the conversion of motion is not needed so that the pulley and belt system can drive a shaft 86 more directly. The shaft 86 is journalled in a sleeve 87 which can be supported from the hood on a flange 85. A wheel 31 having open spokes supports flaps 32 extending downward from the spokes. Rotation of the wheel 31 causes the flaps to sweep the filter bed under water and therefore to stir the silt into the water. Then the pump 39 can suck out the water-borne silt and discharge it, leaving a clean sand filter bed.
Construction of the trench and lining can be easily accomplished by means of the mechanism shown in FIGS. 7, through 12. As shown in these figures, the lining mechanism may be mounted on a truck 71 and is enclosed in a container having sides 46 and a floor 57. This container is mounted so as to be vertically movable through the bed 91 of the truck. In order to avoid interference with the drive train of the truck, the device should be mounted to one side of the centerline of the truck, offset from the drive train. In some cases, it may be desirable to mount the container on a device pulled by the ditching machine. The time would thus be reduced during which the trench walls could collapse, and then placement of the gravel immediately behind the trailer carrying the container would almost certainly assure proper formation of the trench.
The lifting mechanism may be of many forms as will appear to those skilled in the art. I have illustrated a cable system including a winch 92 adapted to pull the cables 93 attached to the corners of the container 46 and running over a sheave 75. In order to prevent binding and unequal pulling, I provide a control arm 47 pivotally attached to the container at pivot 50 and to a bracket 77 mounted on the truck 71. It will be apparent that an hydraulic lifting mechanism could also be used.
The mechanism used to line the trench is best shown in FIGS. 8 and 9. A pair of rolls of plastic film or membrane 51 and 52 are each rotatably mounted on a vertical spindle 58. The spindle is journalled in a thrust bearing 59 (FIG. 10) mounted on the floor 57 of the container. The rolls of membrane 51 and 52 are supported vertically by a plate 60 fixed to the spindle 58. At the upper end of each spindle I provide a bearing 54 mounted on a cross bar or plate 53. This plate may be attached to the sides 46 of the container by wing bolts 56 or other easily detachable means so that the rolls can be replaced readily. From these rolls, the membrane sheets 67 are paid out to the rear of the unit.
As noted in the description of the system itself, the trench is filled with gravel. In order to prevent the gravel from entering the mechanism for laying the lining membranes, I provide a brush assembly 88 (FIG. 9) adapted to sweep the membrane as it runs out of the rear of the mechanism. This assembly is supported from the floor 57 of the container by a bracket 89 having a foot 90 fixed to the floor. The assembly includes a two-part wall 70 adapted to clamp brush members 69 between the two parts. The wall is adapted close the rear of the container except for the part occupied by the brushes. The brushes 69 are placed so as to press the membrane 67 against the walls 46 of the container, and thus to close completely the rear end of the mechanism making entry of gravel into the container impossible.
In order to provide for ease of pulling the device through the trench, I provide novel means for lubricating the sides 46 of the container. This means includes a series of perforated tubes 63 and 64 attached to the inner surface of both sides 46. The perforation 66 extend through the sides 46 so that liquid in the tubes can flow out and wet the sides.
Means for getting the liquid to the perforated tubes 63 and 64 includes a tank 76 mounted on the truck 71 (FIG. 7) connected by a tube or pipe 79 to a junction 80 with a pair of tubes 61. These tubes are flexible so that lifting the container does not interfere with the flow of liquid. The tubes 61 are attached to manifold tubes 62 and 65 which in turn carry the liquid to the perforated tubes 63 and 64.
I also provide means to protect the ports 66 from becoming clogged with soil from the sides of the trench. This means comprises merely small guards or covers 68' (FIGS. 11 and 12) fixed to the side 46 and having lips spaced from the side and overhanging the port. Thus, liquid can always flow from the port 66, down the side 46 and keep the side wet. Although other liquids may be used, I have found that water works well and is my preferred liquid.
In order to provide a somewhat more efficient filter bed, I propose to use a bed forming device as best shown in FIGS. 13 and 14. This device comprises a rake consisting of arms 96 pivoted at 95 to the lower members 101 of a three point hitch on the tractor 27. The upper member 102 of the hitch may be connected to the arms 96 by means of chains 97 thus providing for raising and lowering of the rake. A rake member 98 may be bolted cross ways between the arms 96. This member is formed with teeth 99 formed by notches 100 in the lower edge of the member 98. Although I have shown the rake member 98 as a solid bar, I envision that it might be desirable to perforate the bar or to fabricate it from narrow members forming an open rake so as to permit water on the filter bed freer passage through the rake.
In use, this rake is simply pulled behind the tractor 27 over the surface 103 of the sand bed 14. Ahead of the rake, that surface may be very rough and irregular because of dumping of cleaned sand as described hereafter, or may be very smooth because of the action of the water covering it. In either case, the teeth 99 as pulled over the bed will level out the discharged sand and other irregularities and form a longitudinally corrugated surface 104. This type of surface has a greater area of sand presented to the water for the water to filter through, and also provides a surface in which the silt and other clogging impurities can fall into the valleys of the corrugations while the water filters through the peaks which will remain unclogged. Thus, the filter bed becomes more efficient and will stay useful for longer periods of time.
A means for separating, cleaning and returning sand to the sand bed 14 is shown in FIGS. 15 and 16. This means is mounted on the tractor 27 and is used with the hood 37 and its associated pump and cleaning apparatus which discharges through the pipe 118. It will be evident from the foregoing description that the water being discharged from the pipe 118 will be carrying a certain amount of sand as well as silt and other clogging impurities. By the illustrated device, I propose to recover most of the sand and return it to the bed 14. In some instances it may be desirable to pick up the complete filter bed, wash the sand and return it. This is also possible with this device.
In order to accomplish my purpose, I cut a slot 108 in the bottom of the pipe 118 and provide a dam 117 at the edge of the slot toward the discharge end (at 41) of the pipe. The sand, being considerably heavier than the water will flow along the bottom of the pipe 118 and be blocked by the dam 117 and fall out through the slot 108. Some of the water may also discharge through the slot, but the amount will be relatively small and inconsequential.
The sand 115 falling from the slot is caught by a hopper 109 supported beneath the slot 108. From this hopper, it is removed by an auger 111 running in a trough 110. To prevent silt and the like from being returned to the bed with the sand in the trough 110, I provide for water to be pumped from the recharging water 13 through a pipe 105 mounted at the front of the tractor. The pump 106 then discharges the relatively clean water through a pipe 107 onto the sand in the trough 110 and washes the lighter silt back into the hopper 109. When the level of water reaches the upper part of the hopper, an overflow pipe 113 conducts the water to a discharge end at 116 at approximately the same place as the discharge 41. The pipe 113 may be carried by a support 114 attached to the pipe 118. The cleaned washed sand 112 is dropped from the trough 110 back into the bed 14 where the rake 98 will level it again to form the efficient filter which is the goal of my invention. | A system for recharging an aquifer comprising an opening into the aquifer, means for packing the opening with sized, coarser, clean gravel, filter sand above the gravel and means for cleaning the filter sand. | 4 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Patent Application No. 61/904,808, filed Nov. 15, 2013, which application is incorporated herein by reference in its entirety.
TECHNICAL FIELD
The present disclosure relates to a bearing cage with an inner or outer circumferential surface with a self-lubricating coating of molybdenum disulfide or polytetrafluoroethylene. The present disclosure relates to a method of manufacturing a bearing cage with an inner or outer circumferential surface with a self-lubricating coating of molybdenum disulfide or polytetrafluoroethylene. The present disclosure relates to a bearing assembly including a bearing cage with a self-lubricating coating of molybdenum disulfide or polytetrafluoroethylene.
BACKGROUND
It is known to use spindle bearings with phenolic cages for high-speed applications such as machine tools. Such spindle bearings typically have inner and outer rings, the phenolic bearing cage radially located between the inner and outer rings, and a plurality of roller elements retained by the bearing ring. In a radially outwardly guided configuration, an outer circumferential surface of the bearing cage (the land guiding surface) is engaged with and guided by an inner circumferential surface of the outer ring (land surface). Oil from bearing grease or similar lubricant forms a lubricant film between the land guiding surface and the land surface. In a radially inwardly guided configuration, an inner circumferential surface of the bearing cage (the land guiding surface) is engaged with and guided by an outer circumferential surface of the inner ring (land surface).
Oil from the bearing grease or similar lubricant forms a lubricant film between the land guiding surface and the land surface. Lubrication of the land guiding surface is critical for operation of the bearing. However, at start up, the lubricant film is not yet fully formed between the land surface and the land guiding surface and base oil has only starting to migrate to the land guiding surface. Known spindle bearings do not provide a desired level of lubrication of the land guiding surface at start up.
EP 0 695 884 B1 discloses a greased rolling bearing element with a solid lubricating coating. The description of EP 0 695 884 B1 mentions GB 826 091 A, which described cages with metallic bodies and a plastic coating of polyamide or poly tetrafluorethylene containing about 3% of MoS 2 or graphite.
The description of EP 0 695 884 B1 mentions U.S. Pat. No. 3,500,525, JP-A-62 141 314 and JP-A-3 255 223, all of which disclose a coating of MoS 2 for a bearing cage. However, all these references relate to bearings for use in (high) vacuum and/or at elevated temperatures (250° C. or more). Grease lubrication cannot be used in (high) vacuum and/or at elevated temperatures.
EP 0 695 884 B1 discloses use of a coating of MoS 2 and poly tetrafluorethylene over a steel bearing cage.
SUMMARY
According to aspects illustrated herein, there is provided a bearing cage, including: a body fabricated of phenolic material and having an outer circumferential surface and an inner circumferential surface; and a coating of molybdenum disulfide or polytetrafluoroethylene adhered to the outer circumferential surface or the inner circumferential surface.
According to aspects illustrated herein, there is provided a bearing assembly including: an inner ring including a first outer circumferential surface; an outer ring including a first inner circumferential surface; a bearing cage fabricated of phenolic material and including first and second sides, a second outer circumferential surface connecting the first and second sides, a second inner circumferential surface connecting the first and second sides, and a coating of molybdenum disulfide or polytetrafluoroethylene adhered to the second outer circumferential surface or to the second inner circumferential surface; and a plurality of rolling elements retained by the bearing cage. The second outer circumferential surface is engaged with the first inner circumferential surface to guide the bearing cage. The second inner circumferential surface is engaged with the first outer circumferential surface to guide the bearing cage.
According to aspects illustrated herein, there is provided a method of manufacturing a bearing cage, including: fabricating a body from phenolic material, the body including an outer circumferential surface and an inner circumferential surface connecting first and second sides; and adhering a coating of molybdenum disulfide or polytetrafluoroethylene to the inner or outer circumferential surface.
BRIEF DESCRIPTION OF THE DRAWINGS
Various embodiments are disclosed, by way of example only, with reference to the accompanying schematic drawings in which corresponding reference symbols indicate corresponding parts, in which:
FIG. 1A is a perspective view of a cylindrical coordinate system demonstrating spatial terminology used in the present application;
FIG. 1B is a perspective view of an object in the cylindrical coordinate system of FIG. 1A demonstrating spatial terminology used in the present application;
FIG. 2 is a perspective view of a bearing cage with a self-lubricating coating on an outer circumference;
FIG. 3 a schematic cross-sectional view generally along line 3 - 3 in FIG. 2 ;
FIG. 4 is a schematic cross-sectional view of a bearing cage with a coating on an inner circumferential surface; and,
FIG. 5 is a partial cut-away view of a bearing assembly including a bearing cage with a self-lubricating coating on an outer circumference.
DETAILED DESCRIPTION
At the outset, it should be appreciated that like drawing numbers on different drawing views identify identical, or functionally similar, structural elements of the disclosure. It is to be understood that the disclosure as claimed is not limited to the disclosed aspects.
Furthermore, it is understood that this disclosure is not limited to the particular methodology, materials and modifications described and as such may, of course, vary. It is also understood that the terminology used herein is for the purpose of describing particular aspects only, and is not intended to limit the scope of the present disclosure.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which this disclosure belongs. It should be understood that any methods, devices or materials similar or equivalent to those described herein can be used in the practice or testing of the disclosure.
FIG. 1A is a perspective view of cylindrical coordinate system 80 demonstrating spatial terminology used in the present application. The present disclosure is at least partially described within the context of a cylindrical coordinate system. System 80 has a longitudinal axis 81 , used as the reference for the directional and spatial terms that follow. The adjectives “axial,” “radial,” and “circumferential” are with respect to an orientation parallel to axis 81 , radius 82 (which is orthogonal to axis 81 ), and circumference 83 , respectively. The adjectives “axial,” “radial” and “circumferential” also are regarding orientation parallel to respective planes. To clarify the disposition of the various planes, objects 84 , 85 , and 86 are used. Surface 87 of object 84 forms an axial plane. That is, axis 81 forms a line along the surface. Surface 88 of object 85 forms a radial plane. That is, radius 82 forms a line along the surface. Surface 89 of object 86 forms a circumferential plane. That is, circumference 83 forms a line along the surface. As a further example, axial movement or disposition is parallel to axis 81 , radial movement or disposition is parallel to radius 82 , and circumferential movement or disposition is parallel to circumference 83 . Rotation is with respect to axis 81 .
The adverbs “axially,” “radially,” and “circumferentially” are with respect to an orientation parallel to axis 81 , radius 82 , or circumference 83 , respectively. The adverbs “axially,” “radially,” and “circumferentially” also are regarding orientation parallel to respective planes.
FIG. 1B is a perspective view of object 90 in cylindrical coordinate system 80 of FIG. 1A demonstrating spatial terminology used in the present application. Cylindrical object 90 is representative of a cylindrical object in a cylindrical coordinate system and is not intended to limit the present invention in any manner. Object 90 includes axial surface 91 , radial surface 92 , and circumferential surface 93 . Surface 91 is part of an axial plane, surface 92 is part of a radial plane, and surface 93 is a circumferential surface.
FIG. 2 is a perspective view of bearing cage 100 with a self-lubricating coating on an outer circumference.
FIG. 3 a cross-sectional view generally along line 3 - 3 in FIG. 2 . The following should be viewed in light of FIGS. 2 and 3 . Cage 100 includes axis of rotation AR and body 102 fabricated of phenolic material and having outer circumferential surface 104 and inner circumferential surface 106 . Body 102 can be fabricated of any phenolic material known in the art. Cage 100 includes coating 108 of molybdenum disulfide or polytetrafluoroethylene adhered to outer circumferential surface 104 . That is, surface 104 is at least partially covered with coating 108 . In an example embodiment, the coating is molybdenum disulfide. In an example embodiment, the coating is polytetrafluoroethylene. In an example embodiment, cage 100 includes grease GR. Grease GR is generally located proximate surface 106 . The thickness of coating 108 in FIGS. 2 and 3 has been exaggerated for purposes of illustration.
In an example embodiment, at least a portion of the coating forms a continuous ring, in circumferential direction CD, encircling surface 104 . In an example embodiment, an entirety, that is, all of the coating is continuous in circumferential direction CD on surface 104 . Body 102 includes sides 110 and 112 . Outer circumferential surface 104 and inner circumferential surfaces 106 connect sides 110 and 112 . That is, sides 110 and 112 bound the outer circumferential surface and the inner circumferential surface in axial direction AD. In an example embodiment, at least a portion of coating 108 is continuous from side 110 to side 112 , that is, between side 110 and 112 . In an example embodiment, an entirety, that is, all, of coating 108 is continuous from side 110 to side 112 , that is, between side 110 and 112 . Stated otherwise, surface 104 is completely covered with coating 108 .
FIG. 4 is a schematic cross-sectional view of bearing cage 200 with a coating on an inner circumferential surface. Cage 200 includes axis of rotation AR and body 202 fabricated of phenolic material and with outer circumferential surface 204 and inner circumferential surface 206 . Body 202 can be fabricated of any phenolic material known in the art. Cage 200 includes coating 208 of molybdenum disulfide or polytetrafluoroethylene adhered to inner circumferential surface 206 . That is, surface 206 is at least partially covered with coating 208 . In an example embodiment, the coating is molybdenum disulfide. In an example embodiment, the coating is polytetrafluoroethylene. In an example embodiment, cage 200 includes grease GR. Grease GR is generally located proximate surface 204 . The thickness of coating 208 has been exaggerated for purposes of illustration.
In an example embodiment, at least a portion of the coating forms a continuous ring in circumferential direction CD encircling surface 206 . In an example embodiment, an entirety, that is, all of the coating is continuous in circumferential direction CD on surface 206 . Body 202 includes sides 210 and 212 . Outer circumferential surface 204 and inner circumferential surfaces 206 connect sides 210 and 212 . That is, sides 210 and 212 bound the outer circumferential surface and the inner circumferential surface in axial direction AD. In an example embodiment, at least a portion of coating 208 is continuous from side 210 to side 212 , that is, between side 210 and 212 . In an example embodiment, an entirety, that is, all, of coating 208 is continuous from side 210 to side 212 , that is, between side 210 and 212 . Stated otherwise, surface 206 is completely covered with coating 608 .
FIG. 5 is a partial cut-away view of bearing assembly 300 including bearing cage 100 with a self-lubricating coating on an outer circumference. The following should be viewed in light of FIGS. 2 , 3 and 5 . Assembly 300 includes axis of rotation AR, bearing cage 100 , outer ring 302 , inner ring 304 , and at least one rolling element 306 . Ring 302 includes inner circumferential surface 308 , also referred to as land surface 308 . Outer circumferential surface 104 engages surface 308 .
Advantageously, bearings 100 and 200 addresses the problems noted above regarding the lack of lubrication on the surface of a bearing cage during start-up. Specifically, coatings 108 and 208 provide effective friction reduction prior to the build up of oil on surfaces 104 and 206 , respectively. There are no teachings, suggestions, or motivations in the prior art to use coating 108 on a phenolic bearing cage or that the use of coating 108 on a phenolic bearing cage would be successful.
It will be appreciated that various of the above-disclosed and other features and functions, or alternatives thereof, may be desirably combined into many other different systems or applications. Various presently unforeseen or unanticipated alternatives, modifications, variations, or improvements therein may be subsequently made by those skilled in the art which are also intended to be encompassed by the following claims. | A bearing cage, including: a body fabricated of phenolic material and having an outer circumferential surface and an inner circumferential surface; and a coating of molybdenum disulfide or polytetrafluoroethylene adhered to the outer circumferential surface or the inner circumferential surface. A method of manufacturing a bearing cage, including: fabricating a body from phenolic material, the body including an outer circumferential surface and an inner circumferential surface connecting first and second sides; and adhering a coating of molybdenum disulfide or polytetrafluoroethylene to the inner or outer circumferential surface. | 5 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. Ser. No. 11/311,616, filed Dec. 19, 2005, which is continuation of U.S. Ser. No. 10/825,980, filed Apr. 16, 2004, which is a continuation of U.S. Ser. No. 10/051,418, filed Oct. 30, 2001, now U.S. Pat. No. 6,848,840, which claims priority under 35 U.S.C. § 119(e) from U.S. Provisional Application No. 60/244,390, filed Oct. 31, 2000, all of which are hereby incorporated herein by reference in their entirety.
INTRODUCTION
[0002] The present invention relates generally to the field of optical connectors for circuit boards. More particularly, the present invention relates to electro-optical back plane circuit boards that have both electrical and optical connectors.
BACKGROUND OF THE INVENTION
[0003] Electronics devices are becoming increasingly integrated with optical systems. This has given rise to the need to integrate electronics and optics together into printed circuit board systems. Currently, this integration is somewhat awkward. Although printed circuit wiring is a fairly mature technology, the mixing of printed circuit wiring with optical conduction paths is still at an awkward stage of development.
[0004] Additionally, the connectors for interfacing optical conduction paths on circuit boards with fibers off-board is still a challenge. Specifically, aligning the off-board optical fibers with the connectors on the board remains a reliability problem.
[0005] Thus, what is needed is a printed circuit board configuration that reliably integrates electrical conduction with optic conduction, including stable optical connectors.
SUMMARY OF THE INVENTION
[0006] One aspect of the present invention is an optical connector for use in a multilayer circuit board.
[0007] Another aspect of the present invention is a method for forming an electro-optical multilayer circuit board having embedded optical connectors.
[0008] It is also an aspect of the present invention to embed an optical connector in a multilayer circuit board using a guide plate and pins to align the optical connector with the various layers of the circuit board.
[0009] An additional aspect of the present invention is an electro-optical back plane having both electrical connectors and optical connectors.
[0010] One embodiment of the present invention is an optical connector for use with an electro-optical board. The optical connector includes a right angle interface body that has one or more first optical paths and one or more second optical paths. Each of the first optical paths corresponding to a respective second optical path, and the first optical paths are disposed in a first plane and the one or more second optical paths are disposed in a second plane. The first and second planes being substantially at right angles with respect to one another. The optical connector also includes a female self-alignment body that has a tapered channel substantially aligned with the first plane. The optical connector further includes a tapered male self-alignment body sized to fit closely into the tapered channel of the female self-alignment body, and having one or more third optical paths adapted to align with the first optical paths when the tapered male self-alignment body is engaged with the female self-alignment body. The third optical paths are adapted for connection to one or more optical fibers disposed outside the electro-optical board. The second optical paths are adapted for connection to optical fibers embedded in the electro-optical board.
[0011] Another embodiment of the present invention is a method of integrating into an optical-electrical board an optical connector that includes a right angle interface body, a female self-alignment body having a tapered channel, and an anchor body. The method includes the steps of connecting the right angle interface body to a set of one or more optical fibers, and embedding the right angle interface body and the one or more optical fibers inside the optical-electrical board. The method also includes the steps of forming a hole in the optical-electrical board to expose an upper surface of the embedded right angle interface body, securely fastening the anchor body about the hole, and inserting the female self-alignment body through the anchor body and the hole so as to bring the tapered channel into registration with the embedded right angle interface body.
[0012] Yet another embodiment of the present invention is an electro-optical back plane. The electro-optical back plane includes a fiber management system formed of plural optical fibers, an electrical bus circuit, and a board, wherein the fiber management system and the electrical bus circuit are embedded inside the board. The electro-optical back plane further includes plural optical connectors disposed on the board, each of the optical connectors being coupled to one or more of the plural optical fibers of the fiber management system. Additionally, the electro-optical back plane includes plural electrical connectors disposed on the board, each of the electrical connectors being electrically connected to the electrical bus circuit. Each of the optical connectors includes a right angle interface body embedded into the board for connection to one or more fibers of the fiber management system, an anchor body securely fastened to the surface of the board, and a female self-alignment body having a tapered channel. The female self-alignment body is held by the anchor body so that the tapered channel is in registration with an upper surface of the right angle interface body.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] Additional objects and advantages of the present invention will be apparent in the following detailed description read in conjunction with the accompanying drawing figures.
[0014] FIG. 1 illustrates a sectional exploded view of parts of an optical connector according to an embodiment of the present invention.
[0015] FIG. 2 illustrates a perspective view of a right angle interface body according to an embodiment of the present invention.
[0016] FIG. 3 illustrates a sectional view of the right angle interface body of FIG. 2 .
[0017] FIG. 4 illustrates another sectional view of the right angle interface body of FIG. 2 (orthogonal to the sectional view of FIG. 3 ).
[0018] FIG. 5 illustrates an initial pre-assembly schematic view of various lamination layers for composing a multilayer printed circuit board according to an embodiment of the present invention.
[0019] FIG. 6 illustrates a post-lamination cross sectional view of a multilayer circuit board according to a process embodiment of the present invention.
[0020] FIG. 7 illustrates a cross sectional view of a multilayer circuit board illustrating a machining step of a process embodiment of the present invention.
[0021] FIG. 8 illustrates a cross sectional view of a multilayer circuit board illustrating a connector assembly step of a process embodiment of the present invention.
[0022] FIG. 9 illustrates a cross sectional view of a multilayer circuit board illustrating another connector assembly step of a process embodiment of the present invention.
[0023] FIG. 10 illustrates a cross sectional detail view (per section line X in FIG. 9 ) showing the ratcheted interface between an anchor body and a female self-alignment body that form the female connector portion according to an embodiment of the present invention.
[0024] FIG. 11 illustrates a partial section view of a fully assembled optical connector according to an embodiment of the present invention.
[0025] FIG. 12 illustrates a schematic view of an electro-optical back plane according to an embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0026] Referring to FIG. 1 , and exploded sectional view of a connector according to an embodiment of the present invention is illustrated. A male connector portion 110 is insertable into a female connector portion 120 . The male and female connector portions 110 , 120 are tapered to fit together so as to provide a self-aligning function. A micro machined optical conductor assembly 112 in the male connector portion 110 is cause to be brought into precise alignment with another micro machined optical conductor assembly 132 disposed in a right angle interface body 130 . The female connector portion 120 guides the male connector portion 110 into precise registration with the right angle interface body 130 .
[0027] The housing parts of the optical connector are preferably formed of a high Tg material. Polyetherimide resins, and in particular ULTEM® resin (a product of GE), have been found to be a suitable as housing material to embody the invention.
[0028] The right angle interface body 130 is to be embedded inside a multi-layer circuit board. The female connector portion 120 mounts on a surface of the multi-layer circuit board, with a lower portion thereof extending down into the circuit board to engage the right angle interface body 130 . The micro machined optical conductor assembly 132 is disposed above an integrated mirror 134 that provided a 90° transition for light traveling through the connector. This reflected light also travels through an additional micro machined conductor assembly 136 that provides coupling to a plurality of optical fibers 140 , which are embedded inside the multilayer circuit board.
[0029] An optional feature of the optical connector 100 according to this embodiment is a spring-loaded door 122 inside the tapered passageway 124 of the female connector portion 120 . The spring-loaded door 122 provides two functions. First, it prevents debris from falling down n inside the connector and contaminating the optical interface surface 131 on the top of the right angle interface body 130 . Secondly, the spring-loaded door 122 prevents light from being emitted through the tapered passageway 124 of the female connector portion 120 when no male connector portion 130 is inserted therein.
[0030] The female connector portion 120 is securely held to the surface of the multilayer circuit board via locking connectors 124 that are inserted into holes formed through the multilayer circuit board.
[0031] Off-board optical fibers 150 are connected into the male connector portion 110 so as to be in optical communication with the micro machined optical conductor assembly 112 . In addition to the self-aligning feature provided by the matched tapering shape of the male and female connector portions 110 , 120 , precision of alignment of the optical connector is enhanced by alignment pins 114 extending from the male connector portion that interdigitate with precisely machined alignment holes (not shown in this view) formed in the top side of the right angle interface body 130 .
[0032] Referring to FIG. 2 , a perspective view of the right angle interface body 130 is illustrated. The precision alignment holes 138 are disposed on either end of the optical conductor assembly 132 . Plural optical conductors 137 (preferably glass fibers) embedded in a silicon body 139 to form the optical conductor assembly 132 . The optical conductor assembly is principally formed of silicon. MT type optical connector devices have been found to be suitable for embodying these assemblies.
[0033] Referring to FIG. 3 , a sectional view of the right angle interface body 130 of FIG. 2 is illustrated. Anchor members 135 extend downward from the bottom side of the right angle interface body 130 to provide enhanced mechanical stability inside the multilayer circuit board.
[0034] Referring to FIG. 4 , another sectional view of the right angle interface body 130 of FIG. 2 is illustrated. Extending upwardly from the integrated mirror 134 through the micro machined optical conductor assembly 132 are plural glass fibers 137 .
[0035] Referring to FIG. 5 , an initial pre-assembly schematic view is illustrated, showing the relative position of various lamination layers for composing the multi-layer printed circuit board. One layer is an electrical inner layer 502 according to known prior art practices. A registration plate 504 is provided to keep the board structure flat and having alignment holes to align and fix the optical connector during bonding. A prepreg layer 506 for bonding and embedding optical management structures is provided above the laminate layer 504 . About the right angle interface body 530 . a laminate layer 508 is provided with the perimeter of the fiber management system 540 being routed out to compensate for thickness differences. An adhesive copper tape 512 is layered onto the top surface of the right angle interface body 530 to protect the glass fibers, alignment holes, and other surrounding structures from later processing steps. The copper tape 512 is adhered to the top surface of the right angle interface body 530 by an adhesive. Preferably, the adhesive can withstand a temperature of at least 210° C. and will not leave behind excessive residue when the copper tape 512 is later removed. Above the additional lamination layers 514 , an outer copper foil 510 is layered on as a top layer. The outer copper foil 510 is preferably about 18 micrometers in thickness.
[0036] The circuit board layers may be formed with any suitable materials that are known in the art. Standard circuit board materials are available from a number of manufacturers including Isola of the U.K., Nelco Products, Inc. of Fullerton, Calif., and Polyclad Laminates of Franklin, N.H.
[0037] Referring to FIG. 6 , a cross sectional view of the multilayer circuit board 600 is illustrated, post-lamination. The right angle interface body 530 is shown coupled to a fiber management system 540 , with both being embedded inside a multi-layer printed circuit board 600 . The right angle interface body 530 , a basic alignment component of the entire optical connector, is aligned to the circuit board 600 via a registration plate 504 . The registration plate 504 aligns and fixes the entire optical connector to the electrical pattern of the printed circuit board 600 by fixing the anchor members 539 into the registration plate 504 . The registration plate 504 is aligned to the other layers of the multilayer printed circuit board 600 by using a traditional Lenkheit system.
[0038] The interlocking of the right angle interface body 530 with the registration plate 504 via the anchor members 539 aligns the optical connector both in the x-y plane of the board, as well as along the z axis.
[0039] It is noted that the right angle interface body 530 has angled sidewalls 531 . These angled sidewalls 531 serve a dual purpose. One reason for having the angles sidewalls 531 is to facilitate cleaning around the interface body 530 with a laser that is used to ablate awaythe board layers above the interface body 530 . The second useful purpose for the angled sidewalls is to provide for good alignment with the female connector portion.
[0040] Referring to FIG. 7 , the multilayer printed circuit board 600 is shown after machining steps have been conducted on the board. Holes 602 have been drilled through the board 600 for connecting the female connector portion 920 to the surface of the board. A hole 604 has been machined into the upper surface of the board 600 and so is to expose the right angle interface body 530 . The outer copper foil layer 510 has also been etched to provide conductive runs. At this time the copper tape 512 on the top of the right angle interface body 530 maybe pealed off and the top surface of the right angle interface body cleaned 530 . The protective copper tape 512 is left on the top surface of the right angle interface body 530 until the board 600 has been electrically tested and finally inspected.
[0041] Referring to FIG. 8 , the first step of assembling the female connector portion is illustrated. An anchor body 822 is securely engaged to the surface of the board 600 by inserting its anchors 824 into the holes 602 drilled in the board 600 .
[0042] Referring to FIG. 9 , a second step of assembling the female connector portion is illustrated. A female self-alignment body 924 is forced downward through the anchor body 822 and into the machined out hole 604 in the board 600 until it aligns with the imbedded right angle alignment body 530 .
[0043] Referring to FIG. 10 , a detail view of the interface between the anchor body 822 and the female self-alignment body 924 is illustrated. The anchor body 822 engages the female self-alignment body 924 via a one way ratchet 926 .
[0044] Referring to FIG. 11 , the fully assembled optical connector 1100 is illustrated in a partial section view. A male self-alignment body 910 is inserted down into the female self-alignment body 920 (formed by the combination of the anchor body 822 and the female self-alignment body 924 ) to guide the male connected portion into precise registration with the top surface of the right angle alignment body 530 . To insure precision of engagement between the optical paths of the male connector portion 910 with the optical paths of the right angle alignment body 530 . the alignment pins 914 of the male connector portion 910 are engaged with the precision machined holes 538 of the right angle alignment body 530 .
[0045] Referring to FIG. 12 , an electro-optical back plane 1200 according to an embodiment of the present invention is illustrated. The back plane 1200 has an optical carrier 1210 (preferably a fiber management system) embedded with a number of optical connectors 1220 according to embodiments of the present invention. For interfacing printed circuit boards 1230 to the electro-optical back plane 1200 , optical connectors 1220 are placed adjacent to electrical connectors 1222 . The printed circuit boards 1230 are engaged with the electro-optical back plane 1200 using separate fibers 1224 on the board 1230 slotted into the electro optical back plane 1200 via both the electrical connectors 1222 and their corresponding optical connectors 1220 . Purely optical devices 1250 may also be plugged into the back plane 1200 . For example an optical switch 1252 is shown being connected to optical connectors 1220 alone, as is a splitter coupler device 1254 .
[0046] The present invention has been described in terms of preferred embodiments, however, it will be appreciated that various modifications and improvements may be made to the described embodiments without departing from the scope of the invention. | A circuit board uses both electrical and optical connectors to carry signals in both electrical and light form. The optical connector employs redundant alignment features to provide for reliable connectivity between plug in boards and the electro-optic back plane. A process is of forming the back plane and other multilevel circuit boards so as to embed optical connectors is disclosed. | 6 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to simulating moving lights using nonmoving lights.
2. Related Art
In the art of lighted displays, it is often desired to present a cartoon or picture which gives an impression of motion. When the display itself is stationary (and the lights in the display are themselves stationary), this poses a problem because the impression of motion is necessarily an illusion, and it can be difficult to present an adequate illusion. This problem can be acute where it is desired to give the impression of smooth motion, and particularly when using only a relatively inexpensive display having only a few lights.
One method which is known in the art is to present a sequence of cartoons or pictures, each of which represents a separate still picture in a moving sequence. For example, a moving arrow can be simulated using several still pictures of an arrow. While this method can achieve the illusion of motion, the impression which is given will often be jerky or rough, particularly with a relatively inexpensive display, due to the granular limitation of having only a few lights per foot.
The following patents are examples of the art:
U.S. Pat. No. 3,737,722, "Method And Apparatus For Forming Spatial Light Patterns", issued Jun. 5, 1973, in the name of inventor Meyer J. Scharlack.
U.S. Pat. No. 4,161,018, "Lighted Ornamental Devices", issued Jul. 10, 1979, in the name of inventors James B. Briggs, et al.
U.S. Pat. No. 4,231,079, "Article Of Wearing Apparel", issued Oct. 28, 1980, in the name of inventor Stephen R. Heminover.
U.S. Pat. No. 4,860,177, "Bicycle Safety Light", issued Aug. 22, 1989, in the name of inventors John B. Simms, et al.
U.S. Pat. No. 5,081,568, "Traffic Police Baton With Means To Indicate The Direction In The Night", issued Jan. 14, 1992, in the name of inventors Lu J. Dong, et al.
U.S. Pat. No. 5,327,329, "Lighting Attachments For In-Line Roller or Blade Skates", issued Jul. 5, 1994, in the name of inventor David L. Stiles.
U.S. Pat. No. 5,416,675, "Illuminated Helmet", issued May 16, 1995, in the name of inventor Robert J. DeBeaux.
U.S. Pat. No. 5,438,488, "Illuminated Article of Apparel", issued Aug. 1, 1995, in the name of inventor Larry Dion, and assigned to LaMi Products, Inc.
U.S. Pat. No. 5,457,612, "Bicycle Rear Lighting System", issued Oct. 10, 1995, in the name of inventor Scot Carter.
U.S. Pat. No. 5,544,027, "LED Display For Protective Helmet And Helmet Containing Same", issued Aug. 6, 1996, in the name of inventor Anthony Orsano.
Accordingly, it would be desirable to provide a method and system for providing an illusion of relatively smooth motion in a lighted display, with only a relatively rough granularity and only a relatively small number of lights. This advantage is achieved in an embodiment of the invention in which much smaller degrees of motion are simulated by simulating lights which appear to be partly on and partly off.
SUMMARY OF THE INVENTION
The invention provides a method and system for simulating moving lights using nonmoving lights. A row or column of lights, such as LCDs or LEDs, are each controlled by a processor so as to switch each light at a relatively rapid rate, sufficiently rapid so that the light appears on but at only partial brightness. The apparent intensity for each light is controlled by the processor by controlling the duty cycle of each light. This allows the processor to present an illusion of fade-in at a leading edge of a picture element, and to present an illusion of fade-out at a trailing edge of the picture element.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a block diagram of a system for simulating moving lights.
FIG. 2 shows a timing diagram of a set of waveforms in the system.
FIG. 3 shows a display using nonmoving light elements to simulate a moving light.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
In the following description, a preferred embodiment of the invention is described with regard to preferred process steps and data structures. Those skilled in the art would recognize after perusal of this application that embodiments of the invention can be implemented using one or more general purpose processors operating under program control, or special purpose processors adapted to particular process steps and data structures, and that implementation of the process steps and data structures described herein would not require undue experimentation or further invention.
FIG. 1 shows a block diagram of a system for simulating moving lights.
A system 100 includes a base 101 and a plurality of light elements 110, each of which is affixed to the base 101 and is fixed relative to the system 100 itself. The light elements 110 are disposed in at least one line 120, such as a sequence of rows or columns.
In a preferred embodiment, the light elements 110 are light-emitting diodes (LEDs), but in alternative embodiments, the light elements 110 may be liquid crystal diodes which are backlit and which pass, block, or reflect illumination, or may be incandescent or flourescent lights. As described herein, the invention is not limited to any particular type of light element, so long as the light can be controlled as described herein.
In a preferred embodiment, the light elements 110 are disposed in a plurality of lines 120, each of which comprises a column in a form representing a clock in the shape of an abacus. The abacus includes one line 120 forming a column for each digit of a clock display, thus preferably including two columns for an hourly value 141, two columns for a minutes value 142, and two columns for a seconds value 143. Each column includes at least one light element 110 for each of a set of four "ones" beads, plus at least two light elements 110 representing spaces for "ones" beads to be moved to, and at least one light element 110 for a "fives" bead, plus at least two light elements 110 representing spaces for the "fives" bead to be moved to.
Each light element 110 is independently coupled to a processor 150, which operates under software control to turn each light element 110 on and off. However, in an alternative embodiment, the processor 150 may be replaced with circuits whose special purpose is to control each light element 110 as described herein with regard to control by the processor 150.
Power (not shown) is independently supplied to each light element 110 and provides for each light element 110 to emit light (or reflect or transmit light, as appropriate) as controlled by the processor 150.
FIG. 2 shows a timing diagram of a set of waveforms in the system.
A first waveform 210 represents a light in a partially "on" state. The first waveform 210 is a periodic waveform, such as a square wave, having a light-on voltage 21l representing a light-on state 214 and a light-off voltage 213 representing a light-off state 212. For example, the light-on voltage 211 can be +5.0 volts relative to ground and the light-off voltage 213 can be +0.0 volts relative to ground.
The first waveform 210 has a frequency which is high enough that the human eye is unable to distinguish individual transitions of the first waveform 210 between the light-on state 214 and the light-off state 212, and has a period 215 which is the inverse of its frequency. For example, in a preferred embodiment, the frequency of the first waveform 210 can be about 50 times per second, so the period 215 of the first waveform 210 is thus about 20 milliseconds.
Each period 215 includes one light-on state 214 and one light-off state 212. Within each period 215 the light-on state 214 is a selected fraction of the total period 215, called herein the "duty cycle" of the first waveform 210. For example, if the light-on state 214 is half the total period 215 (so that the light is therefore "on" half of each period 215), the duty cycle of the first waveform 210 is 1/2 or 50%.
A second waveform 220 represents a light in a substantially fully "on" state. It is identical to the first waveform 210 except that it has a duty cycle of about 95%.
A third waveform 230 represents a light in a substantially fully "off" state. It is identical to the first waveform 210 except that it has a duty cycle of about 5%.
FIG. 3 shows a display using nonmoving light elements to simulate a moving light.
A set of light elements 110 in a line 120 at a first time includes a primary "on" light 301, comprising a light element 110 in a substantially fully on state having a duty cycle near 100%, and a set of "off" lights 302, comprising light elements in substantially fully off states having duty cycles near 0%.
The processor 150 generates the primary light 301 by controlling the duty cycle of the selected light element 110. The processor 150 also controls the duty cycle of all other light elements 110, and so effectively generates the "off" lights 302 as well.
The processor 150 can control the duty cycles of the selected light elements 110 directly, such as by transmitting a (separate) waveform for turning each light element 110 on and off directly thereto. The processor can also control the duty cycles of the selected light elements 110 indirectly, such as by transmitting a numeric value to a counter or other controller, which generates and transmits the (separate) waveform for turning each light element 110 on and off directly to the light element 110 itself. In the second case, the counter preferably includes a 7497 rate multiplier chip. In either case, the processor 150 has control over whether each light element 110 is fully on, fully off, or partially on.
The human eye integrates the amount of light it receives from any given point using a relatively long time constant. The apparent intensity of any light element 110 depends on the duty cycle which is assigned to that light element 110, so any light element can be made to appear bright, such as by controlling it to have a duty cycle near 100%, to appear dim, such as by controlling it to have a duty cycle near 0%, or to appear to have any selected degree of partial brightness, such as by controlling it to have a selected duty cycle corresponding to that selected degree of partial brightness.
To simulate a moving light, at a set time, the processor 150 gradually alters the duty cycle of the primary light 301 and the "off" lights 302 in a sequence of steps. In this example, the simulated moving light moves rightward in the figure, but there is no particular requirement that the moving Light must move rightward; it can also move leftward, or up or down if the line 120 of light elements 110 permits.
At a time t0, the primary light 301 is fully on and the "off" lights 302 are fully off. The processor 150 gradually alters the duty cycle of the primary light 301 and selected other light elements 110 to achieve the status shown for the time t1.
At a time t1, the light element 110 for the primary light 301 is only partially on and appears dimmer than did the primary light 301, while the light element 110 to the right of the primary light 301 is also partially on. The two selected light elements comprise secondary lights 303; the total light emitted by the two secondary lights 303 is equal to that originally emitted by the primary light 301. The processor 150 gradually alters the duty cycle of the secondary lights 303 and selected other light elements 110 to achieve the status shown for the time t2.
At a time t2, the light element 110 for the leftmost secondary light 303 is substantially fully off and appears off, while the light element 110 to the right of the rightmost secondary light is partially on. The two secondary lights 303 thus appear to have moved to the right, but the total light emitted by the two secondary lights 303 is still equal to that originally emitted by the primary light 301. The processor 150 gradually alters the duty cycle of the secondary lights 303 and selected other light elements 110 to achieve the status shown for the time t3.
At a time t3, the light element 110 for the leftmost secondary light 303 is substantially fully off and appears off, while the light element 110 for the rightmost secondary light 303 is substantially fully on and now comprises a primary light 301. Thus, the primary light 301 appears to have moved to the right along the path 304.
Other and further patterns of primary lights 301 and secondary lights 302 can be used to present the illusion of moving lights. In one alternative process, the following steps occur: The "off" light 302 directly to the right of the primary light 301 is gradually increased in duty cycle from 0% to 100% (thus becoming a secondary light 303) as the primary light 301 is gradually decreased in duty cycle from 100% to 0% (thus also becoming a secondary light 303). When any secondary light 303 increases to 40% duty cycle, the next light element 110 is also gradually increased from 0% to 100%, and so on. When any secondary light 303 decreases to 60% duty cycle, the next light element 110 decreases is also gradually decreased from 100% to 0%, and so on.
The processor 150 can gradually alter the duty cycles of selected light elements 110 by changing the duty cycles of those light elements 110 by a small amount for a small amount of time, then again altering those duty cycles by another small amount for another small amount of time, and so on until the transition is complete. In a preferred embodiment, the small amount of duty cycle is about 20% and the small amount of time is about 100 milliseconds.
During the transition time it thus occurs that the processor 150 causes the "next" light element 110 to become gradually brighter, while causing the "last" light element 110 to become gradually dimmer.
Alternative Embodiments
Although preferred embodiments are disclosed herein, many variations are possible which remain within the concept, scope, and spirit of the invention, and these variations would become clear to those skilled in the art after perusal of this application.
For example, the invention is equally applicable to moving lights showing picture elements in two dimensions as well as one dimension, thus moving in an array of light elements and possibly not along lines defined by the the array. | The invention provides a method and system for simulating moving lights using nonmoving lights. A row or column of lights, such as LCDs or LEDs, are each controlled by a processor so as to switch each light at a relatively rapid rate, sufficiently rapid so that the light appears on but at only partial brightness. The apparent intensity for each light is controlled by the processor by controlling the duty cycle of each light. This allows the processor to present an illusion of fade-in at a leading edge of a picture element, and to present an illusion of fade-out at a trailing edge of the picture element. | 8 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to robotic end effectors, and more particularly, to a relatively small, lightweight, end effector having a pair of gripping fingers which are suitable for engaging, retaining and releasing a plurality of tools and components.
2. Discussion of the Relevant Art
The art abounds with end effectors utilized in combination with robots to perform a plurality of operations in automatic production lines. Numerous types of end effectors, each designed for a specific function, are in use today. The automatic production lines require numerous robots each performing their function in sequence so that the item being manufactured moves through numerous stations, each station adding a component or performing an operation on the article being manufactured until the article reaches the end of the production line where it is then tested and packaged for shipment.
In order to improve the versatility of the end effectors numerous designs have been attempted which have as a design goal providing three degrees of freedom to the end effector and robotic arm combination permitting manipulations similar to that accomplished by a human arm and hand. Typical of an end effector having force sensors in each finger together with a system providing three degrees of freedom force sensors on each finger utilizing strain gages to measure forces on the fingers as it contacts an article is disclosed in U.S. Pat. No. 4,132,318 issued to S. S. Wang, et al on Jan. 2, 1979. The device disclosed therein is capable of measuring the gripping force and a force vector applied to the object being held by a manipulator finger of the end effector. The end effector disclosed therein is computer controlled and utilizes the strain gages and offset forces to direct the fingers of the end effector to accomplish the desired goal. The type of functions that can be performed with this type of end effector are limited.
In U.S. Pat. No. 3,905,632 issued to H. J. Caylor, et al on Sept. 16, 1975 a gripping head apparatus is disclosed that is designed to be attached to the free end of a lifting boom structure which is configured to grip, position, empty and release containers wherein the head comprises a pair of movably mounted lifting arms arranged in opposed alignment in relation to one another. A rack and pinion arrangement is used to rotate the position of the container once it is picked up by the end effector. The device disclosed herein is utilized for the singular purpose of raising a container, moving it to a new position and then tilting it so the contents thereof can be emptied. The apparatus is designed for use with relatively large containers and would be unsuitable for handling the manipulation of small devices or performing specific functions on relatively small components.
Another mechanism utilized as an end effector on a robotic arm suitable for gripping rigid products is disclosed in U.S. Pat. No. 3,655,232 issued to G. A. Martelee on Apr. 11, 1972. The embodiment disclosed therein utilizes a horizontal ram and from which are suspended hollow vertical telescoping grasping arms each housing a vertical cylindrical ram connected to a compressed oil accumulator that supplies oil to the horizontal ram and to a rotating ram about the vertical suspension pivot. Here again, the device utilizes rack and pinion arrangements which are not suitable for the manipulative functions of which the instant invention is capable.
The apparatus disclosed in the instant invention overcomes the shortcomings found in the prior art by providing an end effector suitable for use on the distal end of a robotic arm capable of performing numerous functions and is capable of engaging and releasing numerous tool elements to aid in performing a plurality of functions while maintaining its small size and weight.
Therefore, it is the object of the present invention to provide a robotic end effector that is relatively small in size, reliable and suitable for performing numerous functions.
It is yet another object of the present invention to provide a robotic end effector suitable for mounting on a plurality of robotic arms.
It is still yet another object of the present invention to provide a robotic end effector that is small in size and provides a relatively large gripper dimension.
It is still yet another object of the present invention to provide a robotic end effector that is capable of bi-directional linear motion suitable for engaging the outer dimension of objects in addition to the inner dimension thereof.
It is still yet another object of the present invention to provide a robotic end effector suitable of engaging and exchanging numerous tool elements.
It is still yet another object of the present invention to provide a robotic end effector that is capable of automatically changing and replacing tool elements and is capable of performing numerous functions.
It is still yet another object of the present invention to provide a robotic end effector capable of sensing when the object it is to engage is in the correct position for engagement thereof.
It is still yet another object of the present invention to provide a sensing arrangement for the robotic end effector providing information to the control computer for the robot that the end effector has moved to a prescribed position and is ready to perform its function.
SUMMARY OF THE INVENTION
An end effector suitable for use on a robotic arm coupled to a central computer capable of providing an electronic command signal and a power source associated therewith, according to the principles of the present invention, comprises in combination; attachment means for removably affixing the end effector to the distal end of the robotic arm; a gripper apparatus which includes a pair of finger members slideably retained within the end effector, the the finger members are adapted to be coupled to a power source and cooperate with and removably retain and release a plurality of end effector tools and components upon receiving an electronic command signal; and computer means for generating the command signal, the command signal being coupled to the finger members for controlling the application of driving power from a power source.
The foregoing and other objects and advantages will appear from the description to follow. In the description reference is made to the accompanying drawing which forms a part hereof, and on which is shown by way of illustration a specific embodiment in which the invention may be practiced. The embodiment will be described in sufficient detail to enable those skilled in the art to practice the invention and it is to be understood that other embodiments may be utilized and that structural changes may be made without departing from the scope of the invention. The following detailed description is, therefore, not to be taken in a limiting sense, and the scope of the present invention is best defined by the appended claims.
BRIEF DESCRIPTION OF THE DRAWING
In order that the invention may be more fully understood, it will now be described by way of example, with reference to the accompanying drawing in which:
FIG. 1 is a front view in elevation of a robotic end effector, according to the principles of the present invention;
FIG. 1A is a pictorial representation of a control computer coupled to a robot having a robotic arm with an end effector disposed on the distal end thereof;
FIG. 2 is an end view in elevation of the robotic end effector shown in FIG. 1;
FIG. 3 is an isometric view, partially broken away, of the robotic end effector shown in FIG. 1;
FIG. 4 is a view in elevation, partially broken away, of the end effector shown in FIG. 3;
FIG. 5 is a cross-section view in elevation of the end effector with portions broken away, in order to more clearly point out the features of the instant invention;
FIG. 6 is a partial top plan view of the pinion and rack gear arrangement shown in FIG. 5;
FIG. 7 is a front view in elevation showing the engaging pins of a typical tool; and
FIG. 8 is a side view in elevation of the tool shown in FIG. 7.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to the figures, and in particular, to FIGS. 1 and 2, there is shown a front view in elevation and a side view in elevation of an end effector 10, according to the principles of the present invention. The upper portion 12 of the housing 14 of the end effector 10 is provided with a reinforced portion 16 that is provided with threaded apertures 18, 20, 22, and 24 provided therein which are adapted to receive threaded bolts 26, 28, 30 and 32 used to affix a universal mounting plate 34 to the reinforced portion 16 of the end effector 10. The universal mounting plate 34 is provided with through apertures 36, 38, 40 and 42 which are adapted to cooperate with and receive bolts 26, 28, 30 and 32 to enable universal mounting plate 34 to be mounted on end effector 10. Through apertures 44, 46, 48 and 50 provided in universal mounting plate 34 permit the end effector 10 to be affixed to the distal end 159 of different types of robotic arms 163 such, as for example, bolts 26, 28, 30 and 32. Thus, by providing proper mounting holes in the universal plate 34 the end effector 10 may be affixed to known robotic arms or by changing plate 34 the mounting holes can be configured to any desired application.
The end effector 10 is provided with a pair of gripper fingers 52 and 54 that extend outwardly from the hollow housing 14. The hollow housing 14 is generally U-shaped and open on the bottom so that the gripper fingers may freely move in the direction of arrows 56 and 58. Each of the gripper fingers 52 and 54 move linearly inwardly and outwardly (bi-directionally) simultaneously, as will be explained hereinafter.
The open front and rear portions of the housing 14 are provided with covers 60 and 62 which are fastened to the housing by means of screws 64, 66, 68 and 70, in a conventional manner. The upper portion of housing 14 may also include indicator lights 72, 74 and 76 which may be used to indicate that the light emitting device 78 disposed in the distal end of gripper finger 52 which provides an infra-red light beam 80 as received by the photoelectric detector 82 disposed in the distal end of gripper finger 54 has been interrupted by an object being interposed therebetween. In addition to illuminating lamp 72 an electronic signal may be sent to the main computer, not shown, that the object to be captured is in position so that the computer may initiate the proper signal to perform the next function of the end effector. Indicator light 74 may be utilized to indicate when a tool has been engaged and is in position as well as provide the necessary signal to the main computer to initiate the next function. In a similar manner, indicator light 76 is illuminated to indicate that the component part has been captured by the tool as will be explained hereinafter, also providing information to the main computer that the end effector 10 is available for its succeeding function.
Preferably, the finger grippers 52 and 54 are covered with resilient boot members 84 and 86 that are provided with a plurality of protrusions 88 and 90, respectively, that increase the surface friction so that the fingers may more readily grip and retain a component or article which it attempts to capture. Apertures 92 and 94 are provided in the boot members 84 and 86, respectively, to prevent interference with the infra-red rays emanating from the light emitting device 78 to the photoelectric detector 82. Gripper fingers 54 and 52 are each provided with elongated through apertures 96, 98, 100 and 102 proximate the distal end thereof, the function of which will become apparent in the description which follows.
Referring now to FIG. 3, which is an isometric view, partially broken away, of the embodiment disclosed in FIGS. 1 and 2. The generally U-shaped housing 14, with its upper portion 12 being closed (inverted U) has centrally disposed a longitudinally disposed shaft 104 which when shown in cross-section resembles an I-beam with the lower portion 106 thereof being slightly larger in size than the upper portion 108. Shaft 104 is held in position by screws 110 and 112 in one arm portion 118 (FIG. 1) of the housing 14 while the other end is held in position by screws 114 and 116 inserted through apertures provided in the other arm portion 120 of housing 14 (see FIGS. 1, 2, 3 and 4). Preferably, shaft 104 is centrally disposed in the housing 14 and also provides structural reinforcement. Centrally disposed in the shaft 104 is a pinion gear 122 which has its axis perpendicular to the axis of shaft 104 and rotates in a plane parallel to the upper and lower portions 106 and 108 of I-beam 104. Pinion gear 122 may be installed with a free wheeling bushing 123 in order to provide minimum frictional losses during rotation thereof. The upper portion 124 of gripper finger 54 is disposed transverse to the axis of shaft 104 and has two apertures 126 and 128 provided proximate the outwardly extending arms thereof into which are mounted circulating ball bushings 130 and 132. Ball bushings such as that manufactured by the Heim Corporation of the State of Connecticut, Model number 887X 250SS which is adapted to receive guide shafts 134 and 136 therein, respectively. Thus, gripper finger 54 may freely slide along and be guided by shafts 134 and 136.
Extending upwardly from the transverse upper portion 124 is a shelf portion 138 upon which a pneumatic double acting cylinder 140 is mounted by means of two pairs of screws 142 and 144 that engage the housing portion 146 of the cylinder 140 thereby affixing the housing of the cylinder with respect to finger 54. A typical cylinder suitable for this application is manufactured by Compact Air Products of Westminster, S.C., Model No. BD118X2-EXD12118. The cylinder 140, being of the double acting type is provided with a centrally disposed rod 148 which extends outwardly from either end of the cylinder and is provided with a central bore on both ends adapted to receive screws 150 and 152 (FIG. 1), which extend through the arm portions 118 and 120 (FIG. 4) of the housing 14 thereby affixing the rod with respect thereto. Thus, it can be seen that by activation of the double acting cylinder 140 the housing 146 thereof can be moved from one end to the other of the rod while the rod remains stationary. Activation or movement of the housing 146 is accomplished by the application of a fluid under pressure, e.g., compressed air, entering, via input nozzle 154 or 156. Input nozzles 154 and 156 are coupled, via a flexible hose 158 and 160, respectively, to a source of compressed air, not shown, the direction of which is electronically controlled by a signal from the central computer 161 coupled to the robot 163, via cabling 165 shown in FIG. 1.
The shelf portion 138 of gripper finger 54 is additionally provided with an upwardly extending portion 162 which is provided with an aperture 164 into which is mounted a circulating ball bushing 166 adapted to receive a guide shaft 168 therein which is affixed to the arm portions 118 and 120 of housing 14 by means of two screws 170 and 172 in a manner similar to that utilized for guide shafts 134 and 136.
A rack gear 174, shown most clearly in FIGS. 4 and 5 is in cooperative contact with pinion gear 122 and is affixed to upwardly extending portion 162 beneath the shelf portion 138 of gripper finger 54 by means of five (5) screws 176, 178, 180, 182 and 184, as is best shown in FIGS. 4, 5 and 6. Screws 176, 180 and 184 are of the shoulder type and are threaded into rack 174 and are inserted through a clearance hole 185 (see FIG. 6). Screws 178 and 182 are set screws which are threaded into aperture 188 provided in the upwardly extending portion 162 of gripper finger 54. Set screw 178 may be provided with a resilient tip, such as nylon. By utilizing the shoulder screws together with the set screws a blind alignment may be accomplished and rack 174 may be aligned to cooperate with and be in intimate contact with pinion gear 122 with a minimum of resistance forces. Shoulder screw 176, when rotated, is capable of moving the rack away from the pinion gear 122 while set screw 188 may move the rack 174 closer to the pinion gear. By careful adjustment, one is able to align the rack in a position which is parallel to the axis of pinion gear 122 providing free movement therebetween. Thus, by providing movement to rack 174 rotation of pinion gear 122 occurs transferring the radial movement to linear movement in rack 186 which is connected in the identical manner to upwardly extending portion 188 provided on gripper finger 52. By the arrangement set forth herein it becomes obvious, that if rack 174 is to move one inch in the direction of arrow 190 (see FIG. 6) the movement will be coupled, via pinion gear 122 causing rack 186 to move in the direction of arrow 192 an equal amount in the opposite direction. Thus, driving rack 174 which is attached to gripper finger 54 by moving one inch in an outwardly direction will cause gripper finger 52 to move an equal distance in the opposite direction, thereby making the total distance between the gripper fingers 52 and 54 equal to two inches.
Rack 186 is connected to upwardly extending portion 188 of gripper finger 52 with the aid of five (5) screws 194, 196, 198, 200 and 202. Preferably, screws 194, 198 and 202 are shoulder screws with screws 196 and 200 being set screws, all of which function in the identical manner to screws 176, 178, 180, 182 and 184 and control the alignment of rack 186. Shoulder screws 194, 198 and 202 are provided with clearance apertures in the upwardly extending portion 188 while set screws 196 and 200 are provided with threaded apertures in the upwardly extending portion 188 thereby providing identical means for alignment without being able to see the cooperating portions of the rack and pinion gears.
In lieu of a shelf portion, the upwardly extending portion 188 of gripper finger 152 is provided with an upright portion 204 which is provided with an aperture 206 into which is mounted a circulating ball bushing 208 that is adapted to receive a guide shaft 210 therein. Guide shaft 210 extends from one arm of the housing 118 to the other end of the housing 120 and is affixed therein by means of grooves in the identical manner as guide shaft 168. The transverse upper portion 212 of gripper finger 52 is also provided with an aperture into which is mounted a circulating ball bushing 214 thereby permitting gripper finger 52 to move freely along the guide shafts 210 and 134 in a manner similar to that of gripper finger 54 except that movement occurs in the opposite direction as explained earlier. Motion between gripper fingers 52 and 54 is linear in nature and bi-directional.
By comparing the location of the components as disclosed in FIGS. 3 and 4, it can be seen that gripper fingers 52 and 54 extend downwardly out of the housing 12 and are permitted unrestricted movement with gripper finger 54 being the driven element and gripper finger 52 being the slave element.
Referring now to FIG. 5, there is shown in cross-section gripper finger 54 which is generally hollow in nature being provided with an elongated hollow or channel 216 into which is mounted a super-slim cylinder 218 with a rectangular cross-section of the type manufactured by Festo Industries of Hauppauge, N.Y., Model No. 9505EZH2, 5/9-10. A cylinder or alternatively, an electrical solenoid 218 is mounted in the hollow 216 with the aid of two (2) screws 220 and 222 and is provided with a rectangularly-shaped piston rod 224 and is biased by a spring 225, to its normal rest position shown in FIG. 5. Transverse pins 226 and 228, preferably roll pins, are positioned in a normal rest position to be proximate apertures 96, 98, 100 and 102. Thus, when cylinder 218 is activated, (supplied with compressed air into the input nozzle 230 which is coupled, via a flexible hose 232 to the source of compressed air), the piston rod 224 will cause pins 226 and 228 to extend into the area of the apertures 96, 98, 100 and 102. Thus, anything inserted into these apertures would be restrained therein by the force generated by the activating air.
Referring now to FIGS. 7 and 8, which disclose a front and side view, respectively, of a typical end effector tool 234 that may be used in conjunction with the gripper fingers 52 and 54, if it is desired to pickup a circularly-shaped object for example. As shown in the figures the end effector tool 234 includes outwardly extending protrusions 236, 238, 240 and 242 which are generally rectangularly-shaped in cross-section and are provided with the grooves 244, 246, 248 and 250, respectively, in each of the protrusions. The protrusions are selected to mate with the apertures 96, 98, 100 and 102 provided in the gripper fingers 52 and 54 and are capable of being inserted on the outwardly extending surface or the inwardly extending surface of the gripper fingers. Once inserted in the apertures, activation of the cylinder 218 causes piston rod 224 to move into V-grooves 244, 246, 248 and 250 causing the end effector tool 234 to be locked into position. This is accomplished by a signal from a master control computer 161 causing the cylinder 218 to be activated at the appropriate time. The tool 234 is, therefore, locked in place until fluid pressure is removed from cylinder 218. The V-grooves provide almost perfect alignment and maintain the integrity and accuracy of the gripper fingers 52 and 54. It is to be noted that although a typical tool is shown herein, any number of tools may be utilized together with gripper fingers 52 and 54.
Typical end effector tools of various types are disclosed in co-pending U.S. application Ser. No. 591,265, filed Mar. 19, 1985 by Mathew L. Monforte and co-pending U.S. application Ser. No. 610,032, filed May 14, 1985 by Mathew L. Monforte and may be utilized in an automatic production line wherein the subject robotic end effector may be used.
In operation, the robotic end effector 10 receives compressed fluid, preferably air, from a fluid source under pressure. The air flow is controlled by the master computer and an electronic signal dictates which of the input nozzles 154 or 156 is to receive the compressed fluid. Thus, the directional movement of gripper fingers 52 and 54 is determined with fluid under pressure being applied to one nozzle to cause movement of the gripper fingers in an inwardly direction, while compressed fluid being applied to the other nozzle causes the gripper fingers to move in an outwardly direction. Engaging or releasing various end effector tools is accomplished by causing the robotic arm to move the end effector to a prescribed location wherein the gripper fingers are caused to engage various end effector tools located in specific coordinates. Once the tools have been located and engaged, energizing cylinder 218 by means of a signal from the central control computer will lock the tool in position wherein the robotic arm then moves it to perform any number of functions.
The end effector tool disclosed herein utilizes a base portion 252 and a resilient portion 254 which is provided with a curved outer surface 256 ideally suited to engage a round object. By utilizing the infra-red light source 78 together with the photoelectric detector 82 the central computer can be notified when the object to be engaged interrupts the light beam occurring between gripper fingers 52 and 54. Thus, the computer can indicate and instruct the gripper fingers to close and engage the object as required, and once retained, the computer can move the robotic arm to its required position, in a conventional manner.
Hereinbefore has been disclosed a relatively simple end effector which is reliable, small in size, having a relatively large gripping dimension for its size and is ideally suitable for use on a plurality of robotic arms. It will be understood that various changes in the details, materials, arrangement of parts and operating conditions which have been herein described and illustrated in order to explain the nature of the invention may be made by those skilled in the art within the principles and scope of the instant invention. | An end effector suitable for use on a robotic arm associated therewith and coupled to a computer includes a universal mounting plate permitting the end effector to be mounted on the distal end of a robotic arm; a gripper mechanism slideably retained within the end effector is responsive to electronic command signals permitting the finger members disposed therein to cooperate with and removably retain a plurality of tools and components upon receiving computer controlled electronic command signal. The electronic command signal controls the driving power from a power source which is coupled to the end effector. | 8 |
BACKGROUND O THE INVENTION
The invention is directed to a device for the transport of toner from the transport container into a developer station of a non-mechanical printer or copier means.
In copier technology and in modern fast data printers that operate on the principle of electrophotography, charge images are generated on a recording medium, for example directly on an intermediate carrier (photoconductive drum) or directly on special paper, and are subsequently inked with a black powder (toner) in a developer station. Given employment of an intermediate carrier, this toner image is subsequently transferred onto normal paper and fixed thereon.
As a rule, a two-component developer that is composed of ferromagnetic carrier particles and of the toner particles carrying the color is used. The developer is conducted past the charge image on the intermediate carrier with a magnetic brush arrangement, the toner adhering thereto as a result of electrostatic forces.
An electrophotographic copier means that develops charge images according to the principle addressed above is disclosed, for example, from DE-AS 21 66 667, and corresponding U.S. Pat. Nos. 3,784,297 and 3,883,240.
Due to the inking of the charge images on the intermediate carrier, the toner concentration in the developer mix of the developer station constantly decreases. It is therefore necessary to constantly supply new toner to the developer mix in metered fashion. Since the toner consumption per time unit is extremely high in fast copier means and high-performance data printers, a roomy toner reservoir is used in such apparatus in order to avoid down time caused by refilling toner. When this toner reservoir is empty, the toner that is usually supplied in handy containers is filled into the reservoir. It is thereby important to fill the toner from the container into the reservoir such that no toner is spilled and thereby contaminates the environment.
German Patent 32 24 296 and corresponding U.S. Pat. No. 4,561,759 discloses an apparatus for filling and sieving toner from a container into a toner reservoir. The toner situated in a transport container, namely in a toner bottle, is thereby supplied to a reservoir in that the toner bottle is inverted into a filling aperture of the reservoir. A strainer basket that is closed from the reservoir with a sieve is arranged in the region of the filling aperture, this strainer basket being in communication with an electrical shaker means that can be triggered as needed. The shaker means is thereby triggered by opening the cover that closes the filling aperture
In such filling devices, there is then the risk that the toner will be spilled given manual decanting from the toner bottle. Since, moreover, the toner is only supplied to the toner reservoir at a defined location, special distributor devices are needed in the toner reservoir in order to guarantee a uniform supply of the toner to the developer station.
Xerox Disclosure Journal, Vol,1, No.8, Aug. 1976, page 47, also discloses that toner be supplied to the developer station from a reservoir arranged at a distance therefrom in that air is blown through the reservoir This air then transports the toner into the developer station
JP-A-61-59 465 discloses a toner delivery means wherein toner is suction from a toner container with the assistance of a suction means and a line system and is supplied to the reservoir of a developer station
EP-A-8 270 also discloses that powdery material be suctioned from a container with the assistance of a suction nozzle that is composed of an inside tube and of an outside tube
SUMMARY OF THE INVENTION
It is an object o the invention to fashion a toner container of the species initially cited such that the toner can be delivered to non-mechanical printer or copier means in a simple way without toner being released contaminating the environment.
In a toner container of the species initially cited, this object is achieved by a suction nozzle displaceably arranged in a guide means inside a toner type protective sheath, this suction nozzle being in communication via a platform with the developer station and by an adapter connected o the protective sheath for releasable toner-type fastening to a filling and emptying opening of a toner container. The suction nozzle immerses through the adapter into the toner container for emptying the toner container.
Advantageous embodiments of the invention are provided in that the guide means that accepts the suction nozzle in vertically displaceable fashion is arranged above a holding mechanism for the acceptance of the toner container such that suction nozzle immerses into the toner container on the basis o its dead weight during the a draw-off event.
The holding mechanism is preferably fashioned to be pivotable out of a means for accepting the toner container. The adapter has a safety means for the suction nozzle that, first, enables an immersion of the suction nozzle into the toner transport container only safe the transport container has been connected to the adapter and, second, prevents release of the connection when the suction nozzle is immersed. Preferably, the adapter includes a cuter means for puncturing the foil that covers the filling and removal opening of the toner container in its filled condition. The protective sheath of a preferred embodiment of composed of a flexible accordion bellows that is secured, first, through the connecting region of the suction nozzle and, second, to the adapter. The adapter comprises a toner stripper ring which accepts the suction nozzle.
In a preferred form, the toner container has a funnel-shaped floor that forms a lowest collecting region of the toner, whereby the filling and emptying opening int the collecting region are arranged relative to one another such that given fastening of the toner container of in the holding mechanism in a removal position wherein the collecting region forms that slowest region of the toner container, the suction nozzle allocated o the printer or copier means immerses in the collecting region. The suction nozzle is preferably an inner tube having take in openings and connected to a pipe line and also comprises an outside tube enveloping the inner tube at a distance therefrom, whereby the outside tube has toner entry openings and an air intake opening so that intake air flowing from the outside tube suctions the toner thought the toner entry opening of the inside tube.
In that the toner is removed from the toner container with the assistance of a suction nozzle that is arranged inside a protective sheath that is connected via an adapter to a filling and emptying opening of the toner container, no toner dust can contaminate the environment.
A safety means sees to it that the suction nozzle cannot dip into the toner container for draw-off until a dust-tight connection between the filling and emptying opening of the toner container and the adapter is established. The same safety mechanism also prevents a release of the closure when the suction nozzle is immersed.
The toner containers are delivered with a sealed filling and emptying opening in an advantageous way. The adapter is thereby fashioned such that the adapter does not penetrate the sealing foil via a cutter means until the toner container is connected to the adapter. It is thus not possible to spill toner when inserting the toner container into the corresponding receptacle device in the printer means.
In an advantageous embodiment of the invention, the changing of the toner container is facilitated in that the container that accepts the toner container is fashioned pivotable out of the printer.
The special shape of the toner container comprising a funnel-shaped floor enables the complete emptying of the toner container with the assistance of the vertically displaceable suction nozzle.
The suction nozzle that comprises delivery openings for toner at its tip is composed of an inside tube and of an outside tube that completely envelopes the inside tube. The air taken in via air intake openings of the draw-in tube initially flows through the outside tube and then flows through the inside tube. Via toner delivery openings in the take-in region of the outside tube, the toner is entrained into the inside tube by the air stream.
The toner container can thus be completely emptied without special aeration openings.
BRIEF DESCRIPTION OF THE DRAWINGS
Embodiments of the invention are shown in the drawings and shall be set forth in greater detail below by way of example. Shown are:
FIG. 1 is a schematic illustration of the toner container;
FIG. 2 is a schematic sectional view of the toner container;
FIG. 3 is a schematic illustration of the toner delivery region of a printer means with an inserted, filled toner bottle before connection to the draw-off device;
FIG. 4 is a schematic sectional view of the toner delivery region of the printer means, partially in sectional illustration with a nearly completely emptied toner container;
FIGS. 5a and 5b is a sectional view of the safety mechanism for the suction nozzle in its, secured condition;
FIGS. 6a and 6b is a sectional view of the safety mechanism for the suction nozzle in its unsecured condition;
FIG. 7 is a schematic sectional view of the adapter region of the draw-off means; and
FIG. 8 is a schematic view of the emptying region of the printer means with inserted toner container as collecting container.
DESCRIPTION OF THE PREFERRED EMBODIMENT
A printer means that operates based on the electrophotographic principle and that is not shown in detail here contains a toner delivery region (FIG. 3) for the acceptance of a toner container 10 manufactured of plastic and having an appertaining draw-off means via which the powdery toner 11 is supplied to a developer station (not shown here) of the printer means. An emptying region (FIG. 8) is also provided in the printer means, an empty toner container 10 as a collecting container for the developer mix being capable of being secured therein when emptying the developer station.
In a known way, a charge image is inked with toner in the developer station of the printer means via a two-component developer mix composed of toner and carrier particles. This developer mix, on one hand, must be refreshed from time to time by adding toner; and on the other hand, it is necessary after a longer operating time to replace the entire developer mix.
The toner container 10 is designed for the acceptance of about 3 kg of toner powder. Its container walls thereby form planar surface, whereby one surface 12 is designed as a supporting surface. The upper wall surfaces of the toner container form a cuboid having parallel surfaces, this enabling a space-saving stacking of the toner containers. A handle 13 is thereby arranged such integrated into the wall surfaces that, first, easy carrying of the toner container 10 is enabled and, second, a stacking of a plurality of toner containers is not impeded. Adjoining the supporting surface 13, the container walls 12/5 and 12/6 together with the container wall 12/1 and the supporting surface 12 form a funnel-shaped collecting region for the toner. A filling and emptying opening 14 is situated lying opposite this collecting region and can be closed with a cover 16 having an insert 9 of expanded material and that is captively secured via a clip 15.
After being filled with toner powder 11, the opening 11 itself is sealed with an aluminum foil 17.
The collecting region and filling and emptying opening 14 are arranged such relative to one another that, according to FIG. 1, the suction nozzle 18 introduced from above into the toner container penetrates up to the collecting region after a corresponding draw-off of the toner powder.
In this characteristic removal position shown in FIG. 1, the collecting region forms the lowest point of the toner container. With reference to the vertical axis A of the introduction or, respectively, removal position of the toner container, the walls thereby describe an angle B that amounts to less than 45°.
This means that all walls in the illustrated emptying position of FIG. 1 have a slant relative to the vertical axis A that prevents the toner from adhering to the walls of the container given removal with the suction nozzle 18 in combination with a beater/shaker means. During emptying, the toner collects in the collecting region formed by the walls 12/5 and 12/6 or, respectively, 12 and 12/1 that forms the lowest location of the container and can be completely drawn off from there.
In order to be able to supply the toner from the toner container 10 to the developer station in functionally reliable fashion without contaminating the environment, the toner delivery region comprises a draw-off means for the toner and comprises a corresponding holding mechanism for the toner container 10.
The draw-off means is thereby composed of the suction nozzle 18 arranged in vertically displaceable fashion between guide rods 19, this suction nozzle 18 being in communication via a flexible suction pipe 20 with a blower of the printer that is not shown here. The blower suctions the toner out of the toner container 10 via the suction nozzle and deposits it in the developer station.
According to FIG. 4, the suction nozzle 18 comprises an inside tube 21 cut wedge-like at its bottom end that is in communication with the flexible suction tube 20 and comprises draw-in openings 22 for the toner. The inside tube 21 is completely surrounded by an outside tube 23 arranged at a distance therefrom that, first, comprises an air intake opening 24 at its upper part that opens into the environment and, second, comprises toner entry openings 25 at its tip in the take-in region. The spacing and the guidance of the inside tube 21 are effected by spacer elements (not shown here) that, for example, can be composed of three strips of expanded cellular material uniformly distributed over the circumference.
In order to keep lumpy toner residues away from the delivery to the printer station, the toner entry openings 25 can be covered by a toner sieve that covers the take-in region of the suction nozzle.
The suction nozzle itself is arranged in vertically displaceable fashion via a handle 26. Carrier elements 27 are provided to this end that guide the suction nozzle between the guide rods 19. In order to protect the suction nozzle and in order to prevent an emergence of toner into the environment, the suction nozzle 18 is surrounded by a sheath in the form of a rubber accordion bellows 28. This sheath 28 is secured to the carrier elements 27 at the top and bottom, whereby the lower carrier element 27 is fashioned as an adapter for connecting the toner container 10 and as a lower guide for the suction nozzle 18. The adapter is thereby stationarily arranged and contains an annular stripper ring 29 (FIG. 7) for stripping toner residues from the suction nozzle 18; further, a safety means fashioned according to FIGS. 5a, 5b, 6a and 6b is also provided, this to be set forth later. The actual connector part for the toner container is composed of a sealing ring 30 of expanded cellular material for the filling and emptying opening and of a cutting ring 31 that has the job of cutting through the foil 17 when the toner container 10 is introduced.
Further, the receptacle means contains a receptacle container 32 for the toner container that comprises two wall surfaces between which retaining rods 33 for the toner container are arranged. The receptacle container 32 is pivotably secured to a rotary hinge 34, wherewith the receptacle container 32 can be pivoted out of the interior of the receptacle region (device compartment) of the printer.
The receptacle container 32 is also vertically pivotable around the fastening axis 35 at the rotary hinge 34 and comprising a clamp mechanism 36 that interacts with a corresponding hook 37 at the adapter of the draw-off devices.
According to FIGS. 5a, 5b, 6a and 6b, a catch nose 38 is located in a side wall of the receptacle container 32, this catch nose 38 interacting with a corresponding pin 39 of a lifter rod 40 that is resiliently seated in the adapter. The lifter rod 40 seated in the adapter is in communication via a toggle lever 14 with a retaining pin 42 secured therein. A spring 43 encircles the lifter rod 40.
The function of the described apparatus is then as follows: the toner container 10 comprising foil seal 17 and hinged-open cover 16 is swivelled into the inside of the receptacle region of the printer in the receptacle container 30, being swivelled via the rotary hinge 34. By turning around the fastening axis 35, a clamp mechanism 36 brings the toner container 10 arranged in the receptacle container 32 into engagement with the adapter. Before, however, the neck 44 of the toner bottle engages into the sealing ring 30 of expanded cellular material, a circular sector of about 340° is cut into the foil seal by the cutting ring 31.
When the neck 44 of the toner bottle engages into the sealing ring 30 of expanded cellular material, the safety mechanism of FIGS. 5a, 5b, 6a and 6b releases the suction nozzle 18. The suction nozzle 18 is fixed by a retaining pin 42 that is connected to the toggle mechanism 41. Due to the swivel motion of the receptacle container 32 around the fastening axis 35, the pin 39 on the lifter rod 40 enters into engagement with the catch nose 38 arranged on the receptacle container and having an appertaining leading bevel. The lifter rod 40 is lifted and the retaining pin 42 moved by the toggle lever 41 releases the suction nozzle 18. As a result of its dead weight, the suction nozzle 18 penetrates into the toner container 10 and thereby presses the slit foil seal 17 that is connected only at a tongue into the interior of the bottle where the actual toner delivery can now begin. The catch nose 38 prevents the receptacle container 32 from being swivelled away when the suction nozzle 18 is introduced.
After the conclusion of the conveying event, i.e. when the toner container 10 is changed, the suction nozzle 18 is drawn from the toner container 10 with the handle 26. The toner adhering to the suction nozzle 18 is removed by the stripper ring 29 when the suction nozzle 18 is withdrawn and falls back into the inside of the bottle. The rubber bellows 28 covers the suction nozzle 18 that may still be slightly contaminated and thus offers protection against accidental contact.
Upon compression of the rubber bellows 28, i.e. given penetration into the toner bottle 10, a pressure equalization takes place through a bore 45.
When the suction nozzle 18 has been entirely withdrawn from the toner bottle 10, the compression spring 43 can press the lifter rod 40 in downward direction and thereby inhibit the suction nozzle 18 with the retaining pin 42. At the same time, the pin 39 that interacts with the catch nose 38 is released and the receptacle container 32 together with the toner container 10 can be swivelled away.
In order to assure a reliable delivery of the toner 11 into the draw-off region of the suction nozzle 18 when the suction nozzle is introduced, a shaker means can be provided (FIG. 4) in the receptacle region, this shaker means, for example, being composed of a beater hammer 46 that is swivelably arranged in the receptacle means and that can be deflected via an electromagnet 48 opposite a spring power 47. This beater hammer 46 thereby forms a type of shaker means that strips toner that may still be potentially adhering to the inside walls of the toner container 10.
Given printer means operating according to the principle of electrophotography, the residual toner remaining on the photoconductive drum after the transfer event must be conveyed away from the photoconductive drum by a brush cleaning station applied to an underpressure and must be deposited in a collecting container by a cyclonic filter.
According to FIG. 8, an empty toner container 10 can serve as collecting container for this residual toner. To this end, an empty toner container is inserted into a holding container 49 that comprises a wedge-shaped insert 50 in its bottom region, this insert 50 being shaped to correspond with the bottom supporting surface 12 of the toner container 10. Via appropriate clamp mechanisms 51 and 52, the holding container 49 together with the empty toner container 10 arranged therein can be secured to the hook 53 of the exit pipe 54 of the cyclonic filter (not shown here). Although other modifications and changes may e suggested by those skilled in the art, it is the intention o the inventors to embody within the apparent warranted hereon all changes and modifications as reasonably and properly come within the scope of their contribution to the art. | In a toner transfer system of a printer or copier, a suction nozzle inside a toner-tight protective sheath is arranged in verticallly displaceable fashion in a guide in the printer or copier, this suction nozzle being in communication via a pipe line with a developer station of the printer or copier. At it slower end, the guide has an adaptor for connection to a toner container. When the toner container is to be changed, the toner container is swivelled via a holding mechanism and a new container is connected to the adaptor. A cutter on the adaptor then punctures a sealing foil over the filling and emptying opening of the toner container. For emptying, the suction nozzle moves vertically into the toner container whose floor is fashioned funnel-shaped to form a toner collecting region. | 6 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. application Ser. No. 13/614,474, filed on Sep. 13, 2012, entitled “Nanoadhesion Structures for Sporting Gear,” which is a divisional of U.S. application Ser. No. 12/819,378, filed on Jun. 21, 2010 and issued as U.S. Pat. No. 8,424,474, entitled “Nanoadhesion Structures for Sporting Gear,” which is based upon and claims priority under 35 U.S.C. §119(e) to U.S. Provisional Application No. 61/218,735, filed on Jun. 19, 2009. The entire contents of each of these disclosures are incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] Field of the Invention
[0003] This invention relates to sporting gear having at least one surface equipped for nanoadhesion, more specifically to swimming goggles having a nanofiber surface to attach to the user's body, a shoe having a nanofiber surface on an outsole to attach to a nanofiber surface on a midsole, a nanoadhesive seam to connect panels as part of athletic apparel, and a nanofiber zipper.
[0004] Description of the Related Art
[0005] Today's sporting gear, including sporting apparel and sporting equipment, may be a combination of the latest innovations of technology from various scientific disciplines. The resulting products are a system of innovative advances all contributing to the performance, safety, and comfort of the athlete. One significant area to improve sporting gear is to attach different sporting gear components together or attach components to the wearer's body. Traditional processes to adhere components to each other and to the user have been imperfect.
[0006] In the case of swimming goggles and scuba masks, suction and compression have been traditional approaches to adhere a mask to the user's upper face. However, swim goggles utilizing these approaches frequently leak water into a space between a goggle lens and user's eye causing the user to lose the ability to properly see out of that eye resulting in a loss of potential performance. The swim goggle user may tighten the goggles and thereby push the goggles further into the skin around the eyes in an effort to create a more durable watertight seal. Unfortunately there are negative consequences to tightening goggles because they frequently create red rings around the user's eyes and cause swelling in this skin area by limiting blood flow and lymphatic return.
[0007] In the case of shoes, traditional chemical-based adhesives such as epoxy cement have permanently attached outsoles to lower midsoles. For users requiring new outsoles to repair those that have been worn down after miles of use, the practical solution has been to replace the whole shoes.
[0008] In the case of athletic seams used in clothing, there is a need for a better technique to bind clothing together at a seam to supplement or replace mere thread. After repeated uses of an article of clothing in athletic events or practice events the thread used for seams may break or tear the adjacent clothing to cause the clothing to become unusable.
[0009] In the case of zippers, there is a need for a better zipper. Metal zippers can tear at fabric and plastic zippers may mechanically jam and not allow either opening and/or closing. Further, zipper alternatives provide significant disadvantages. For example, hook and loop fasteners may attach to the wrong surface and cause surface damage.
[0010] There has been previous attempts to create goggles having no leaks, shoes having replaceable outsoles, and apparel having more robust seams and zippers. Yet these efforts have produced sporting gear that suffers from either deficiencies in performance, comfort, or safety.
[0011] There are adhesive systems in nature that have not been applied to sporting gear. For example, the adhesive system on the feet of some insects and lizards, such as Geckos, Anolis lizards, and skinks has attracted research interest. These organisms have been able to attach and detach their feet to climb smooth surfaces such as glass. The adhesion system involves the use of tiny slender natural protrusions known as setae (singular “seta”) attached to their feet. For example, a Tokay gecko lizard possesses seta having a diameter of five microns and a height of 110 microns. The seta may include a set of sub-protrusions which contact other surfaces and have even smaller dimensions. As these organisms climb up smooth surfaces such as glass, the setae help geckos form a temporary attachment so they do not slip and fall. Although aspects of a gecko-like adhesive system have been observed in nature, the technology has not yet been successfully applied to commercial products.
[0012] Although foregoing research efforts have met with varying degrees of success, there remains an unresolved commercial need for more leak-proof swimming goggles, shoes with replaceable soles, and athletic apparel with more robust seams and zippers.
SUMMARY OF THE INVENTION
[0013] One aspect of the present invention may be to address and resolve the above limitations of conventional sporting gear.
[0014] A man-made adhesive mechanism may be customized as part of sporting gear having a mounting surface that may be attached to a second surface. The adhesive mechanism may include a first plurality of nanofibers attached to the mounting surface. The first end of each nanofiber may be attached to the mounting surface using a flocking process along with the application of either thermal or radio frequency bonding. The second end of each of the first plurality of nanofibers may be placed in contact with the second surface not having nanofibers or a plurality of second nanofibers attached to the second surface to form a temporary attachment called nanoadhesion which may include a van der Waals force contribution.
[0015] The nanoadhesion attachment may be detached by pulling the first plurality of nanofibers away at an angle from the second surface. Each nanofiber may include a fiber shaft less than 100 microns in length with a diameter of less than half a micron.
[0016] In a first aspect, the present invention may be adapted to attach swimming goggles to the wearer's face. Goggles may include a lens component, also known as a lens cup, for each eye. A lens component may have a lens surface and a mounting surface. The mounting surface may be configured to form a seal with the skin around a wearer's eye. The mounting surface may be made of the same material as the lens surface or the mounting surface may be included as part of a lower modulus of elasticity material attached as part of the lens component.
[0017] Nanofibers are attached to goggles at the mounting surfaces of each lens component and form a protrusion emanating from the mounting surface that contacts the skin around the wearer's eyes. The nanofibers may be attached around the entire perimeter or only in areas of the mounting surface that are prone to separate from the skin during use of the swimming goggles (such as to the right and left of the eye). The nanofibers may provide a nanoadhesion force to better keep the mounting surface attached to the skin during use and may easily be detached from the skin at the end of use by pulling the mounting surface away from the skin.
[0018] In a second aspect, the present invention may be adapted to attach and detach components of an athletic shoe having an outsole, midsole assembly, and upper. The outsole contains a bottom surface to contact the ground and a top surface to contact the midsole assembly. The top surface of the outsole contains a first mounting surface with a first set of nanofibers attached. The midsole assembly may contain several components to provide shock absorption and stability such as a rear lower midsole, a directional cradle, and a primary midsole. A bottom surface of the midsole assembly may contain a second mounting surface having a second set of nanofibers attached. The outsole may be attached to the midsole assembly by bringing the first and second set of nanofibers together.
[0019] Other sets of nanofibers and mounting surfaces may be included to attach the midsole assembly to the upper and/or the midsole components together. The attachment process allows worn components to be replaced and different components to be swapped out to provide several different shoe configurations for the same upper. The attachment process also improves manufacturing efficiency.
[0020] The shoe assembly may include sunken surfaces and complementary three-dimensional shapes to define the mounting surfaces and to thereby assist in a mechanical interference to keep the outsole in place while the shoe may be used. Further the shoe may include seals and/or gaskets to keep contaminants such as dirt or water away from nanofibers.
[0021] In yet a third aspect, the present invention may be adapted to create a nanofiber seam to attach woven panels to form various athletic gear such as shirts, jackets, shorts, pants, hats, socks, and/or shoes. Nanofibers may also be used to create attachments between garments, for example from a glove to a jacket or a coat to a pant, or a pant to a boot.
[0022] An apparel item may be made up of various components (herein “panels”) that are attached at one or more seams. The panels are cut to the proper size. Panels may have nanofibers attached via the flocking process along an edge of each panel where a seam may be intended to join the panels. The nanofibers may be attached to one side or both sides of each of the edges. The panels are then attached by bringing the nanofibers in contact. The panels may also be folded over to allow additional nanofibers to come into contact and to be attached together. The nanofibers may be pulled apart to allow the panels to be orientated in a different position to each other. The seam may be supplemented by thread for strength.
[0023] In yet a fourth aspect, the invention may be adapted to create a nanofiber-based zipper for athletic gear such as apparel, gym bags, footwear, and the like that contain panels as described above. The nanofiber zipper may be used to attach a first edge of a first panel with a second edge of a second panel. The first and second panels may have nanofibers attached via the flocking process along an edge of each panel where the nanofiber zipper may be intended to attach the panels. The nanofibers may be attached to one side of the first panel edge and to one side of the second panel edge. The panels are then attached by bringing the nanofibers in contact. The user may unzipper the nanofiber zipper by pulling the nanofibers apart at an angle through the use of a zipper slider that may be outfitted with a control handle. The nanofiber zipper may be supplemented by other fasteners such as traditional hooks or buttons.
[0024] As should be apparent, the invention can provide a number of advantageous features and benefits. It is to be understood that, in practicing the invention, an embodiment can be constructed to include one or more features or benefits of embodiments disclosed herein, but not others. Accordingly, it is to be understood that the preferred embodiments discussed herein are provided as examples and are not to be construed as limiting, particularly since embodiments can be formed to practice the invention that do not include each of the features of the disclosed examples.
BRIEF DESCRIPTION OF THE DRAWINGS
[0025] 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:
[0026] The invention will be better understood from reading the description which follows and from examining the accompanying figures. These are provided solely as non-limiting examples of the invention. In the drawings:
[0027] FIG. 1 illustrates a nanofiber according to an embodiment of the present invention;
[0028] FIGS. 2A-2E illustrate a process to attach the nanofiber to a mounting surface using an adhesive according to an embodiment of the present invention;
[0029] FIGS. 3A-3E illustrate a process to attach the nanofiber to a mounting surface using heat or high frequency radio waves according to an embodiment of the present invention;
[0030] FIG. 4A illustrates a pair of swimming goggles according to an embodiment of the present invention as viewed from the top;
[0031] FIG. 4B illustrates the pair of swimming goggles according to an embodiment of the present invention as viewed from the front;
[0032] FIG. 5A illustrates the swimming goggle according to an embodiment of the present invention as viewed from the back;
[0033] FIG. 5B illustrates the swimming goggle according to an embodiment of the present invention as viewed from the top and including a close-up of nanofibers attached;
[0034] FIG. 6A illustrates a swimming goggle according to an embodiment of the present invention without a head band as viewed from the back;
[0035] FIG. 6B illustrates the swimming goggle according to an embodiment of the present invention without a head band as viewed from the top and including a close-up of nanofibers attached;
[0036] FIG. 7A illustrates a ski goggle according to an embodiment of the present invention without a head band as viewed from the front;
[0037] FIG. 7B illustrates the ski goggle according to an embodiment of the present invention without a head band as viewed from the top and including a close-up of nanofibers attached;
[0038] FIG. 8A illustrates a set of skin areas or regions designed to be in contact with the swimming goggles according to an embodiment of the present invention as viewed from the front;
[0039] FIG. 8B illustrates a skin area or region designed to be in contact with the ski goggle according to an embodiment of the present invention as viewed from the front;
[0040] FIG. 9 illustrates a shoe having components attached by nanofibers according to an embodiment of the present invention as viewed from the side;
[0041] FIG. 10 illustrates a lower from the shoe having components attached by nanofibers according to an embodiment of the present invention as viewed from the upper side;
[0042] FIG. 11 illustrates a pair of mounting surfaces being attached by nanofibers connected to each of the mounting surfaces according to an embodiment of the present invention as viewed from the side;
[0043] FIG. 12 illustrates an athletic garment having a seam and a zipper utilizing nanofibers according to an embodiment of the present invention as viewed from the front;
[0044] FIG. 13A illustrates a set of two apparel panels having nanofibers prior to attachment according to an embodiment of the present invention as viewed from the side;
[0045] FIG. 13B illustrates the set of two apparel panels having nanofibers attached and folded according to an embodiment of the present invention as viewed from the side;
[0046] FIG. 13C illustrates the set of two apparel panels having nanofibers attached, folded, and double-stitched with thread according to an embodiment of the present invention as viewed from the side;
[0047] FIG. 14A illustrates a set of two apparel panels having double-sided and single-sided nanofibers prior to attachment according to an embodiment of the present invention as viewed from the side;
[0048] FIG. 14B illustrates the set of two apparel panels having double-sided and single-sided nanofibers attached according to an embodiment of the present invention as viewed from the side;
[0049] FIG. 14C illustrates the set of two apparel panels having double-sided and single-sided nanofibers attached and double-stitched with thread according to an embodiment of the present invention as viewed from the side;
[0050] FIG. 15A illustrates a set of two apparel panels having single-sided nanofibers prior to attachment according to an embodiment of the present invention as viewed from the side;
[0051] FIG. 15B illustrates the set of two apparel panels having single-sided nanofibers attached according to an embodiment of the present invention as viewed from the side, this FIG. 15B also illustrates the preferred embodiment of the nanofiber zipper;
[0052] FIG. 15C illustrates the set of two apparel panels having single-sided nanofibers attached and double-stitched with thread according to an embodiment of the present invention as viewed from the side;
[0053] FIG. 16A illustrates first and second nanofiber folds as part of a nanofiber zipper detached in an open state as viewed from the top;
[0054] FIG. 16B illustrates first and second nanofiber folds as part of the nanofiber zipper attached in a closed state as viewed from the top;
[0055] FIG. 17A illustrates a cross section of an upper section of a nanozipper slider showing first and second nanofiber folds as viewed from the top;
[0056] FIG. 17B illustrates a cross section of a lower section of the nanozipper slider showing first and second nanofiber folds as viewed from the top;
[0057] FIG. 18A illustrates the nanofiber zipper slider from the front;
[0058] FIG. 18B illustrates the nanofiber zipper slider from the left;
[0059] FIG. 18C illustrates the nanofiber zipper slider as part of the full nanofiber zipper;
[0060] FIG. 19A illustrates a nanofiber watch attached to a wrist using a strap as viewed from the side;
[0061] FIG. 19B illustrates the nanofiber watch attached to a wrist without the strap as viewed from the side;
[0062] FIG. 19C illustrates the nanofiber watch attached to a wrist without the strap as viewed from the top;
[0063] FIG. 19D illustrates the nanofiber watch with nanofibers attached and the wrist as viewed from the side;
[0064] FIG. 20A illustrates a second device attached to an arm using a strap as viewed from the front;
[0065] FIG. 20B illustrates the second device watch attached to the arm without the strap as viewed from the front;
[0066] FIG. 20C illustrates the second device as viewed from the front;
[0067] FIG. 20D illustrates the second device with nanofibers attached and the arm as viewed from the side;
[0068] FIG. 21A illustrates the second device attached directly to a piece of clothing using nanofibers as viewed from the front;
[0069] FIG. 21B illustrates the second device as viewed from the front;
[0070] FIG. 21C illustrates the second device with nanofibers attached and the piece of clothing as viewed from the side; and
[0071] FIG. 21D illustrates the second device with nanofibers attached and the piece of clothing with nanofibers attached as viewed from the side.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0072] Referring now to the drawings, wherein like reference numerals designate identical or corresponding parts throughout the several views.
[0073] Reference will now be made in detail to the present preferred embodiments of the invention, examples of which are illustrated in the accompanying drawings. Wherever possible, the same reference characters will be used throughout the drawings to refer to the same or like parts.
[0074] FIG. 1 illustrates an adhesive protrusion hereafter known as a nanofiber preferably having a length from 5 to 100 microns in length. The nanofiber diameter may be preferably 0.05 times its length which may range from 250 nanometers to a micron. A first terminal end 22 of a nanofiber shaft 23 may not be attached to a mounting surface. The opposite terminal end 24 of the nanofiber shaft may be attached to a mounting surface via an adhesive or other attachment method such as thermal or high frequency radiation induced bonding or the like.
[0075] When the first terminal end 22 of the nanofiber 20 contacts another surface, attraction forces, including van der Waal forces, adhere the nanofiber end 22 to the other surface. The other surface may also have a second nanofiber attached by adhesive that adheres to the nanofiber and/or the mounting surface. The attraction forces produced by contact with the nanofiber is referred here as nanoadhesion. The resulting attraction forces mimic the action of setae on a gecko's foot.
[0076] The nanofibers are constructed using various methods. These methods generally involve casting or molding the fibers, growing them in a solution, or deposition. One method may be to use lithography methods where a recess may be etched in a semiconductor substrate and nitride and oxide layers are deposited on the substrate. The surface then may be patterned and etched. When the underlying structure is etched, a stress difference between the oxide and nitride layers causes the structure to curl and to form a shaft structure. The ends 22 of the shaft may be roughened to increase surface area available for contact by using wet etching, radiation, plasma roughening, electrochemical etching and others.
[0077] A preferred method of making nanofibers involves creating yarns of sub-micron diameter fibers. These yarns may be cut from the yarns to release the fibers in lengths such that when adhered to a mounting surface, in a position perpendicular to the mounting surface, the nanofiber will not collapse under its own weight.
[0078] The nanofibers may be then collected and prepared for attachment to the mounting surface. The nanofibers may be cleaned to remove contaminants and then chemically treated to accept an electric charge. The nanofibers may be spin-dried and then oven-dried to a specific moisture content. Conductivity may depend on moisture content, so it may be preferable that some moisture remain with the nanofibers. The nanofibers 20 are then packaged in moisture-proof containers 4 to maintain optimal moisture until a later attachment of the nanofibers 20 to a mounting surface.
[0079] The nanofibers 20 may then be attached to a mounting surface via a flocking process. There are various types of flocking methods available, but an electrostatic-based flocking method may be preferred for attaching nanofibers to a mounting surface because of its ability to better align the nanofibers to the mounting surface.
[0080] Two electrostatic-based flocking processes are preferred for permanently attaching the nanofibers 20 to the mounting surface. The first process involves an adhesive to attach the nanofibers 20 to the mounting surface and the second process involves heat instead of the adhesive.
[0081] In the first process shown in FIGS. 2A to 2E , the flocking process begins by applying a chemically-compatible adhesive to the mounting surface which has been properly cleaned. In the case of a textured mounting surface having peaks and valleys, the adhesive may only be applied to the peaks. Various adhesives may be used such as: a low viscosity ultra-violet cure epoxy, uncured silicone rubber, polyurethane resin, plastisol (polyvinyl chloride particles suspended in a plasticizer), or the like.
[0082] As shown in FIG. 2B , the adhesive may be applied to the mounting surface in the area(s) where the nanofibers 20 are desired to be attached. The adhesive thickness applied may be dependent upon the adhesive used and the mounting surface. A statistical process control methodology may begin with a preferred adhesive thickness that may be approximately ten times the shaft diameter of the nanofiber. The thickness may then be adjusted to optimize the reliability of the adhesive to hold the nanofiber and the efficacy of the final product.
[0083] This methodology will create a scaled fiber assembly substantially similar to that encountered in nature within the gecko's foot, and in a manner that lends itself to large scale industrial production.
[0084] After the adhesive 3 may be applied, the mounting surface 2 may be placed between the flock hopper 5 and a grounded electrode 8 as shown in FIG. 2C . The flock hopper 5 may be filled with the many nanofibers transferred from the moisture-proof containers 4 . The flock hopper 5 may have rotating flock stirrers with a plurality of arms configured to allow the nanofibers 20 to become airborne randomly to produce a uniform pattern at the exit of the hopper. The airborne nanofibers may then pass through an electrode grid 6 at the exit of the flock hopper which imparts a charge on the airborne nanofibers 20 that is an opposite electric charge compared to the grounded electrode 8 .
[0085] The temperature and humidity of the flocking environment may be critical in controlling the charge on the airborne nanofibers. Humidity too low may cause the nanofibers to not effectively take on an electrical charge and humidity too high may cause the nanofibers to undesirably stick or clump to each other. These humidity and temperature levels may be optimized according to the nanofiber characteristics and the adhesive used.
[0086] Once the nanofibers 20 are electrically-charged and released from the flock hopper 5 to be airborne above the mounting surface as elements 7 , the nanofibers 7 will align themselves with the magnetic field between the electrodes 6 , 8 and accelerate towards an oppositely-charged electrode 8 arranged below the mounting surface 2 . The aligned and accelerated nanofibers 7 collide with and embed into the adhesive 3 in a position substantially perpendicular to the mounting surface 2 .
[0087] Alternatively, the adhesive may be electrically charged instead of having a grounded electrode beneath the mounting surface. The nanofibers 20 would similarly embed into the adhesive 3 in the position substantially perpendicular to the mounting surface 2 .
[0088] As shown in FIG. 2D , the mounting surface 2 may then be removed from between the flock hopper 5 area and excess nanofibers 21 which are not embedded into the adhesive 3 may be removed via vacuum 9 or other suction device. The adhesive 3 may be allowed to cure and the nanofibers 20 remain attached and generally perpendicular to the mounting surface as shown in FIG. 2E .
[0089] The second process may be shown in FIGS. 3A to 3E . The nanofibers 20 used in this process may be made of thermoplastic which may form a bond with the mounting surface 2 greater than a certain temperature. Various thermoplastics may be used such as Poly(methyl methacrylate) or PMMA, polyethylene (PE), Polystyrene (PS), or the like.
[0090] As represented in FIG. 3A , the mounting surface 2 may first be prepared for the attachment of the nanofibers 20 by cleaning using surfactants or other cleaning agents available to remove contaminants that may inhibit the subsequent process steps. Next, as shown in FIG. 3B , the mounting surface 2 may be heated. The heater 10 may be an oven, a frequency radiation emitter, or the like. The heater 10 may use heating means 11 such as radiation heat transfer or convention heat transfer to heat the mounting surface 2 to a temperature above the melting point of the material used to make the nanofibers 20 . For example, the melting point of PMMA is approximately 135 degrees Celsius, polyethylene is between 105 to 130 degrees Celsius, and polystyrene melts at roughly 240 degrees Celsius.
[0091] After heating, the mounting surface 2 may be placed between the flock hopper 5 and a grounded electrode 8 as shown in FIG. 3C . The flock hopper 5 may be filled with the many nanofibers transferred from the moisture-proof containers 4 . The flock hopper 5 converts the nanofibers 20 into airborne nanofibers 7 which then pass through an electrode grid 6 at the exit of the flock hopper to impart a charge on the airborne nanofibers 20 that is an opposite electrical charge compared to that of the grounded electrode 8 .
[0092] Once the airborne nanofibers 7 are electrically-charged and released from the flock hopper 5 to be airborne above the mounting surface, they will align themselves with the magnetic field between the electrodes 6 , 8 and accelerate towards an oppositely-charged electrode 8 arranged below the substrate 2 . The aligned and accelerated nanofibers 7 collide with the heated mounting surface 2 and nanofibers 7 partially melt at the contact point between the nanofibers 20 and the heated mounting surface 2 to form a permanent attachment point.
[0093] The mounting surface 2 may then be removed from between the flock hopper 5 area and the excess nanofibers 21 that are not attached to the mounting surface 2 are removed via vacuum 9 or other suction device as shown in FIG. 3D . The mounting surface 2 may be allowed to cool and the nanofibers 20 remain attached and generally perpendicular to the mounting surface as illustrated in FIG. 3E .
First Embodiment—Nanofiber Swimming Goggles
[0094] Sporting gear provides useful applications for nanoadhesion. In the first embodiment, swim goggles are commonly used to enable swimmers to keep water out of their eyes. The swim goggles 101 are illustrated in FIGS. 4A to 7B . The swim goggles 101 may include two eye components 102 , a nose bridge 108 and a head band 104 . The nose bridge 108 may be designed to hold each of the eye components 102 a fixed distance apart. The head band 104 may fit around the head of the wearer and be attached at each end to the eye components 102 . Each eye component 102 may include a lens surface 103 , a connector interface 107 , a head band interface 105 , and a sealant surface 106 . The connector interface 107 may connect the nose bridge 108 to the eye component 102 . The head band interface 105 may connect the head band 104 to the eye component 102 . The sealant surface 106 may contact a skin contact area 123 , 124 of the left or right eye 121 , 122 as shown in FIG. 8A . The shape of the sealant surface 106 may be similar to the shape of the skin area 123 , 124 to allow contact all around the eye 121 , 122 . The sealant surface 106 may be the same material as the lens surface 103 .
[0095] As shown in FIG. 5B , the sealant surface 106 may have many nanofibers 20 attached at the terminal end 24 . The unattached terminal ends 22 of the nanofibers 20 are configured to contact the skin contact area 123 , 124 when the goggles 101 are worn by a user and thereby form a nanoadhesion attachment with the skin contact area 123 , 124 .
[0096] The nanofibers 20 are not configured to penetrate the skin contact area 123 which is composed of several skin layers including the epidermis and dermis. The human epidermis is the outer skin layer and its minimum thickness is 50 microns at the eyelids. The human epidermis has five sub-layers and the cells divide at the inner layers and are gradually pushed to the exterior layers where their cells flatten and die to be shed every two weeks. The nanofibers 20 may be configured to merely contact the outer layers of the epidermis to avoid skin injury.
[0097] Another embodiment of the goggles may have a rubber gasket. The rubber gasket may act as the sealant surface 106 and may be merely attached to the eye component 102 via adhesive such as epoxy cement or the like. The gasket 106 may be made from rubber, silicone, or other soft material. One end 24 of each nanofiber 20 may be permanently attached to the rubber gasket 106 using one of the flocking processes 1 , 12 . The skin contact area 123 , 124 contacts the unattached end 22 of the nanofibers 20 when the swim goggles 101 are worn and a nanoadhesion attachment may be made between the nanofiber 20 and the skin contact area 123 , 124 .
[0098] Embodiments of the goggles 101 are intended to be used by the wearer in a similar way. The wearer places the eye components 102 , 109 over the eyes 121 , 122 , so that the end 22 of the nanofibers 20 attached to the sealant surface 106 contacts the skin contact area 123 . The wearer then fastens the head band 104 around the wearer's head to provide a comfortable fit which pulls the sealant surface 106 against the skin 123 in order to form a watertight seal. The wearer may also slightly depress the eye component 102 against the skin 123 to force a small amount of air to be pushed out from between the eye compartment 102 and the eye 121 . When this air is pushed out, the watertight seal keeps the air from returning and thereby maintains a negative suction between the eye component 102 and the corresponding eye 121 to improve the watertight seal. The negative suction is an absolute pressure less than ambient pressure. The user may also depress the eye component 109 to achieve a similar negative suction to improve the watertight seal related to the other eye 122 .
[0099] As the wearer engages in a water activity involving immersing the user's head and swim goggles 101 in water, the watertight seal may be maintained because the skin 123 remains in contact with the sealant surface 106 as a result of the negative suction, the pull of the head band 104 , and the nanoadhesion attraction between the nanofibers 20 and the skin 123 . This watertight seal may be more robust than goggles without nanofibers 20 , because as the wearer engages in vigorous activities while wearing the goggles 101 the tight seal may be vulnerable to compromise as the contact skin area 123 changes shape relative to the sealant surface 106 during the water activity.
[0100] When the water activity has been completed, the wearer merely releases the head band 104 from the back of the wearer's head and the wearer pulls the eye components 102 , 109 from the skin contact areas 123 , 124 .
[0101] A second aspect to this first embodiment may be swim goggles without a head band 104 , connector interface 107 , and nose bridge 108 as shown in FIGS. 5A and 5B . In this second aspect, each eye component 102 is identical to each other and has nanofibers 20 attached to the sealant surface 106 . Just prior to the wearer engaging in a water activity involving immersing the user's head and swim goggles in water, an eye component is placed in contact with each of the respective skin areas 123 , 124 so that the nanofibers 20 are in contact with the respective skin areas 123 , 124 . A watertight seal may be maintained as described with respect to a single eye component because the skin 123 remains in contact with the sealant surface 106 as a result of negative suction and the nanoadhesion attraction between the nanofibers 20 and the skin 123 . When the water activity has been completed, the wearer merely pulls each eye component from the respective skin areas 123 , 124 .
[0102] As shown in FIGS. 7A and 7B , ski goggles may be a second aspect of this first embodiment. The ski goggles 130 may include a lens 131 and a sealant surface 132 . The ski goggles 130 may or may not also include a strap (strap not shown). The sealant surface 132 has nanofibers 20 attached using at least one of the flocking processes mentioned earlier. Just prior to the wearer engaging in a skiing activity, the nanofibers 20 are placed in contact with a skin area 125 as shown in FIG. 8B . A nanoadhesion attraction between the skin area 125 and the nanofibers 20 is created which keeps the ski goggles 130 attached to the skin area 125 . When the skiing activity has been completed, the wearer merely pulls the sealant surface 132 away from the skin area 125 . Other sports goggles, prescription or non-prescription, are also embodied in this application and can be similarly constructed.
[0103] In yet another embodiment, the sealant surface 132 having nanofibers 20 may be located instead on a waistband or shirt cuff to grip the nearby skin better.
Second Embodiment—Replaceable Shoe Components
[0104] Another embodiment utilizing the nanofibers 20 is illustrated in FIG. 9 as an athletic shoe 200 having an upper 201 and a lower 202 . FIG. 10 shows the lower 202 for a left foot, but the right shoe has a similar construction. The lower 202 may include a full-length primary midsole 210 , a directional cradle 211 , a first cushion 212 , a second cushion 213 , a third cushion 214 , a rear lower midsole 215 , a rear outsole 220 , a lateral outsole 221 , a medial outsole 222 , a center outsole 223 , and a front outsole 224 . The directional cradle 211 may be attached to the primary midsole 210 . The cushions 212 , 213 , 214 may be attached to both the directional cradle 211 and the rear lower midsole 215 . The components of the outsole 220 , 221 , 222 , 223 , 224 may be attached to the rear lower midsole 215 , directional cradle 211 , and/or primary midsole 210 . Any of the components that are part of the lower 202 may be attached together where as shown in FIG. 11 a first set of nanofibers 241 are permanently attached to first mounting surface 240 and a second set of nanofibers 231 are permanently attached to a second mounting surface 230 via the flocking processes 1 , 12 . The mounting surfaces 230 , 240 may be part of the components of the lower 202 . Then, using the process of nanoadhesion, the first and second nanofibers 231 , 241 are placed in contact as the components of the lower 202 are placed in contact to form a nanoadhesion attachment. The attachment may be temporary because the user may pull the lower components (elements 210 - 215 and/or 220 to 224 ) apart to remove or replace the component with a second component.
[0105] The nanoadhesion embodiments of shoe 200 are intended to be used by the wearer in a similar way. The wearer inserts her foot into the upper 201 and fastens the upper 201 comfortably to the foot so the foot may be disposed between the upper 201 and the lower 202 . The wearer may engage in whatever activity desired so that the outsole components 220 , 221 , 222 , 223 , 224 may have a set of impacts with the ground.
[0106] When the activity has been completed, the upper 201 may be unfastened and the wearer's foot removed from the shoe 200 . When one or more of the components of the lower 202 become worn beyond repair and need to be replaced, then the wearer will pull the set of nanofibers 231 permanently attached to the worn component from the set of nanofibers 241 attached to another component. Next, the wearer may attach a replacement component having a new set of nanofibers 231 on a mounting surface 230 to the old corresponding set of nanofibers 241 on the other component by bringing them in contact.
Third Embodiment—Nanofiber Seams
[0107] Yet another embodiment may be to produce a nanofiber seam to connect woven panels as part of athletic gear such as shirts, jackets, shorts, pants, hats, socks, and/or shoes. Various seam configurations may be created with nanofibers. For example, FIG. 12 illustrates an athletic shirt 300 having a first woven panel 310 and a second woven panel 320 attached by a nanofiber seam 301 .
[0108] The woven panels 310 , 320 may first be cut to the proper size prior to being attached by the seam 301 . The woven panel 310 has a top side 312 and a bottom side 313 as shown in FIG. 13A . The woven panel 320 has a top side 322 and a bottom side 323 . The panels 310 , 320 may have nanofibers 231 , 241 attached via the flocking process 1 , 12 along an edge of each panel where a seam may be intended to join the panels. The nanofibers 231 may be attached to one side of the panel 310 at a panel edge 311 as shown by FIG. 13A . The nanofibers 241 may be permanently attached to one side of the panel 320 at a panel edge 321 using the flocking process 1 , 12 . The panels 310 , 320 are then attached by bringing the nanofibers 231 , 241 in contact at the panel edges 311 , 321 . FIG. 13B shows the attached panel edges 311 , 321 after being folded over. FIG. 13C shows thread stitches 302 , 303 added to add strength and to form a nanofiber seam 304 . Prior to the stitching 302 , 303 being applied, the nanofibers 231 , 241 may be pulled apart to allow the panels 310 , 320 to be reattached in case they have been incorrectly positioned together the first time.
[0109] In yet an alternative embodiment, the nanofibers 231 , 241 may be attached to the panels 310 , 320 in both single-sided 412 , 422 and double-sided 411 , 421 nanofiber areas as shown in FIG. 14A . In this embodiment two of the double-sided nanofiber areas 411 , 421 are first placed in contact, then folded over to allow the remaining two double-sided nanofiber areas 411 , 421 to attach to the single-sided nanofiber areas 412 , 422 as shown in FIG. 14B . Threaded stitching 402 , 403 may be added for strength and to form a second nanofiber seam 404 as shown in FIG. 14C .
[0110] In another embodiment, a nanofiber seam 504 may be produced by attaching nanofibers to panels, 310 , 320 to form a set of single-sided nanofiber areas 511 , 521 as shown in FIG. 15A . The nanofiber panel edges 511 , 521 are attached together using nanoadhesion by being placed in contact as shown in FIG. 15B . Stitching 502 , 503 is applied to add further strength to the nanofibers and thereby produce the nanofiber seam 504 as shown in FIG. 15C .
[0111] The nanofiber seams 304 , 404 , 504 , may be used by apparel designers to construct various athletic gear products from one or more woven panels. When the athletic gear is utilized by the final user, the nanofiber seam should keep one or more woven panels reliably together.
[0112] In yet another embodiment, the seam arrangement represented by the nanofiber panel edges 511 , 521 may be used to reconfigure a pocket on clothing so that the location and the shape of the space that can be accommodated within the pocket may be changed by adjusting the contact area between the panel edges 511 and 521 at a perimeter of the pocket and clothing that the pocket is mounted upon.
[0113] In a further embodiment, the seam arrangement represented by the nanofiber panel edges 511 , 521 may be used to connect a jacket to pants, e.g., sporting apparel such as running jackets and pants, warm-up jackets and pants, and/or ski jackets and pants. This may improve warmth by keeping the wind out of the area between the jacket and the pants. The panel edge 511 may be on the bottom of the jacket edge and the panel edge 521 may be on the top of the pants as shown in the FIG. 15A . When the pants are attached to the jacket at the panel edges 511 , 521 , then the panels may create the nanoadhesion attachment as shown in FIG. 15B .
[0114] In yet a further embodiment, the seam arrangement represented by the nanofiber panel edges 511 , 521 may be used to connect cuff-tabs on shirt sleeves to eliminate the need for buttons.
[0115] In another embodiment, the seam arrangement represented by the nanofiber panel edges 511 , 521 may be used to adjust the size of air vents in clothing so that the user may decide to enlarge vents during strenuous activity and then reduce the size of the vents after the activity has finished.
[0116] In a further embodiment, the seam arrangement represented by the nanofiber panel edges 511 , 521 may be used to attach and detach removable clothing elements, such as hoods and sleeves.
[0117] In yet another embodiment, the seam arrangement represented by the nanofiber panel edges 511 , 521 may be used to attach and detach packaging components so the packaging closure may be curved instead of straight.
Fourth Embodiment—Nanofiber Zipper
[0118] Yet another embodiment that may utilize the nanofibers 20 in sporting gear is a nanofiber zipper 600 , as shown in the athletic shirt 300 shown earlier in FIG. 12 . The zipper may also be adapted for use in athletic gear such as apparel, gym bags, footwear, and the like.
[0119] The nanofiber zipper 600 may be illustrated in FIGS. 12, 16A, 16B and 18C where the nanofiber zipper may be configured to detach a first panel edge 606 from a second panel edge 616 ( FIG. 16A ) and then later reattach the panels 606 , 616 ( FIG. 16B ). The first panel 606 includes both a top side 607 and a bottom side 608 . The second panel 616 includes both a top side 617 and a bottom side 618 . The nanofiber zipper 600 may include a zipper slider 630 configured to open and close the zipper, a first nanofiber fold 602 as part of first panel edge 606 , a first set of nanofibers 603 attached as part of first panel edge 606 , a second nanofiber fold 612 as part of second panel edge 616 , and a second set of nanofibers 613 attached as part of second panel edge 616 . The nanofiber zipper 600 may include a first set of thread stitches 604 , 605 to add strength to the first nanofiber fold 602 and a second set of thread stitches 614 , 615 to add strength to the second nanofiber fold 612 . The first nanofiber fold 602 may include a top fold side 620 and a bottom fold side 621 . The second nanofiber 612 fold may include a top side 622 and a bottom side 623 .
[0120] The first and second nanofiber folds 602 , 612 as well as the first and second nanofibers 603 , 613 may be created and attached using the same concepts already discussed as part of the processes used to make the nanofiber seams 304 , 404 , 504 .
[0121] FIGS. 16B and 17B show the nanofiber zipper 600 in the closed state where the nanofibers on the first nanofiber fold 602 have attached to the second set of nanofibers 613 using nanoadhesion. Also, the nanofibers on the second nanofiber fold 612 have attached to the first set of nanofibers 603 using nanoadhesion.
[0122] The zipper slider 630 opens and closes the zipper 600 and includes a control handle (not shown) for the user to control the zipper 600 . The control handle may be attached at an attachment point 650 as shown in FIGS. 18A, 18B, and 18C .
[0123] FIGS. 17A and 18A show a cross section at the top 651 of the zipper slider 630 where the panel edges 606 , 616 are unattached to each other. The first and second nanofiber folds 602 , 612 are used to guide the panel edges 606 , 616 through the zipper slider 630 . FIG. 17B shows a cross section at the bottom 652 of the zipper slider 630 where the panel edges 606 , 616 are attached via nanoadhesion.
[0124] A close-up of the zipper slider 630 is shown at FIG. 18A . The slider top 651 is wider than the slider bottom 652 . FIG. 18B shows the left side of the zipper slider 630 with an open groove 652 for the first panel edge 606 to travel.
[0125] The nanofiber zipper 600 may be supplemented by other fasteners such as traditional hooks or buttons.
[0126] The nanofiber zipper 600 is operated by the user by grabbing a control handle (not shown) attached to the 650 attachment at the zipper slider 630 . The user moves the zipper slider 630 up 700 along the length of the panel edges 606 , 616 to close the zipper 600 . The user may open the zipper 600 by moving the zipper slider 630 down 701 along the length of the panel edge 606 , 616 and the nanofibers on the panel edges 606 , 616 may be pulled apart by the zipper slider. The process is reversible and the zipper 600 may be opened and closed many times.
[0127] Although various zipper embodiments are possible with nanoadhesion, the preferred embodiment is shown in FIGS. 15A-15B . The preferred zipper includes panels 310 , 320 with nanofibers attached at nanofiber panel edges 511 , 512 . The nanofiber panel edges 511 , 521 are attached together using nanoadhesion by being placed in contact as shown in FIG. 15B . The nanofibers panel edges 511 , 512 may be later detached by pulling them apart.
Fifth Embodiment—Device Attachment
[0128] Yet another embodiment that may utilize the nanofibers 20 in sporting gear is a nanofiber attachment, as demonstrated by a wristwatch 800 in FIG. 19A . The nanofiber attachment may be adapted for other devices other than wristwatches, for example, global positioning system devices, music players or video entertainment devices, communication devices, heart rate monitors, biometric sensors, and the like.
[0129] The nanofiber watch 800 may include a strap 801 while worn on the wrist 126 or may be attached to the wrist 126 directly using nanofibers 20 as shown in FIGS. 19B-19D . The watch 800 includes nanofibers 20 that may be attached using one or more of the flocking processes 1 , 12 discussed earlier. The watch 800 may be attached directly to the wrist 126 by placing the nanofibers 20 in contact with the 126 or arm 127 to form a nanoadhesion attachment. The wearer engages in whatever activities desired and the nanoadhesion attachment keeps the watch 800 attached to the wrist 126 . When the watch 800 is to be removed from the wrist 126 , then the wearer may pull the watch 800 away from the wrist 126 to separate the nanofibers 20 from the wrist 126 .
[0130] A second aspect to the device attachment is to attach a second device 810 to the arm 127 as shown in FIG. 20A-20D . The second device may be a time measuring device, heart monitor, location device, music or video entertainment device, medical sensor, athletic performance measuring sensor, communication device, or the like. The second device 810 may include a strap 811 while worn on the arm 127 or may be attached to the arm 127 directly while solely using nanofibers 20 . The second device includes nanofibers 20 that may be attached using one or more of the flocking processes 1 , 12 discussed earlier. The second device 810 may be attached directly to the arm 127 by placing the nanofibers 20 in contact with the arm 127 to form a nanoadhesion attachment. The wearer engages in whatever activities desired and the nanoadhesion attachment keeps the second device 810 attached to the arm 127 . When the second device 810 is to be removed from the arm 127 , then the wearer may pull the second device 810 away from the arm 127 to separate the nanofibers 20 from the arm 127 as shown in FIG. 20D .
[0131] In a third aspect to the device attachment embodiment, a second device 810 is attached to a piece of clothing 812 as shown in FIGS. 21A-21C . The second device 810 may be attached directly to the clothing 812 . The user merely attaches the second device 810 to the clothing 812 so that the nanofibers 20 on the device 810 come in contact with the clothing 812 to form a nanoadhesion attachment. When the second device 810 is to be removed from the clothing 812 , then the wearer may pull the second device 810 away from the clothing 812 to separate the nanofibers 20 from the clothing 812 as shown in FIG. 21C . The piece of clothing 812 may be shirts, pants, socks, shoes, jackets, or the like.
[0132] In yet a fourth aspect to the device attachment embodiment, the second device 810 is attached to a piece of clothing 812 having nanofibers 815 attached to the clothing 812 . In this aspect a nanoadhesion attachment is formed between the nanofibers 20 attached to the second device 810 and the nanofibers 815 attached to the clothing 812 using the one or more of the flocking processes described earlier. The user merely attaches the second device 810 to the clothing 812 so that the nanofibers 20 on the device 810 and the nanofibers 815 on the clothing 812 come in contact with each other to form a nanoadhesion attachment. The user engages in whatever activity is desired and the nanoadhesion attachment keeps the device 810 attached to the clothing 812 . When the second device 810 is to be removed from the clothing 812 , then the wearer may pull the second device 810 away from the clothing 812 to separate the nanofibers 20 , 815 as shown in FIG. 21D .
[0133] In yet a fifth aspect to the device attachment embodiment, the second device 810 illustrated in either FIGS. 21C or 21D could be a component designed to cushion the impact of certain body parts during sporting activities. The component could be functionally equivalent to shin pads used by soccer players, modular protection zones used by football players on football pants and other protective gear, or localized padding used in biking shorts used by cyclists to lessen the shock and bumps from a bicycle seat to contact points on the human body. The component may have nanofibers 20 attached to the component and may have nanofibers 815 attached to the contact area on the clothing.
[0134] In yet a sixth aspect to the device attachment embodiment, the second device 810 may be a backpack and a set of associated straps that may be attached to a wearer's clothing using nanofibers 20 attached to the associated straps. The nanofibers 20 may be attached to nanofibers 815 on the wearer's clothing to form a nanoadhesion attachment. An advantage of using nanofibers 20 , 815 to attach the straps to the clothing may be to reduce chafing during activity. Other embodiments may have a backpack without straps and the backpack attached directly to the clothing with a nanoadhesion attachment.
[0135] In a seventh embodiment, a bottle closure (broadly represented as element 810 in FIG. 21C ) may have nanofibers 20 to form a nanoadhesion attachment with a bottle (broadly represented as element 812 in FIG. 21C ) to replace threaded closures used on bottles, such as soda cans, water bottles, and the like.
[0136] In an eighth embodiment, a roof rack may to interface with an automobile (the roof rack broadly represented as element 810 in FIG. 21C ) may have nanofibers 20 to form a nanoadhesion attachment with an exterior surface of an automobile (broadly represented as element 812 in FIG. 21C ). The roof rack may be used to transport bicycles, boats, sporting equipment, packages in transit, or the like.
[0137] In a ninth embodiment, a clothing hanger (the hanger is broadly represented as element 810 in FIG. 21C ) may have nanofibers 20 to form a nanoadhesion attachment with clothing that is desired to be hung from the hanger (the clothing broadly represented as element 812 in FIG. 21C ). The clothing may or may not have nanofibers to attach with those nanofibers 20 on the hanger.
[0138] In a tenth embodiment, a clothing price tag or information tag (the tag is broadly represented as element 810 in FIG. 21C ) may have nanofibers 20 to form a nanoadhesion attachment with clothing that the tag is associated with (the clothing broadly represented as element 812 in FIG. 21C ).
[0139] In an eleventh embodiment, a portion of a surface of a glove (the portion of the glove surface is broadly represented as element 810 in FIG. 21C ) may have nanofibers 20 to form a nanoadhesion attachment with an item that the glove is gripping while the glove is in the user's hand (the item is broadly represented as element 812 in FIG. 21C ). The item may be a basketball, water polo ball, a hockey stick, a tennis racquet, or other item similarly to be gripped by a glove.
[0140] In a twelfth embodiment, a gripping surface (the gripping surface broadly represented as element 810 in FIG. 21C ) may have nanofibers 20 to form a nanoadhesion attachment with a surface of a hand or glove (the surface of the hand or glove broadly represented as element 812 in FIG. 21C ). The gripping surface may be a hockey stick gripping area, a tennis racquet grip, or other surface similarly gripped by a glove or hand. The glove may also have nanofibers 20 attached to interface with the nanofibers on the gripping surface.
[0141] Further, it should be appreciated that the exemplary embodiments of the invention are not limited to the exemplary embodiments shown and described above. While this invention has been described in conjunction with exemplary embodiments outlined above, various alternatives, modifications, variations and/or improvements, whether known or that are, or may be, presently unforeseen, may become apparent. Accordingly, the exemplary embodiments of the invention, as set forth above are intended to be illustrative, not limiting. The various changes may be made without departing from the spirit and scope of the invention. Therefore, the systems and methods according to exemplary embodiments of this invention are intended to embrace all now known or later-developed alternatives, modifications, variations and/or improvements.
[0142] 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 apparatus including a first surface configured to attach the apparatus to a second surface of another object, and a plurality of elongated nanofibers. Each nanofiber has one end connected to the first surface and an opposite end extending away from the first surface. The plurality of elongated nanofibers is configured to adhere to the second surface by nanoadhesion when brought into contact with the second surface. | 1 |
This is a continuation of application Ser. No. 279,338 filed Aug. 10, 1972, now abandoned.
BACKGROUND OF THE INVENTION
It is an indisputable fact that a substantial segment of the world's population periodically is under the influence of alcohol, to varying degrees and for a variety of reasons. It is not our purpose to become involved in the moral aspects of alcohol consumption, or to delve into philosophical questions concerning the relative amounts of pleasure and pain experienced by people in general as a result of alcohol consumption. It is rather our purpose to mitigate or eliminate, to a significant degree, the most obvious physical effects of alcohol consumption.
Broadly, the two most obvious effects of alcohol consumption are intoxication, and what is commonly referred to as hang-over. Either of these effects may be experienced over a wide spectrum, ranging from barely noticeable to severe. For many years, efforts have been made to find methods or means to counter these effects. Unfortunately for the drinking public, and also for non-drinkers who may be adversely affected by members of the drinking public, previous attempts to counter the effects of alcohol consumption have generally been ineffective, or at best only of limited effect.
No attempt will be made to document all the previous attempts to counter the effect of alcohol consumption, but a few of the more popular methods will be briefly discussed to provide a reference framework. The most popular method of treating an intoxicated person, in an effort to sober the person up quickly, probably is to have the person drink coffee. Unfortunately, coffee has no significant effect on the state of intoxication, and the primary effect of coffee is to change a sleepy drunk into a wide-awake one. It has generally been accepted that the only effective remedy for intoxication is time. That is, the body must be given time to metabolize the alcohol in the blood stream and body tissues. No satisfactory manner of speeding up the process is presently known.
Ethyl alcohol is a carbohydrate. Carbohydrates are metabolized through what is known as the "Krebs Cycle" or the "Citric Acid Cycle." Ethyl alcohol causes intoxication, and an enzyme known as alcohol dehydrogenase, which is produced in the liver, breaks the ethyl alcohol down to carbon dioxide and water. The secondary effect or hangover is thought to result from oxidation of the alcohol which causes a speed up in breathing, heart action and muscle action which breaks down blood sugar to lactic acid. An enzyme known as lactic acid dehydrogenase reverses this process, and converts lactic acid back to blood sugar, thereby eliminating the hangover.
As to methods of relieving the after-effects of alcohol consumption (hangover), their number is great, and they range from various concoctions of food, beverage or medicine to such things as breathing concentrated oxygen. While certain of these methods provide a degree of relief for some people, unfortunately nothing to date is completely and satisfactorily effective.
One of the greatest present problems involving persons who consume alcoholic beverages is that they often unwittingly reach a degree of intoxication greater than desirable for the activity they plan to engage in after cessation of alcohol consumption.
Thus, there is obviously a need for something that will counter the effects of alcohol consumption quickly and effectively, and such is provided by this invention.
SUMMARY OF THE INVENTION
According to this invention, a composition and method are provided for countering the effects of alcohol consumption. More specifically, a composition containing a combination of ingredients in specific proportions is provided, which when administered to a person after consumption of alcoholic beverage can reduce or eliminate the effects of intoxication and hang-over quickly and dramatically.
The composition includes thiamine, riboflavin, niacin, and preferably an edible yeast. The composition preferably is in tablet form, but may be powdered and prepared as a slurry or liquid suspension shortly before use, or may be a capsule containing the ingredients. Also, the composition could be in the form of a canned fluid.
The method comprises orally administering an effective amount of the composition to a person, preferably shortly after cessation of consumption of alcoholic beverage.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The following detailed descriptions of preferred embodiments of the invention, including examples, will illustrate the best known versions of the invention, but it should be noted that additional variations and modifications would fall within the actual scope of the invention.
Certain terms are used throughout the specification and claims which should be defined at this point. Thiamine is intended to represent vitamin B 1 , or thiamine as the hydrochloride or mononitrate salts. Thiamine is readily available from a number of sources, either as a natural or synthetic product, and generally is in a powder form. Riboflavin, or vitamin B 2 , is similarly available in natural or synthetic form as a powder. Niacin is used to mean nicotinic acid, and is sometimes referred to in the art as anti-pellagra vitamin. As used herein, the term yeast is used to define any pharmaceutically suitable yeast or extract thereof and includes substances sometimes referred to as edible yeasts, brewers yeast, pasteurized yeast, etc. A specific example of a preferred yeast is Saccharomyces cerevisiae, but many others are equally applicable.
The term "alcohol" as used herein always refers to ethyl alcohol, and "alcoholic beverage" refers to any of the popular spirits or blends containing ethyl alcohol and intended for human consumption. When reference is made to a volume of alcohol consumed, unless indicated otherwise the amount has been calculated as actual ethyl alcohol volume, rather than volume of a liquor. In the following tests, however, commercially available liquors were used.
The following examples are representative of a large number of tests illustrating the dramatic effects obtainable from this invention. It will be appreciated that both intoxication and hang-over are relative terms, not generally amenable to precise measurement or description. Nevertheless, despite the subjective nature of the tests the dramatic effect of the invention is clearly apparent.
It should also be pointed out that the following examples do not represent all the results of tests that were performed. In some cases, the subjects showed little or no beneficial effect from the invention, particularly in cases where the test subject had consumed enough alcohol to be at or near the "passed-out" condition. Also, due to undetermined differences in individual persons tested, certain persons simply did not make satisfactory test subjects. It will be appreciated that the testing procedure was complicated by the fact that in many cases the testing area initially was occupied by a substantial number of intoxicated persons who interacted.
However, in most cases where the tests were not completely or substantially demonstrative of the sobering effect of the invention, the failure could be traced to a quality control problem such as improper formulation or handling of the composition. For example, the composition loses effectiveness if subjected to excessive heat, light, oxygen or moisture over a period of time. Also, the inclusion of interfering or inhibiting materials during compounding or formulation in some cases resulted in loss of effectiveness.
The composition of the invention includes, as essential ingredients, thiamine, riboflavin and niacin (nicotinic acid). The preferred embodiment of the invention also includes yeast, although in at least one test successful results were obtained with a yeast-free composition. Preferred versions of the invention include thiamine and riboflavin in about equal amounts, and niacin in about one third the amount of either thiamine or riboflavin.
The upper limit of thiamine and riboflavin which a person can consume without harm is thousands of times higher than the estimated daily requirement, and within the framework of the levels used in this invention toxicity is not a consideration. Niacin (nicotinic acid) is relatively non-toxic, but vasodilation, seen as intense flush of the skin, may follow oral intake of excessive amounts of niacin. Partly for this reason, the niacin content of the composition of the invention is preferably only about one third that of the thiamine or riboflavin. The yeast is recognized as a nutritionally excellent substance.
It should be pointed out that while various vitamin preparations or supplements are widely available which include, among other ingredients, part or all of the essential elements of this composition, the products in fact are neither similar nor even related to the composition of this invention. The levels of the critical components of this composition are much higher than the levels found in the common supplemental vitamin formulations, which would be essentially ineffective for the purpose of this invention.
While it is not known for certain just what the mechanism of the reduction in intoxication is, it has been demonstrated dramatically in the following tests.
EXAMPLE I
In this example, eight persons each consumed a distilled alcoholic liquor (average 86 proof) in amounts of from 3 to 91/2 fluid ounces over a relatively short period of time. Shortly after cessation of alcohol consumption, a slurry containing 120 mg thiamine, 120 mg riboflavin, 40 mg niacin, and 1520 mg yeast was orally administered to each of the test subjects who were in varying states of intoxication. Within 40 minutes, all but one of the persons had "good" restoration of mental and physical faculties. The one exception was observed to have "fair" restoration of mental and physical faculties within 65 minutes.
EXAMPLE II
In this example, twelve persons each consumed between 3.4 and 9.5 ounces of a distilled alcoholic liquor (average 86 proof) within a relatively short time, and reached varying degrees of intoxication. Shortly after cessation of alcohol consumption, four tablets, each containing 34 mg thiamine, 34 mg riboflavin, 11 mg niacin, 300 mg yeast, 25 mg corn starch, 15 mg gum arabic and 70 mg microcrystalline cellulose were orally administered to the test subjects. In less than one hour, all but one of the test subjects had made good recovery of mental and physical faculties. The other subject made fair recovery.
The inclusion of corn starch, gum arabic and microcrystalline cellulose in the tablets was strictly for aiding in tablet formation, and these ingredients are considered inert and not as contributing to the effect of the composition. Equivalent materials, such as other forms of starch or gums, might be substituted, the only requirement being that such materials be inert as to the proper performance of the essential ingredients of the invention.
EXAMPLE III
In this example, five persons each consumed from 4.7 to 12.3 ounces of distilled alcoholic liquor (average 86 proof) over a relatively short period of time, reaching varying degrees of intoxication. Shortly after cessation of alcoholic consumption, four tablets each containing 34 mg thiamine, 34 mg riboflavin, 11 mg niacin and 50 mg starch were orally administered to each person. In this test, no yeast was present in the tablets. Within 26 minutes of taking the tablets, four of the persons, including one who had consumed 12.3 ounces of liquor, had good restoration of both mental and physical faculties. The remaining person had good restoration after 30 minutes.
EXAMPLE IV
This example is illustrative of the type of test performed on several hundred subjects, and is representative of the results obtained. The subject, a male person weighing 140 pounds, consumed 200 ml of Scotch whisky over a period of 48 minutes. Approximately 30 minutes after cessation of alcoholic consumption, and while the subject was seriously intoxicated, he was given four tablets each containing 34 mg thiamine, 34 mg riboflavin, 11 mg niacin, 300 mg yeast, 25 mg starch, 15 mg gum arabic and 70 mg microcrystalline cellulose. The subject was observed as to ability to sit, walk, stand, talk and see, and was questioned as to numbness of face and extremities, fuzzy eyesight, thickness of tongue, and general condition. Within 24 minutes of taking the tablets, the subject felt that his degree of intoxication had noticeably lessened. This was confirmed by observation. Within slightly less than 1 hour, the subject appeared to be, and felt himself to be, substantially sober.
In the above tests, the observations as to recovery of faculties involved subjectively evaluating such things as speech, visual changes, light mental exercise, motor coordination, and comparative writing, drawing, etc.
In addition to the above tests, several hundred additional persons were similarly tested using varying total amounts and proportions of the essential ingredients of the invention. These tests indicated that in instances where the test formulation had not deteriorated, such as happened in certain cases due to inadvertent overexposure to light, heat, air or moisture, a composition containing at least 40 mg thiamine, at least 40 mg riboflavin, and from 10 to 80 mg niacin was effective in most cases in dramatically countering the intoxicating effect of alcohol. The use of more than about 200 mg of thiamine or riboflavin, while effective, provided no significant improvement in effect over the use of lesser, but effective, amounts. The inclusion of from 800 to 1600 mg of yeast was observed to generally result in more consistent results. The reduction of hang-over effect, while obviously subjective, was consistently noted by the test subjects.
The addition of starch, gums, microcrystalline cellulose and equivalent materials, inert as to the proper performance of the essential ingredients of the invention, may desirably be added for purposes of forming tablets.
The composition, whether in tablet form or otherwise, should be protected from overexposure to heat, light, moisture and oxygen. The composition in tablet form is desirably packaged in a sealed container under controlled conditions to insure maximum shelf life.
It is again pointed out that the above examples are exemplary, are illustrative of the preferred embodiments of the invention as determined by extensive testing, and are not to be considered as limiting the invention. Neither are they to be construed as representing that the invention is always effective regardless of the amount of alcohol consumed or of other factors. They do describe the invention in the most preferred form known, and they are representative of the dramatic and surprising results obtainable from the invention. | A composition and method for countering the effects of alcohol consumption by a person. The composition includes a specifically proportioned combination of thiamine, riboflavin, niacin and yeast, preferably in tablet form. The method includes orally administering the composition to a person under the influence of alcohol. | 0 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to medical devices designed to assist a physician in performing a mediastinoscopy procedure. More specifically, the invention provides a kit of various systems that work together to improve access, sampling, and visualization during the procedure. Most specifically, the invention relates to inflatable devices for dilating a lumen or cavity in order to prepare a target site, including a mediastinal region, for access by instruments.
2. Description of the Related Art
The term mediastinoscopy refers to an examination of the mediastinum through an incision above and behind the sternum (breastbone) with a suprasternal incision. The mediastinum is the partition separating the right and left thoracic cavities. It is formed from the two inner pleural walls and includes all of the viscera of the thorax except for the lungs. More specifically, the organs in the mediastinal region include the heart and its vessels, the lymph nodes, the trachea, the esophagus, and the thymus. The individual devices and comprehensive self-sufficient kit of the present invention are designed to facilitate the process of inspecting, biopsying, and treating the mediastinum and surrounding areas to observe, detect, and ameliorate cancer or other abnormal tissue conditions.
A mediastinoscopy is an early stage or first step procedure performed in patients suspected of having lung cancer prior to thoracic surgery or other advanced therapy. Typically, a mediastinoscopy is performed to sample or biopsy lymph nodes in the paratracheal and parabroncial regions for cancer staging. Mediastinoscopy is also used to detect lymphoma, Hodgkin's disease, sarcoidosis (a chronic disease of unknown cause characterized by granulomatous tubercles or lesions of the lymph nodes, lungs, and other structures), and other conditions.
Problems with conventional devices and approaches for mediastinoscopy are numerous. First, traditional access is through a percutaneous incision in the neck. This leaves a visibly obvious, slow-healing, and painful scar through the many sensitive muscles and nerves in the neck. Second, visualization is typically poor and even with the assistance of an endoscopic monitor and ultrasound, skilled surgeons have difficulty accessing nodes and assessing whether a node, nodule, or tumor they are about to resect or sever from surrounding tissue is in fact the intended target. Additionally, operating within dark narrow working spaces increases the risk that the surgeon will inadvertently injure or at least aggravate critical vulnerable structures (including coronary arteries, valves, the heart itself) or puncture a lung in the same general region as the nodes while trying to reach the nodes. Third, the elongated instruments presently available require reaching out to grasp nodes, cutting, and dangling the severed, potentially abnormal tissue within the cavity prior to removal. This method risks dropping the sample prior to removal and can cause scattering of malignant particulate material for redistribution in the body amongst healthy tissue.
U.S. Pat. No. 7,232,414 (from hereon “USP '414”) entitled “System and method for capturing body tissue samples” by Hugo X. Gonzalez and assigned to Spiration, Inc. (Redmond, Wash.) discloses a system and method that reduces the risk of scattering abnormal cells during sampling. The system includes a bag means with an open end for receiving a sample and a vacuum suction tube for first pulling a portion of tissue into a protected cove prior to resecting and then for drawing the resected portion to a proximal end of the instrument for removal, collection, and histological analysis. This system and method however, do not address improving the initial visualization of and access to nodes in crevices or at angles out of the direct trajectory through which an instrument has been inserted.
U.S. Pat. No. 6,852,108 (from hereon “USP '108”) entitled “Apparatus and method for resecting and removing selected body tissue from a site inside a patient” by Robert Lawrence Barry, et al. and also assigned to Spiration, Inc. also focuses on reducing the chance of scattering material while resecting a sample. USP '108 elaborates to a greater extent than USP '414 on the position and design of an electrode used for resecting and on a collection chamber at the proximal end of the instrument with a plurality of compartments for indexing samples and preventing cross-contamination. For example, FIG. 9 shows electrode 100 housed within the protected interior of resection lumen 115 into which the vacuum draw 105 directs a portion of tissue (left upper paratracheal node 71l) prior to it being contacted by the electrode. The blade electrode may be made extendable as shown in FIG. 10. Alternatively, it may be designed in the shape of a lasso 120 to form a loop 122 as shown in FIG. 13. In any case, all of the action takes place inside the resection lumen 115 of the tubular member 92 (FIGS. 7-15 are illustrative). The tubular member is inserted percutaneously through the skin after “making an incision at the sternal notch 27 just above the sternum 25” and it is placed “through the incision and between the trachea 28 and the top of the sternum 25” (7:19-34 and FIG. 6). There is no mention of using natural orifices to deliver the tubular member. There is also no disclosure of dilation elements or balloons to protect the trachea, sternum, etc. from agitation by the tubular member. A built-in improved viewing component is not taught as part of the device (7:31-34).
U.S. Pat. No. 5,941,819 (from hereon “USP '819”) entitled “Apparatus for creating a mediastinal working space” by Albert K. Chin and assigned to Origin Medsystems, Inc. (Menlo Park, Calif.) focuses more precisely on space creation in the mediastinal cavity. However, the system provided is a mechanical lifting retractor with two sharply angled rotatable arms (14a, 14b) rather than a pneumatically inflatable assortment of curved balloons. Further, the method provided is aimed at creating a working space for cardiac surgery specifically by “temporarily expanding the space between the rib cage and the pericardium” and involves insertion between a pair of adjacent ribs (FIGS. 7-8 and Abstract). There is no mention of the trachea or bronchus.
Very few patents are directed specifically at instruments and methods for performing a mediastinoscopy as indicated by reference to “mediastinoscopy” in the claims. U.S. Pat. No. 7,473,530 (from hereon “USP '530”) entitled “Method to detect lung cancer” by Maik Huttemann and assigned to Wayne State University (Detroit, Mich.) discloses methods of detecting cancer that involve comparing the levels of RNA for a specific component (COX4-2) in a first lung sample suspected to have cancer and a second lung sample known not to have cancer. The claims include a reference to “mediastinoscopy” along with several other possible diagnostic tests in the context of performing at least one additional test to confirm the lung cancer diagnosis based on the results of the first test comparing RNA (claim 20).
Similarly, there are relatively few United States patents referring to the “mediastinum” in the claims and of those that do almost all are directed at imaging methods, data analysis, or pharmaceutical treatment.
No patents can be found directly addressing atraumatic mechanical dilation of the mediastinal space.
With respect to the preferably toroidal design of the dilating element, U.S. Pat. No. 6,053,891 (from hereon “USP '891”) entitled “Apparatus and methods for providing selectively adjustable blood flow through a vascular graft” teaches that the mediastinum is exposed in order to install a shunt by dividing the sternum. However, the patent is not directed at mediastinoscopy procedures. It cites to U.S. Pat. No. 3,730,186 (from hereon “USP '186”) by Edmunds, et al. for disclosing the use of a “toroidal balloon” to occlude a native artery by placing the balloon around the outside of the artery. It teaches away from the use of a toroidal balloon because it is “believed to create crimps or infolds in the arterial wall even at low degrees of constriction” and “[s]uch crimps or infolds, which project into the flow field of the artery, are expected to disrupt laminar flow within the artery and serve as thrombogenic sites” (2:64-3:11). In the present invention this crimping problem would be avoided as the toroidal balloons herein are used inside conduits as dilators rather than outside conduits as occluders. Further, the toroidal balloons of the present invention are designed for use in larger conduits, canals, and cavities where they are not likely to be in the path of blood flow, rather than being used within or around the outsides of arteries and other blood vessels.
It would not be obvious to use toroidal balloons inside cavities and conduits as dilators including in the area alongside the trachea and in the pleural region. In the patent literature concerning medical devices and toroidal balloons they appear to be disclosed exclusively as occluders on the outside for preventing distal embolization around the heart. For example, see U.S. Pat. No. 7,458,980, U.S. Pat. No. 7,452,352, U.S. Pat. No. 7,396,329, U.S. Pat. No. 7,374,561, U.S. Pat. No. 7,335,192, etc.
None of the above patents provide systems, kits, or methods to dilate, easily sample, and improve visualization in the region outside the trachea during a mediastinoscopy procedure. Further, none of the above patents suggest accessing nodules on the outer trachea, bronchi, mediastinum, or lymph nodes without a neck incision by way of a natural orifice (including the mouth or nose) and natural lumens (including the throat and bronchi).
BRIEF SUMMARY OF THE INVENTION
The present invention provides a kit for performing a mediastinoscopy that improves access, sampling, and visualization. The various elements of the kit are designed to complement one another and be used together. However, any single element (i.e. the pieces for access only, sampling only, or visualization only) could also be used independently or with other commercially available products for mediastinoscopy or other procedures.
First, the access system includes expandable and collapseable elements for dilation extendable from the distal end of an instrument. These may take the form of inflatable balloons. More specifically, there may be one or more toroidal balloons having a hollow center region when expanded (similar to an inner tube flotation device used for the water sport “tubing” having the basic shape of a donut as but one example). The balloons can have any shape as long as they have a hollow center through which instruments can pass. When expanded, the toroidal ballons push against the inner walls of a channel in which they are inserted with their outermost outer surface (outside perimeter). They gently expand the channel and create a protected access and working zone (through their innermost outer surface or inside perimeter) for delivery and operation of instruments. Such instruments may include cameras, sampling and biopsy tools, needles, drug-delivery syringes, electrosurgical cutting and sealing tools, etc.
The toroidal balloons may be used for several purposes. One purpose is to expand a portion of the mediastinal cavity into which light from an endoscope may be directed for improved node visualization prior to grasping. Another purpose is to expand a difficult-to-reach portion of the mediastinal cavity, such as a crevice or narrow interstice between two adjacent structures, for easier access by grasping instruments to a node situated within the interstice. The toroidal balloons can also be used with other regular, non-toroidal balloons that block off an entire portion of the mediastinal cavity to protect sensitive structures or redirect flow, leaving unintended areas undisturbed as the sampling instrument (i.e. MEDIAGOPHER™ sampling instrument as discussed herein) goes after a target node. The atraumatic, flexible surface of an inflatable element such as a balloon provides minimal or no irritation to sensitive structures compared to what a grasping instrument with prongs or a cutting instrument with electrodes and/or blades would do.
Second, the sampling system of the present invention, the MEDIAGOPHER™ sampling instrument, includes a substantially circular head at the distal end 115 of an elongated body 101 with a small diameter and a low profile. The head has two jaws that form a mouth for “biting” samples. The “biting” process is used to cut/resect/separate tissue samples for biopsy or removal. The “biting” can be done with physically sharp elements (i.e. teeth, barbs, etc.) for mechanical cutting and/or electrodes for ablating, welding, and electrosurgically cutting, including combination teeth that are physically sharp and also electrically conductive to cut in more than one manner. The overall structure of the head and mouth assembly is similar to the PACMAN™ video game character in that it resembles a pizza or pie with a slice removed to form a mouth. The size of the missing slice can vary as the jaws open and close (increasing and decreasing the angle between them) to the extent necessary depending on the dimensions of the sample to be grasped and removed. The MEDIAGOPHER™ sampling instrument is termed a “gopher” because it burrows through the hollow spaces or holes in the center of the toroidal balloons after they are advanced and expanded. The MEDIAGOPHER™ sampling instrument waits for and follows the expanded toroidal balloons rather than being advanced before them so that it does not irritate the lumen through which it passes. In an alternative design, the toroidal dilating elements and the tissue resecting tool (MEDIAGOPHER™ sampling instrument) or another tool may work together such that a sensor on the unexpanded balloon detects the approaching tool and automatically expands in response thereto before the tool passes through it.
Third, the visualization system comprises a camera that provides a three hundred and sixty degree (360°) view positioned in the “throat” of the MEDIAGOPHER™ sampling instrument. The camera has a broad range of motion. Initially, it is positioned inside the small, narrow, elongated tube upon which the sampling jaw structure is mounted. In this position the camera is proximal to the sampler and the toroidal balloons. The camera can also be advanced to the region just between the sampling jaws for a direct close-up view of the sampling action. The camera can be advanced further beyond the MEDIAGOPHER™ sampling instrument and through more distal expanded toroidal balloons to explore an area before the MEDIAGOPHER™ sampling instrument jaws or other sampling instruments go there. The camera may also be advanced before balloons are advanced and expanded if it is unlikely to cause agitation. This on-site check keeps the sampler on track and confirms that the directions provided by any secondary navigation system (i.e. grid or coordinate system using ultrasound or X-ray data) are accurate. Optionally, communication between transmitters and receivers on the camera and already advanced balloons may be used to set-off expansion of the balloons just before or as the camera passes through them. By using the visualization system to explore a region before advancing other tools the trauma to the patient is minimized. Additionally, misalignment of the patient's body with a secondary navigation system can be quickly detected when the secondary system is instructing for the sampling instruments to move into an area in which there is no abnormal tissue, as seen by the on-site camera. Finally, according to a preferred embodiment, the 360° camera is also capable of doing a U-turn to look back upon the sampling jaws of the MEDIAGOPHER™ sampling instrument from a location distal to the sampling action to watch the biopsy process as it occurs from another perspective. This ability to do a U-turn compensates for any blind spot that may otherwise exist, even with “eyes in the back” and a 360° field of view, at a point where the instrument shaft attaches to the camera (for wiring, etc.).
Copending, commonly owned U.S. provisional application Ser. No. 61/090,510 entitled “Adaptable dilation system for mediastinoscopy and method of using” (filed Aug. 20, 2008) discloses the basic elements of the balloon dilation system. Copending, commonly owned U.S. provisional application Ser. No. 61/148,916 (filed Jan. 30, 2009) specifically discloses that the balloons can be toroids or donut-shaped with hollow spaces in the center through which instruments can pass.
The present invention provides a system and method to overcome the shortcomings in the reference art by focusing on the initial access phase of a mediastinoscopy procedure for lymph node sampling. The invention can be complementary or supplementary to existing mediastinoscopy tools by improving target visualization and access prior to the insertion of resecting tools with blades, electrodes, vacuums and compartmentalized collection chambers.
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. Advantages of the invention may be realized and obtained by means of the instrumentalities and combinations particularly pointed out hereinafter.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate embodiments of the invention, and together with the general description given above and the detailed description of the embodiments given below, serve to explain the principles of the invention.
FIG. 1 is a side view of a generalized schematic representation of a multi-component dilation system of the present invention showing three expandable elements (balloons) spaced apart to dilate different regions outside of a working channel formed within a natural channel and enhanced with inflation from a proximal end of the dilation instrument.
FIG. 2 illustrates cross-sections of the toroidal balloons of the present invention according to four different shapes of exemplary embodiments: (A) double circle or donut, (B) elliptical or oblong curved, (C) irregular curved, and (D) polygon.
FIG. 3 illustrates several exemplary toroidal balloons of the present invention deployed alongside a working channel to expand against and retract sidewall tissue in order to create a working channel through their centers in which an instrument can freely operate with reduced trauma.
FIG. 4 illustrates a distal end of a sampling resecting instrument according to the present invention.
FIG. 5 illustrates various exemplary embodiments and positions for a mouth with two jaws having cutting elements thereon to resect and detach tissue to be treated or sampled. The mouth may open to different degrees from slightly (A) to severely (D) with physically sharp and/or electrically conductive elements thereon for mechanical and/or ablative cutting and/or sealing.
DETAILED DESCRIPTION OF THE INVENTION
For the access system the toroidal balloons can have any one of several shapes (including but not limited to donut, elliptical, oblong curved, irregularly curved, and polygonal) and sizes. The shape, size, and material of the balloons may be specially designed or selected depending on the shape, size, and other features of a canal, lumen, or cavity that must be dilated and through which other working instruments will be introduced. Therefore, the toroidal balloons can be chosen based on an individual's anatomy. The size of the toroidal balloons should be specially adapted to fit within the mediastinum including inside the trachea when deflated and outside the trachea when inflated. The shape, size, and material of the balloons can also be tailored to accommodate the working instruments themselves. The material and thickness chosen will influence the flexibility, strength, burst-resistance, maximum pressure, and other properties of the balloon. For example, smaller constricted passageways (trachea, bronchi, bronchioles, etc.) may need balloons of thicker or stronger material capable of withstanding greater pressure during the extent of dilation required to allow instruments to pass through them. Likewise, the balloons may be made thicker and from material with a higher resistance to bursting to accommodate bulkier instruments.
According to some embodiments, the balloons may be ribbed or textured on their surface to provide better traction (with less reliance on inflation) to stabilize them against adjacent structures.
The toroidal balloons may be deployed and activated (expanded or inflated) in any manner and to any extent that permits and facilitates the introduction of an instrument through them and reduces trauma to adjacent anatomical structures (i.e. the walls of a canal or cavity) without too much pressure from their expansion. Preferably, the balloons are deployed before the introduction of an instrument in order to dilate, expand and prepare a canal or cavity for receiving an instrument. According to one embodiment, the toroidal balloons may be deployed separately from an introducer instrument other than the instrument to be inserted through them. The introducer instrument can deploy and activate (expand) the balloons first before another sampling instrument is permitted to pass through them. The balloons can be attached to one another by string or wire and shot or propelled out of the distal end of an introducer instrument.
According to a second embodiment, the toroidal balloons may be directly connected to a cannula or directly connected to an instrument to be inserted through them. In this case the toroidal balloons may be deployed from the distal end and/or sidewalls of the cannula or instrument housing. Preferably, the cannula or instrument advances telescopically such that a balloon initially deployed from a distal tip becomes located at a sidewall as the remainder of the cannula/instrument is advanced through it and past it after expansion of the balloon. Before advancement and deployment the balloons may be stored in flaps on the outside walls of the instrument. Alternatively, balloons may be stored on the inside walls if there is a hole in the walls through which the balloons can pass to the outside, with the balloons themselves sealing the holes through which they are deployed.
The toroidal balloons absorb shock caused by manipulating instruments within them that would otherwise be absorbed by the inner walls of the lumen. By absorbing shock, the toroidal balloons reduce the sensation and soreness experienced by the patient. The balloons thereby permit a greater range of motion and force of pressure for the instruments while protecting the walls of bodily lumens and cavities from abrasion and irritation.
The present invention can be used with secondary navigation systems (other than primary navigation provided by direct on-site visualization via endoscopic camera or a surgeon's direct vision) such as those that map a coordinate grid on the body to identify and target nodes and then guide instruments in reaching them. Examples of such systems include those that incorporate ultrasound, X-rays, fluoroscopy, and/or radioactive isotopes to identify abnormal tissue and/or guide a surgeon to it. A problem with such systems is that they do not provide real-time identification or feedback. Identification and mapping typically precedes the sampling and if the body position moves or is disrupted during surgery the tracking will be off and the directions inaccurate. The camera of the present invention can be used to recognize these inaccuracies and re-establish a correspondence or tracking between the secondary navigation system and the body.
Alternatively, the 360° visualization provided by the camera of the present invention is powerful and comprehensive enough to be used alone to identify target sites for sampling without another secondary guidance system. To assist this process, one or more chemical compounds or dyes that are known to be selectively absorbed by abnormal tissue (i.e. via nanoparticle guidance or other means) can be administered in the vicinity of a target region preceding introduction of the camera. The camera that provides 360° visualization should be capable of providing this range of vision at any of several points along a trajectory extending from a region proximal to a target site, at the target site, and distally past a target site. Optionally, the camera may turn from side to side or even be capable of a complete U-turn to ensure a complete field of vision, including with backwards sight unobstructed by a “blind spot” at the point at which the extendable, bendable shaft attaches to the camera. This U-turn feature may be most useful after the camera has extended distally past the slit and the jaws, in order to look back at the slit and the jaws, such as to ensure target tissue has been effectively trapped by the jaws and, after removal, to ensure that no tissue remains caught in the jaws. The design of the jaws may include a canal therein that allows the camera shaft to remain extended through the jaws with the camera distal to the jaws while the jaws are closed. Preferably, the camera is configured to rotate about an axis along which it is extended and to articulate outside of the axis along which it is extended, including 180° U-turn articulation to look back upon the axis along which it is extended.
In its broadest form the visualization system of the present invention may be used in other surgical procedures as well and comprises a system configured to be advanced along a path from a region proximal to a target zone, through the target, to a region distal to the target zone, and to provide 360° of view from each position along the path. The target zone may be a cutting zone, a sealing zone, another type of treatment zone (such as where drugs are delivered), or a zone to be monitored.
With respect to the sampling system and the MEDIAGOPHER™ sampling instrument, the electrodes and/or physically sharp mechanical cutting elements can be integral with the jaws or formed from separate materials and embedded therein or mounted thereon. Although a two jaw PACMAN™ video game character style design is emphasized for simplicity, according to alternative embodiments, there may also be three or more pieces to the jaw structure that connect in the center when closed and open like a blossoming flower.
The access, sampling, and visualization systems of the present invention are designed to be used in modern minimally invasive surgical procedures, including endoscopic procedures and procedures that rely solely upon natural orifices for access (NOTES procedures: Natural Orifice Transluminal Endoscopic Surgery). When possible, accessing the mediastinum through the natural orifices and natural canals of the body (rather than cutting and carving out new openings and conduits) to the greatest extent practical is preferred. Avoiding external percutaneous incisions is especially preferred by patients for cosmetic reasons because it eliminates visible scars.
However, sometimes providing incisions in key locations can be advantageous to expand the range of sampling and/or improve visualization and perspective. For example, according to a preferred method of using the systems of the present invention, the instruments are inserted through the natural orifice of the mouth and then an incision is made through the trachea so that the instruments can freely move and collect samples along the outside of the trachea. This expands the range of sites that can be easily sampled. Conventional mediastinoscopy procedures involve an endotracheal tube with a small incision through the chest. These procedures can miss abnormal “exotracheal” tissue outside the trachea. It is easier to access the region outside the trachea along the way as instruments are introduced through the mouth rather than reversing direction after an incision through the chest thereby tearing up the chest to reach the outside of the trachea after an endotracheal entry.
In a preferred embodiment there is a plurality of toroidal balloons and each toroidal balloon is independently expandable and collapseable. This allows the surgeon greater control over the size and shape of the passageway created by toroidal balloon dilation. The toroidal balloons may be programmed to be inflated or collapsed sequentially, one after the next, or simultaneously all together at the same time. A combination of sequential and simultaneous inflation patterns may also be used in which the toroidal balloons within a group inflate/collapse simultaneously with respect to other toroidal balloons in the same group while the different groups of balloons inflate/collapse sequentially with respect to the other groups.
The toroidal balloons are preferably formed of an atraumatic biocompatible material including PEBAX™ block copolymer, nylon, polyester, polyvinylchloride (PVC), polyethylene terephthalate (PET), polyethylene (PE), or other materials, including combinations of any of the aforementioned materials. Different toroidal balloons may be made of different materials or of different amounts of materials (size and thickness) for different degrees of distensibility, maximum inflation pressure, volume, and/or diameter.
Different toroidal balloons can be made forwardly extendable to different degrees from the same reference point such as a distal tip of an insertion instrument. Preferably, each toroidal balloon is independently extendable and retractable. Preferably, each toroidal balloon may be steered or maneuvered radially about an axis and also turned/articulated (i.e. while extending longitudinally) at angles (to curve outside of and away from the axis of extension/advancement) to a central insertion axis after initial placement. These features permit navigation through tortuous pathways and around obstructions to allow for fine-tuning instrument position to hone in on a target sampling site.
The toroidal balloons may be used together with non-toroidal balloons without holes therein. The ordinary non-toroidal balloons can be inflated to an extent sufficient to seal off entire portions of the mediastinal cavity, thereby creating two or more distinct air and/or fluid tight compartments. These segregated compartments enable the use of gases for insufflation to collapse structures as needed to improve visualization. The compartments also make it safer and more efficient to aspirate or flush selected regions without overbroad application that risks redistributing particulates or drowning organs.
FIG. 1 shows the basic features of the dilation system according to the present invention including a working channel 101 , expandable elements (inflatable balloons) 102 , a proximal port for an inflation system 103 , and a proximal port for a visualization system 104 .
FIG. 2 shows four exemplary embodiments for the shape of the expandable elements 102 . Among other options, they may be: donut-shaped toroid 105 with both inner and outer perimeters circular; elliptical or oblong curved toroid 106 with both inner and outer perimeters curved but not circular; irregularly curved toroid 107 with both inner and outer perimeters curved and in which inner and outer perimeters may or may not be completely symmetrical such that the thickness or volume of inflated space between them may or may not be uniform around the perimeter; and polygonal toroid 108 with sharper angles at turns rather than smooth curves (alternatively and not shown, a sharp-angled toroid need not a be a regular polygon but may also be any irregular enclosed form).
FIG. 3 shows some of the different types 105 - 108 of expandable elements 102 as in FIG. 2 , with the working channel 101 worming through them. The individual ports through which each expandable element may be individually inflated through an inflation pipe in the working channel are not shown. At a distal end 115 of the working channel 101 are the sampling jaws 109 of the MEDIAGOPHER™ sampling instrument and a camera 110 at the distal end of the visualization system. Elongated shafts upon which both the sampling jaws 109 and camera no are mounted may be housed within the working channel 101 and are not shown (i.e. see camera shaft in shown in FIG. 4 ).
The distal end of the sampling instrument has a mouth that resembles the PACMAN™ video game character (circular shape like a pie or pizza but with one or more slices missing from a single region) with two or more jaws 109 having cutting elements thereon for grasping and resecting tissue. The distal end also includes a spherical camera 110 to provide 360° visualization.
FIG. 4 shows the camera 110 in three different positions relative to the sampling jaws 109 . In (A) the camera 110 is just beginning to protrude through the jaws 109 . In (B) the camera 110 has been moved distally past the jaws 109 by extension of the shaft 111 upon which it is mounted through the working channel 101 . In (C) the extendable shaft 111 , upon which the camera 110 is mounted, has been bended such that the camera 110 is turned 180° from its original position to look back upon the jaws 109 .
FIG. 5 shows the sampling jaws 109 with three different alternative types of cutting elements for severing tissue. Also, from (A) to (D) the jaws progressively move from a near completely closed position in (A) to a near completely open position in (D) as needed to receive a target (i.e. tissue, lymph nodes, etc.). In (A) and (B) the cutting elements are electrodes 112 which may also be used for sealing in addition to cutting before, during, or after cutting. Sealing assists with hemostasis. In (A) the electrodes 112 are embedded within the mouth of the jaws and in (B) the electrodes 112 are mounted on the surface inside the mouth. In (C) the cutting elements are physically sharp triangular teeth 113 that cut mechanically and may or may not also be electrically conductive for ablation. In (D) the cutting elements are physically sharp barbs 114 that cut mechanically and may or may not also be electrically conductive for ablation. Alternatively, separate electrode elements may be incorporated upon or within the sharp mechanical cutting elements or the sharp elements may be mounted upon or within the electrodes for a multifaceted (electrical and mechanical) approach to resecting and/or sealing.
The present invention is not limited to the embodiments described above. Various changes and modifications can, of course, be made, without departing from the scope and spirit of the present invention.
Additional advantages and modifications will readily occur to those skilled in the art. Therefore, the invention in its broader aspects is not limited to the specific details and representative embodiments 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. | The present invention provides various systems, a kit, and a method for accessing, sampling within, and visualization of areas within the mediastinal cavity for assisting a surgeon in performing a mediastinoscopy procedure. The access system includes one or more preferably toroidal balloons that can be expanded to dilate and protect the inner walls of a bodily conduit. Instruments pass through hollow spaces within the expanded toroidal balloons. The proximally positioned balloons are expanded first and the unexpanded balloons to be positioned distally are passed through them and subsequently expanded. The sampling system includes an instrument with a rounded head having two or more jaws and a slit therein at the distal end of an elongated tubular body. The visualization system includes a 360° camera that can be positioned from proximal to distal a target site and can also do a U-turn about its axis of extension. | 0 |
Background of the Invention
This invention relates to a modification of the surface of finely divided particulate matter such that it has a stronger affinity for cellulose fibers. More specifically, the invention involves the charge reversal of finely divided pigments and fillers such as clay, titanium dioxide, calcium carbonate, silicas and silicoaluminates by treating these fillers and pigments with a water soluble cationic polyamide resin.
These fillers and/or pigments are typically used in the papermaking industry to improve the optical and physical properties of the sheet. In some instances, the cost of manufacturing the paper will decrease because the fillers are often less costly than the fiber.
The introduction of fillers and/or pigments by wet-end addition (before a sheet is formed) requires their effective deposition on fibers suspended in water. Since most of the fillers and/or pigments are negatively charged, they do not deposit on the similarly charged pulp fibers without the addition of some retention aids and careful process control. The deposition of these fillers and pigments is enhanced if the fillers or pigments are rendered cationic.
These fillers or pigments can be rendered cationic by various standard techniques including utilizing inorganic salts, cationic surfactants, natural polymers, and polyethylenimine.
While capable of rendering the fillers or pigments cationic, these techniques can deleteriously affect the characteristics of the fillers or pigments. Some of the characteristics affected include wetting properties of the filler material, foaming tendency, wet strength, dry strength, ink penetration, and sizing. Another disadvantage of these methods can be that the filler or pigment will only retain its cationic character over a narrow pH range.
Polyethyleneimine has been used most often to render fillers and pigments cationic. The cationic charge on polyethyleneimine is high at low pH and becomes much less substantial at higher pH. Treating a filler or pigment with such a weak polymer will render the filler or pigment cationic at low pH while at high pH the charge will return to that of the mineral's surface. Many times this causes the mineral to be amphoteric rather than truly and strongly cationic.
U.S. Pat. No. 3,804,656 discloses a process for making cationic clays and other fillers utilizing a combination of nonionic and cationic surface active agents in conjunction with a strong base. The patent notes at column 2, lines 52-54, that cationic surfactants used alone are incapable of providing predispersed aqueous pigment suspensions having suitable rheological properties. In addition to requiring the use of a nonionic surfactant, the patent also requires the presence of a strong base. In contrast, the present invention utilizes only a cationic dispersant and does not require the presence of a strong base.
An article by von Raven, Strittmatter and Weigl in Tappi, J. Dec. 1988) pp. 141-148, entitled "Cationic Coating Colors-A New Coating System" describes a method for producing cationic coating pigments such as CaCO 3 , kaolin, and talcum at relatively high solids by utilizing cationic dispersing agents such as quaternary ammonium compounds; polyamine-amide fatty acids compounds, and highly degraded cationic galactomannans of low molecular weight.
Chem Abstract 112:38499p discloses cationic polymers obtained from a polyethylene glycol polyhalohydrin ether by the reaction with 0.1 to 10,000 parts aziridine compounds and polyamines mixed with pigment for use as paper coating.
Neither the von Raven article nor the Chem Abstract reference disclose the specific polymers containing cyclic quaternary functional groups as utilized in the present invention.
U.S. Pat. 4,874,466 discloses a papermaking filler composition comprising a pigment, preferably titanium dioxide, and a cationic water soluble polymer selected from the group consisting of polymers comprised of at least 50% by weight of repeating units consisting of a quaternary ammonium salt moiety and from 2 to 10 carbon atoms, wherein the carbon atoms form alkyl or aryl moieties or combinations of alkyl and aryl moieties which may be substituted with hydroxy amine or halide, and polyaluminum chloride and mixtures thereof. This treatment imparts a positive charge to the titanium dioxide. The patent does not disclose the use of other materials such as clays or silicoaluminates.
European Patent Application 382427A2 filed on Feb. 2, 1990, discloses a stable fluid acidic slurry comprising particles of calcined kaolin containing a dispersant of a water soluble cationic quaternary ammonium polymer salt in an amount imparting a positive zeta potential to the pigment. The use of quaternary ammonium cationic polyelectrolytes obtained by copolymerizing aliphatic secondary amines with epichlorohydrin is disclosed. This reference does not utilize the same type of fillers or pigments as the present invention.
Accordingly, some of the objects of this invention are to be able to render fillers and pigments cationic at high solids concentrations, maintain a cationic zeta potential throughout all applicable pH values, and provide fillers and pigments which have enhanced retention on the fibers in a cost effective manner.
Description of Figures
FIG. 1 shows the breakover curve and zeta potential curve for Klondyke clay treated with Polymer A.
FIG. 2 shows the breakover curve and zeta potential curve for Rutile TiO 2 treated with Polymer A.
FIG. 3 shows the breakover curve and zeta potential curve for CaCO 3 , treated with Polymer A.
FIG. 4 shows the breakover curve and zeta potential curve for bentonite clay, treated with Polymer A.
FIG. 5 shows the breakover curve for Hydrafine clay treated with Polymer A.
FIG. 6 shows the breakover curve and zeta potential curve for Klondyke clay treated with Polymer D.
DESCRIPTION OF THE INVENTION
The present invention involves the charge reversal of finely divided pigments and fillers such as clays, TiO 2 , CaCO 3 , silicas, and silicoaluminates. This is accomplished by adsorbing water soluble cationicpolyelectrolyte polymers at the filler/pigment solution interface.
In general, cationic water soluble polymers composed of the reaction product of epichlorohydrin and compounds containing cyclic quaternary functional groups are suitable for use in effecting the charge reversal ofthe present invention. These cyclic groups can be four-membered azetidiniumions containing the structure ##STR1##where R 1 and R 2 are residues of the polymer chain, or can be five-membered cyclic quaternary ions having the structure ##STR2##where R is a C 1 to C 5 alkyl group.
Preferably, R is a C 1 to C 3 alkyl group. It is thought that 30 to80% cyclic quaternary groups will be effective for cationizing fillers and pigments. Preferably the compound has 50 to 80% cyclic quaternary groups. Examples of the cationic polymers used in the present invention are: (1) the reaction product of methyldiallylamine and epichlorohydrin; and (2) the reaction product of a polyalkylene amine compound such as bis(hexamethylenetriamine) (BHMT) and epichlorohydrin. The cationic polymers used in the examples which follow are described below:
Polymer A-the reaction product of BHMT and epichlorohydrin.
Polymer B-the reaction product of epichlorohydrin and an aminopolyamide derived from adipic acid and diethylenetriamine
Polymer C-the reaction product of a condensate derived from the reaction ofdiethylenetriamine, and cyanoguanidine, then reacted with epichlorohydrin.
Polymer D-the reaction product of methyldiallylamine and epichlorohydrin.
In accordance with the present invention, a 20 to 60 wt. % solids cationic filler dispersion is prepared as follows:
1. disperse the cationic polymer in an appropriate amount of water,
2. stir the mixture for about 2 minutes using an electric stirrer with a Cowles blade,
3. sprinkle filler into mixture while stirring until the appropriate amountof filler has been added,
4. allow the dispersion to stir for about 30 minutes after all the filler has been added,
5. measure the viscosity and/or zeta potential. The cationic polymer is present in the amount of from about 0.1 to 8 wt. % based on the pigment offiller.
The magnitude and sign (positive or negative) of the electrical charge on the particles cited in the examples and elsewhere herein are measured using the Lazer Zee meter, Model 501, a product of Pen Kem, Inc. The measurement involves the determination of the velocity of migration of charged particles under a known potential gradient. The measurement is carried out in a dilute suspension of the slurry. From the measured electrophoretic velocity, the particle charge (zeta potential) can be calculated. Cationic and anionic particles migrate in opposite direction at velocities proportional to the charge. Other methods of measuring the magnitude and sign of the electrical charge on the particles can be used.
Typically when concentrated anionic dispersions of fillers are titrated with a cationic polymer, as described above, the viscosity will increase drastically. If the molecular weight of the cationic polymer is not too high and it functions as a dispersant, further addition of the cationic polymer may reduce the viscosity to produce a "redispersed system". This curve of viscosity vs. concentration of cationic polymer will usually havea high maximum viscosity which occurs in the range of the point of zero charge when the particles have their charge neutralized. Once the particles begin to show a positive charge, the viscosity also begins to decrease due to redispersion. This viscosity curve has been termed a "breakover" curve. Examples of these breakover curves are illustrated by FIGS. 1 to 6.
The following examples illustrate the present invention.
EXAMPLE 1
A kaolin type clay known as Klondyke clay is treated with the reaction product of bis(hexamethylenetriamine) and epichlorohydrin (Polymer A). Klondyke clay is normally used as a filler clay and has a larger particle size than clay used for paper coatings.
The Klondyke clay is treated as follows with Polymer A to make it cationic:
a) 30 g of Klondyke clay is dispersed in 100 ml of water,
b) 0 to 0.7% of Polymer A per unit weight of clay is added incrementally,
c) the dispersion is stirred for about 30 minutes.
Viscosity and zeta potential measurements were made at this point.
FIG. 1 shows the breakover curve (solid curve) and the zeta potential curve(dashed curve) for Klondyke clay. The breakover curve goes through a breakover maximum and then the viscosity decreases. The Klondyke clay is dispersed at about 29% solids. Aliquots were taken periodically and diluted to measure the zeta potential. The dashed curve of FIG. 1 shows zeta potential measurements which have been made on diluted aliquots from the concentrated samples used for the breakover curve.
In the first part of the breakover curve, the viscosity is increasing whilethe negative zeta potential is tending toward zero. The maximum viscosity occurs close to the point of zero charge. Past this point redispersion begins to occur and the viscosity decreases again. At about 0.5 mls of Polymer A, the viscosity is minimal and the zeta potential is greatest. This is the point of maximum dispersion. At this point, the viscosity is lower than the initial viscosity.
EXAMPLE 2
TiO 2 is made cationic by treatment with the polymers in accordance with the present invention. Rutile TiO 2 is treated with Polymer A as follows:
a) 30 g of Rutile TiO 2 are dispersed in 100 ml of water,
b) 0 to 0.4% of Polymer A per unit weight of clay is added incrementally,
c) the dispersion is stirred for about 30 minutes.
The viscosity is measured and a breakover curve generated.
FIG. 2 shows the breakover curve (solid curve) and the zeta potential curve(dashed curve) for Rutile TiO 2 . The viscosity of the final dispersion is much lower than the initially dispersed material. This suggests that very highly concentrated slurries of TiO 2 may be possible by using Polymer A. Cationic TiO 2 has increased retention and enhanced opacifying efficiency.
EXAMPLE 3
FIG. 3 shows the breakover curve (solid curve) and the zeta potential curve(dashed curve) for a commercially available CaCO 3 paper filler sold byOMYA, Inc. under the trade name Hydracarb. The Hydracarb is treated with Polymer A and is prepared in a similar fashion to Examples 1 and 2. 30 g of Hydracarb is dispersed in 100 ml of water and stirred. 0 to 0.7% of Polymer A per unit of Hydracarb was added incrementally. The viscosity is then measured. The curve shows a typical breakover. Complete redispersion seems to occur at about 0.6 ml (0.5%) or greater.
As shown by Examples 1 to 3, the present invention can be utilized to render inorganic particles cationic. Some of the uses for these cationic particles are in paper coatings, fillers and pigments.
EXAMPLE 4
This example illustrates the cationic character of treated kaolin over an acid to alkaline pH range. A 10% dispersion of kaolin clay, a low ion exchange capacity clay which does not swell much in water, is dispersed byultrasonication in water at neutral pH. The zeta potential is measured witha Lazer Zee Meter® as previously described. Untreated kaolin had a zetapotential of -31 mvolts. After treatment of the kaolin dispersion with the cationic polymers the charge reversal shown in Table 1 was observed.
TABLE 1______________________________________ Zeta PotentialPolymer % Treated pH (m volts)______________________________________A.sup. 5% 4.1 +63 6.1 +56 9.0 +53B.sup.1 5% 4.1 +63 6.0 +51 9.3 +37C.sup.2 15% 4.1 +63 6.0 +65 8.9 +54______________________________________
As the results indicate, polymers A and C are quite stable at about pH 4 toabout pH 9. Polymers A and C preserve much of their charge at high pH whereas polymer B has many weak amine groups, consequently its zeta potential drops at high pH.
EXAMPLE 5
Bentonite is an example of a high ion exchange capacity clay. It is classified in the montmorillonite family. Bentonite, especially in the sodium exchanged form, swells dramatically in water. When this is allowed to occur, it is very difficult to neutralize the charge by adsorbing an ionic species. It would therefore be even more difficult to reverse the charge of bentonite especially after the clay is hydrated.
A cationic bentonite slurry at 2% solids is prepared by conventional means.Polymer A is added to the clay suspension in increments; at each addition, the suspension is stirred for 10 minutes and the viscosity and zeta potential are measured. The results are shown in Table 2.
TABLE 2______________________________________Polymer A/Clay Viscosity @ 20 rpm Z.P., mv______________________________________no Polymer A 25 -38.90.0095/g.clay 30 -23.60.019/ 110 -11.40.038/ 82 +8.90.057/ 78 +21.20.076/ 12 +30.2______________________________________
When Polymer A was added to the water before the addition of the clay, the clay would not disperse, instead it would settle out. A redispersed, cationic form of bentonite is achieved at 0.076 g Polymer A/g clay or 7.6%.
The breakover (solid curve) and zeta potential (dashed curve) curves are shown in FIG. 4.
The cationic bentonite is then used as a filler in a newsprint handsheet experiment at a 3% loading. Table 3 illustrates the properties of the newsprint when cationic bentonite is used as a filler.
TABLE 3______________________________________ Filler Dry WetSample Retained Brightness Opacity Tensile Tensile______________________________________Control 48.7 67.1 11.1 0.52(Newsprint)bentonite 84.3% 48.4 68.5 4.8 0.30cationic 93.8% 48.2 67.7 11.7 0.55bentonite______________________________________
The retention is increased and the tensile properties were returned. Actually, the tensile properties were enhanced which is the opposite of what is expected when any filler is used.
Cationic bentonites may also be useful as scavengers for anionic trash and as microparticulate retention aids.
EXAMPLE 6
A cationic paper coating is formulated by rendering the coating pigment cationic and using a cationic viscosifier binder. Hydrafine clay, a conventional coating clay having a particle size of 90 to 92 wt. % less than 2 microns available from J. M. Huber Corporation, Clay Division, is treated as follows to make it cationic.
132 g of Hydrafine clay is added to 510 g of water and stirred with a Caframo stirrer equipped with a Cowles blade. After all the clay is added,18 g of Polymer A (38% solids) is added to the slurry and mixed for 10 minutes. The clay Polymer A slurry is centrifuged for 30 minutes at 2500 rpm and the supernatant is decanted. The centrifugate is dried in an oven at 105° C. for 4 hours. The sample is then cooled and ground with amortar and pestle. This dried clay is then used to prepare a 60% solids dispersion (120 g of Polymer A treated clay in 80 g of distilled water).
The treated clay is then made into a cationic paper coating as follows.
Eight parts Staley J-4 starch/100 parts clay are added to the Hydrafine clay slurry to obtain a Brookfield viscosity of 2000 cps at 100 rpm (used spindle #6). An aliquot of the coating is diluted to take a zeta potentialmeasurement on a Lazer Zee Meter, model 501. The zeta potential is measuredas +40.9 mvolts, indicating a highly cationic character.
The breakover curve is shown in FIG. 5.
EXAMPLE 7
A measured amount of silica or silicate pigment is added, with stirring, todistilled water to form a certain solids content dispersion as shown in Table 4. The dispersions are stirred for 30 minutes. Polymer A is incrementally added to the pigment dispersion. At each addition, the dispersion is stirred for 10 minutes and the zeta potential is measured. The silica or silicate shown by trade name in Table 4 are commercially available from the J. M. Huber Corporation. They are all synthetic amorphous precipitated silicas or silicates. Zeofree 80 is silicon dioxide, Hydrex and Huberfil 96 are sodium magnesium aluminosilicates, andHysnap is sodium magnesium alumino and aluminum silicate.
TABLE 4______________________________________ Wt. % of Wt. ofSilica or Silicate Polymer/Pigment Z.P., mv. % Solids______________________________________Zeofree 80 0 -25.1 10 0.56% 0 0.76 +14.4 7.6 +25.6Huberfil 96 0 +8.1 20 0.21% +21.1Hydrex 0 -34.5 20 0.84% 0 1.14 -10.8 1.67 +21.2Hysnap 943 0 -25.3 20 0.61% 0 0.85 +12.7 1.06 +23.4______________________________________Treatments needed to achieve +20 to +25 may vary from 0.2% to 7.6%. Most treatments are less than 2%.
Zeolex 23P® is a commercially available sodium aluminosilicate from J. M. Huber Corporation which can also be rendered cationic with Polymer A. When this is used in newsprint at 3% loading as a filler, the opacity and the wet tensile are enhanced as shown in Table 5.
TABLE 5______________________________________ Dry WetSample % Ash Brightness Opacity Tensile Tensile______________________________________Control 0.58 48.7 67.1 11.1 0.52(newsprint)Zeolex 23P 1.57 49.4 68.0 11.8 0.54cationic 1.59 49.1 69.0 11.8 0.65Zeolex 23P______________________________________
EXAMPLE 8
This example illustrates the cationization of a Kaolin type clay with the reaction product of methyldiallylamine and epichlorohydrin (Polymer D). A clay slurry having a final concentration of 50% solids is prepared and treated as described in example 1 with the amount of Polymer D shown in Table 6 below. The zeta potential of each sample is determined and shown in Table 6. FIG. 6 illustrates the zeta potential curve based on the data presented in Table 6.
TABLE 6______________________________________Polymer Dg/g clay pH Z.P. (mv)______________________________________0 6.3 -43.90.00388 +13.50.00776 +21.40.01163 +25.70.01551 6.55 +27.40.01939 6.5 +29.60.02327 +29.40.02715 +27.30.03103 +27.20.03490 +30.10.03878 +30.80.04266 +31.8______________________________________
While this invention has been described with respect to particular embodiments thereof, it is apparent that numerous other forms and modifications of this invention will be obvious to those skilled in the art. The appended claims and this invention generally should be construed to cover all such obvious forms and modifications which are within the true spirit and scope of the present invention. | Fillers and pigments, such as clay, titanium dioxide, calcium carbonate, silicas, and silicoaluminates, can be rendered cationic by treating the fillers or pigments with the reaction product of a polyamine or polyamide and epichlorohydrin. The resulting water soluble cationic fillers or pigments are useful in the paper industry as fillers for paper and can also be utilized in coating paper. | 3 |
FIELD OF THE INVENTION
[0001] The present invention relates to a method for interpreting a plurality of m-dimensional attribute vectors (m≧2) assigned to a plurality of locations in an n-dimensional interpretation space (n≧1). The interpretation space can in particular represent a subsurface formation. The invention can be used in a method of producing hydrocarbons from a subsurface formation.
BACKGROUND OF THE INVENTION
[0002] The interpretation of a large amount of data obtained for an interpretation space can be a very complex task. A particular example is the analysis of seismic and sometimes other data obtained for a subsurface formation, in order to allow discrimination among regions and layers of particular properties. The expression ‘subsurface formation’ is used herein to refer to a volume of the subsurface. A volume of the subsurface typically contains a plurality of layers. The subsurface formation can in particular include one or more layers containing or thought to contain hydrocarbons such as oil or natural gas, but it can also and even predominantly include other layers and geological structures.
[0003] Frequently, two or more data sets are available, each providing values of a distinct scalar parameter for different locations throughout the interpretation space. It is desired to interpret these data sets in conjunction so as to identify certain classes of regions in the interpretation space.
[0004] In the case of interpreting data obtained for a subsurface formation, so-called Amplitude Variations with Offset (AVO) technology is frequently applied. In the article “Successful AVO and Cross-Plotting” by S. Chopra, V. Alexeev and Y. Xu, GSEG Recorder, November 2003, p. 5-11, cross-plotting is discussed as a technique enabling simultaneous and meaningful evaluation of two attributes. In conventional cross-plotting, the values of two separate scalar parameters (attributes) belonging to a particular location in the interpretation space (in the subsurface formation) are plotted as a point in a separate two-dimensional space which can be referred to as attribute space. The two dimensions of the attribute space represent the two attributes considered.
[0005] In Example 1 of the Chopra article, the interpretation space is 1-dimensional along the trajectory of a wellbore through a subsurface formation. Along the wellbore, several well-log parameters (attributes) have been measured or derived from measurements, e.g. P-velocity V p , S-velocity V s , Rho, Mu, and Lambda (the Lamé parameters, representing respectively the bulk density, the shear modulus, and the compressional influence on the elastic moduli). 2-dimensional cross-plots of V p vs. V s , Lambda-Rho vs. Mu-Rho are presented, and also two cross-plots in which a three-dimensional attribute space was used. Geologic layers are identified along the wellbore, and in the cross-plot the points representing data from a specific type of geologic layer are plotted with a specific colour. In the cross-plot, clusters of points having mainly or exclusively the same colour can be seen. Conversely, by drawing a polygon around each of the clusters the operator can mark log zones along the well from which these data points originated.
[0006] A particular embodiment of the polygon method is discussed in a paper by P. Brenton and O. D. Duplantier “When Geology meets Geophysics—optimised Lithoseismic Facies Cubes for Reservoir Needs”, EAGE 68 th Conference & Exhibition—Vienna, Austria, 12-15 Jun. 2006. In this paper, polygons drawn to separate facies groups in a cross-plot of log data are updated using petrophysical data. The occurrence probability of certain petrophysical parameters such porosity in certain facies or groups of facies is statistically analysed, and used to refine the facies group definition by polygon boundaries in the cross-plot. After the refined polygons have been determined, a 3D visualization of the result in interpretation space is done by the geologist.
[0007] There is a need for an improved interpretation method. In complex situations, such as when the distributions of the various classes are under-sampled or overlapping, and in particular when no or only few petrophysical data are available, the operator cannot confidently draw the polygons to distinguish among several classes of data. Also, when considering an attribute space with three or even more dimensions, the polygon method is insufficient.
[0008] It will be understood, that vector data can be considered as an assembly of scalar data, in particular scalar datasets for a corresponding plurality of locations. In particular, attribute vectors can always be considered to represent an assembly of co-located scalar datasets.
SUMMARY OF THE INVENTION
[0009] In accordance with the invention there is provided a method for interpreting a plurality of m-dimensional attribute vectors (m≧2) assigned to a plurality of locations in an n-dimensional interpretation space (n≧1), which method comprises the steps of
[0010] arranging at least a subset of the attribute vectors as points in an m-dimensional attribute space;
[0011] defining k classes (k≧2) of attribute vectors by identifying for each class at least one classification point in attribute space;
[0012] postulating a classification rule for points in attribute space;
[0013] determining a class-membership attribute of a classified point in attribute space using the classification points and the classification rule to obtain a classified point, wherein the class-membership attribute of the classified point comprises k probabilistic membership values, each representing a probability that the classified point belongs to a selected one of the k classes; and
[0014] assigning a display parameter to the classified point which is related to the class-membership attribute, wherein the display parameter is a mixed display parameter derived from the probabilistic membership values.
[0015] In the method of the invention, k classes are defined through classification points in attribute space. One or more such classification points per class are identified in the attribute space. Depending on the information available to the operator, the identification can be done by a selection directly in attribute space, or by identifying a location in interpretation space that is known or expected to belong to a particular class. In the latter case, the attribute vector belonging to the selected location is thereby identified as the classification point needed to define the particular class.
[0016] Once this definition of classes is completed, a class-membership attribute is determined for each classified point, on the basis of the identified classification points, and of a classification rule that has been postulated for points in space, typically for any point in the attribute space considered.
[0017] In a particular embodiment of the method, defining a class comprises assigning a probability density function to the class, so that the class-membership attribute of the classified point can be determined from the probability density functions of the classes. The probability density function indicates the probability that a point in attribute space belongs to a given class. More in particular, the class-membership attribute of the classified point comprises k probabilistic membership values each representing a probability that the classified point belongs to one of the classes given the attribute values at that point.
[0018] Once an initial classification of points in attribute space has been obtained, an operator can update (adapt or “fine-tune”) the definition of classes, in particular interactively, in one or more iterations, wherein the updating in a next iteration is done in response to the result obtained from one or more previous iterations. Updating can be done by revising earlier choices, or by applying an algorithm such as Expectation-Maximization or K-means, as for example described in M. W. Mak, S. Y. Kung, S. H. Lin; “Expectation-Maximization Theory”, Biometric Authentication: A Machine Learning Approach, Prentice-Hall, 2004.
[0019] On the basis of the class-membership attribute, a display parameter is assigned to each of the points in attribute space. The mixed (“blended”) display parameter can in particular be a mixed colour. Suitably, a k-dimensional attribute-to-colour map or table is used for displaying at least part of the interpretation space and/or attribute space.
[0020] Suitably at least part of the attribute space is displayed together with displaying at least part of the interpretation space. Displaying the classified points in attribute space and at least in part of the interpretation space at the same time, using the mixed display parameter, on one or more computer displays, allows in particular to update the definition of classes in response to the display interactively.
[0021] In a further aspect of the invention there is provided a method for interpreting a plurality of m-dimensional attribute vectors (m≧2) assigned to a plurality of locations in an n-dimensional interpretation space (n≧1), which method comprises the steps of
[0022] arranging at least a subset of the attribute vectors as points in an m-dimensional attribute space;
[0023] defining k classes (k≧2) of attribute vectors by identifying for each class at least one classification point in attribute space;
[0024] postulating a classification rule for points in attribute space;
[0025] determining a class-membership attribute of a classified point in attribute space using the classification points and the classification rule;
[0026] assigning a display parameter to the classified point which is related to the class-membership attribute; and displaying the classified points in attribute space and at least in part of the interpretation space at the same time, using the display parameter, on one or more computer displays.
[0027] The simultaneous display of attribute space and at least part of the interpretation space allows the beneficial interactive updating of the classification by an operator of the method. The number of classes as well as classification points can be adapted using both interpretation and attribute spaces. Classification rules can also be adapted and the results are immediately visible.
[0028] In a particular embodiment, defining a class comprises assigning a probability density function to the class, so that the class-membership attribute of the classified point can be determined from the probability density functions of the classes. More in particular, the class-membership attribute of the classified point comprises k probabilistic membership values each representing a probability that the classified point belongs to one of the classes given the attribute values at that point.
[0029] In another embodiment, the class-membership attribute of the classified point is determined from the location of the classified point with respect to the classification points, for example on the basis of the distance in attribute space from the classified point to the various classification points.
[0030] The invention also provides a computer program product for interpreting a plurality of m-dimensional attribute vectors (m≧2) assigned to a plurality of locations in an n-dimensional interpretation space (n≧1), which computer program product comprises
[0031] computer program code means for arranging at least a subset of the attribute vectors as points in an m-dimensional attribute space;
[0032] computer program code means for defining k classes (k≧2) of attribute vectors by identifying for each class at least one classification point in attribute space;
[0033] computer program code means for postulating a classification rule for points in attribute space;
[0034] computer program code means for determining a class-membership attribute of a point in attribute space using the classification points and the classification rule to obtain a classified point, wherein the class-membership attribute of the classified point comprises k probabilistic membership values, each representing a probability that the classified point belongs to a selected one of the k classes; and
[0035] computer program code means for assigning a display parameter to the classified point which is related to the class-membership attribute, wherein the display parameter is a mixed display parameter derived from the probabilistic membership values.
[0036] The invention moreover provides a computer program product for interpreting a plurality of m-dimensional attribute vectors (m≧2) assigned to a plurality of locations in an n-dimensional interpretation space (n≧1), which method comprises the steps of
[0037] computer program code means for arranging at least a subset of the attribute vectors as points in an m-dimensional attribute space;
[0038] computer program code means for defining k classes (k≧2) of attribute vectors by identifying for each class at least one classification point in attribute space;
[0039] computer program code means for postulating a classification rule for points in attribute space;
[0040] computer program code means for determining a class-membership attribute of a classified point in attribute space using the classification points and the classification rule;
[0041] computer program code means for assigning a display parameter to the classified point which is related to the class-membership attribute; and
[0042] computer program code means for displaying the classified points in attribute space and at least in part of the interpretation space at the same time, using the display parameter, on one or more computer displays.
[0043] There is furthermore provided a computer system executing any one of these computer program products.
[0044] The invention also provides a method of producing hydrocarbons from a subsurface formation, comprising
[0045] obtaining a plurality of m-dimensional attribute vectors (m≧2) for a plurality of locations in an interpretation space representing the subsurface formation, each attribute vector characterizing at least two parameters of the subsurface formation at the respective location;
[0046] interpreting the plurality of attribute vectors according to the method of interpreting a plurality of attribute vectors of the present invention;
[0047] identifying a region in the subsurface formation containing a hydrocarbon reservoir using the interpretation;
[0048] producing hydrocarbons from the hydrocarbon reservoir.
BRIEF DESCRIPTION OF THE DRAWINGS
[0049] The invention will now be described in more detail and with reference to the accompanying drawings, wherein
[0050] FIGS. 1 a and 1 b show schematically a 3-dimensional interpretation space and an attribute space, respectively, with data points (crosses) and classification points (filled symbols) indicated;
[0051] FIGS. 2 a and 2 b show schematically a 3-dimensional interpretation space and an attribute space, respectively, with classification points and classified points (open symbols) indicated;
[0052] FIGS. 3 a and 3 b show schematically a 3-dimensional interpretation space and an attribute space, respectively, after a so-called “hard” classification, in which each attribute vector is assigned to belong entirely to only one of the several classes;
[0053] FIGS. 4 a and 4 b show schematically a 3-dimensional interpretation space and an attribute space, respectively, with probabilistic classification of the classes in the attribute space, in which each attribute vector may have partial membership in more than one class.
[0054] FIG. 5 shows a particular display of several cross-sections through a 3-dimensional interpretation space with events.
[0055] Where the same reference numerals are used in different Figures, they refer to the same or similar objects.
DETAILED DESCRIPTION OF THE INVENTION
[0056] Reference is made to FIGS. 1 a and 1 b . FIG. 1 a shows a 3-dimensional interpretation space, and for the purpose of illustration it will be assumed that it is a space in the earth's subsurface. So the three axes relate to co-ordinates x,y,z (spatial), or x,y,t, since the “vertical” dimension is frequently displayed in units of seismic travel time. The interpretation space can be any n-dimensional volume of a physical space. The interpretation space could also have for example two or one dimension(s), if data are obtained only in less than three dimensions such as in a plane or along a trajectory such as a wellbore.
[0057] For a large number of locations P in the interpretation space, where a cross is indicated in FIG. 1 a , data are available or obtained, perhaps even continuously throughout the space. For the method of the invention, at least two data sets are considered, which can for example originate from different measurements, or from different parameters derived via processing of raw data from the same measurement(s). Each data set represents values of a specific attribute. The data can be available in any form, for example it can be stored in a computer's memory or on a mass storage medium, in different scalar data sets for the volume of interpretation space considered. It can also be stored as vector data, in which the individual vector components correspond to the various attributes.
[0058] Whatever the physical storage of data for the various attributes, to each of a plurality of locations in the interpretation space m attributes are assigned, which is considered assigning an attribute vector, having the m respective values of the attributes as components, to the respective locations. The attribute vectors typically represent data such as raw or processed physical data that are obtained or available for locations in the interpretation space. The crosses in FIG. 1 a are to illustrate the attribute vector assigned to the respective location. In the present example we will consider the specific case of m=2 attributes, mainly for the ease of illustration, but 3 or more attributes can be handled in the same way. The two attributes considered are aa and bb, and examples are near- and far-offset reflectivity; lambda-rho and mu-rho; shear- and compressional-wave impedance; local amplitude envelope and semblance; local dip magnitude and azimuth; gravity-derived density and seismic-derived interval velocity.
[0059] FIG. 1 b shows the two-dimensional attribute space having aa and bb as axes.
[0060] Attribute vectors assigned to locations P in the interpretation space are then arranged in attribute space. This can be all the attribute data available, or only part thereof. For example, only attribute vectors assigned to specific part or region of the interpretation space can be arranged in attribute space, such as from a slice from the 3-dimensional interpretation space. The crosses in FIG. 1 b illustrate the attribute vectors arranged in attribute space.
[0061] In a next step, k classes of attribute vectors (k≧2) are defined. To this end, for each class at least one classification point is identified in attribute space. This is illustrated in FIG. 1 b by the solid square, circle and triangles. These are shown taking the place of an ordinary cross, but this is not needed in general—a classification point can be defined in attribute space independent on the availability of actual data for that point. Experience from analysing geophysical data has shown that subsurface structures such as a particular lithology, fluid fill, facies, can often be characterized in attribute space by a certain region of attribute values. The practical difficulty is, however, how to determine the boundaries of such region.
[0062] For the purpose of illustration, FIG. 1 b shows three well-separated clusters of attribute vectors, and each cluster contains one or more classification point(s) that define the classes. The selection of classification points for certain classes in attribute space can be based on, for example, the operator's observations of the data, or his understanding of the meaning of a region in attribute. It is important to note, however, that identification of classification points can also be done through interpretation space. If for example it is known to the operator that the location of the solid square in FIG. 1 a is a type-case for a particular class of a subsurface feature, the attribute vector assigned to this location may be used to define that class. Such knowledge can for example come from log data available for that location. Another point to note is that several locations in interpretation space can happen to have the same attribute vector, as illustrated by the circles in FIGS. 1 a and 1 b . By selecting the point of the circle in attribute space, or one of the locations of the circles in interpretation space, all the other occurrences of the solid circle are likewise identified.
[0063] In the polygon method discussed in the Chopra article, the operator would now draw a polygon around each of the clusters to complete the classification. In more complicated cases than the illustrative example here, drawing a particular boundary may be misleading, since its location is highly subjective and uncertain. With the method of the present invention the uncertainty can be represented instead of ignored.
[0064] According to the present invention, a classification rule for points in attribute space is postulated. For the classification of a point in attribute space, a class-membership attribute is assigned to that classified point. The class-membership attribute is determined on the basis of the classification points and the classification rule.
[0065] The classification rule can take many forms. In a relatively straightforward embodiment, a point can be classified on the basis of the distance defined in attribute space from the classification points. For example, it can be taken to belong to the class of the nearest classification point.
[0066] The result of such classification is shown in FIGS. 2 a,b , wherein the attribute vectors at classified points (open symbols) in attribute space are assigned to the class of the nearest classification point (solid symbols).
[0067] In more sophisticated embodiments, one can work with probabilities. To this end a probability density function can be assigned to the class, describing the probability that a point in attribute space belongs to the given class as identified by the classification point(s) of that class. When such a probability density function is defined for each of the k classes, k probabilities can be determined for a classified point representing the likelihood of belonging to a selected one of the classes. Bayes' formula discussed below can be used in this process. The class-membership attribute can in such case comprise the plurality of fractional probabilities, e.g. in form of a vector of probabilities, having the dimension k for k classes.
[0068] A probability density function can assume many functional forms. A convenient approach is based on Gaussian functions, in particular a Gaussian Mixture Model also known as sum of Gaussians. With a mixture model any probability function can be represented with arbitrary accuracy (e.g. by increasing the number of classification points), and easily visualized, both conceptually and practically. The Mixture Model is easily generalized to other kernels than the Gaussian functions.
[0069] Formally, the conditional probability density function p(a|c) for an attribute vector a to belong to class c can be denoted as
[0000]
p
(
a
|
c
)
=
∑
j
w
j
g
θ
j
(
a
)
[0000] wherein g designates a kernel density function such as a Gaussian function. Here, the class c is characterized by a weighted sum of Gaussians over the attribute space. The weights w j suitably sum to 1, and each can be interpreted as the prior probability associated with the j-th kernel. Parameters such as centroid and standard deviation of a Gaussian are symbolized by θ j .
[0070] Whatever functional form postulated for p(a|c), Bayes' formula yields the “posterior” class-membership probability p(c|a) for a given attribute vector a to belong to a particular class c of a set of classes p(c|a)=p(a|c)p(c)/p(a),
[0071] wherein p(a) is a normalizing factor readily obtained by the summation of p(a|c)p(c) over all classes c, and where p(c) is the a priori probability to observe class c irrespective of the attribute value a or any available data, as presumed by the operator.
[0072] It is not necessary, nor even advisable in all circumstances, that the defined classes cover the entire classification space. In can be beneficial to include an “anything else” class, for example having a quasi-uniform probability density function and a prior probability selected as an a priori risk of encountering an unclassifiable point.
[0073] So far, we have assumed that the parameters of the probability density function are known and fixed by the operator. In many cases however, the operator has no such certainty and desires to estimate model parameters from any data available. After an initial selection, the classification is to be updated, if needed iteratively, to find a useful representation of the interpretation space.
[0074] Updating can be done manually by e.g. adapting the selection of classification points, the parameters such as Gaussian parameters assigned to one or more classes, or in fact the classification rules. A particular way to update more objectively is the so-called Expectation-Maximization (EM) algorithm, which is very generic—a special case being the so-called k-means clustering method—enabling a broad suite of statistical pattern recognition methods to be deployed in the framework of the present invention. The EM algorithm has some desirable mathematical properties; such has guaranteed convergence to likelihood maxima of the parameters being estimated. In combination with the (Gaussian) Mixture Model, it is also very efficient to implement and execute. Details can be found for instance in M. W. Mak, S. Y. Kung, S. H. Lin; “Expectation-Maximization Theory”, Biometric Authentication: A Machine Learning Approach, Prentice-Hall, (2004). Another way is the K-means algorithm.
[0075] In a probabilistic classification, the classification points need not have a membership probability of 100% for the classes they indicate. Classification points can often also become classified points. They can, either initially or in an interactive classification step, be assigned a lower probability to belong to the class they indicate.
[0076] The selection of the classification points and the postulated classification rule determine the result of the classification. When fractional probabilities for a classified point have been determined, a “hard” classification can be obtained by e.g. assigning the point to the class with the highest (posterior) probability. The class-membership attribute then simplifies to a simple indicator of the class to which an attribute vector is assigned, similar to the classification according to the nearest classification point.
[0077] Such a hard classification divides the attribute space into zones, as illustrated in FIG. 3 b . Dashed lines indicate zone boundaries, so that each attribute vector belongs to only one of the classes. If a location in interpretation space has an associated attribute vector, that vector belongs to one of the classes. Attribute vector A lies in the triangle class, vector B lies in the circle class, and each of both vectors is found at several locations in the interpretation space. For the sake of clarity, only a few characterizing points are shown in interpretation and attribute space. Note that the boundaries of classes obtained by such a classification are in general not plane surfaces or straight lines/polygons, but are typically curved. In interpretation space several regions can be distinguished in which attribute vectors of a particular class are found.
[0078] It is also possible to maintain the “soft” or “fuzzy” classification with a plurality of probabilities during further interpretation. Before this will be further discussed, we will first discuss the display parameter.
[0079] From the class-membership attribute of a point in attribute space a display parameter is derived for visualization of the classification result. In a hard classification, this can straightforwardly be obtained by assigning a specific colour to all attribute vectors of a given class. FIG. 3 b can in this case be displayed as a map of three distinct colours with sharp boundaries between them, and the interpretation space is coloured accordingly.
[0080] In order to use the information available from a probabilistic or “soft” classification in the further interpretation, colour mixing can be used. To this end, selected colours are assigned to the classes or classification points, and other points are assigned a mixed colour derived from the fractional probabilities. A simple example is illustrated in FIGS. 4 a,b.
[0081] An interpreter user has selected type cases G and B as classification points, has assigned labels “Green” and “Blue” to the associated classes, and has chosen functions to describe partial membership in the classes. In attribute space, vectors on the solid circles have equal membership in the Blue class, and smaller circles indicate a higher degree of membership in Blue. (Similarly the dashed circles represent fractional membership in Green. It shall be clear that circles are a simple example, and that in more complex probability density functions the isosurfaces or -lines of equal probability can and typically will have a different shape.) At point C, and elsewhere along the dotted line, membership is equally likely for Green and Blue. If the display parameter is colour, and Green and Blue are numerical representations of the colours with those names, then the display parameter assigned to C is the numerical representation of cyan. On a colour screen, the attribute space would be represented as a two-dimensional map with nearly pure blue and green at the respective points (note that even G and B need not be 100% members of the classes they indicate) and colours obtained from weighted mixing using the relative probabilities as weights everywhere. The dotted line would appear cyan. We note that the map is in general truly a general function of all the attributes, i.e. is not restricted to separable functions or linear combinations of one-dimensional colour bars.
[0082] In the interpretation space of FIG. 4 a , the interpreter can observe that several distinct features are apparent, displayed as blue (cross-hatched, “B”), green (bricked, “G”), and cyan (dotted, “C”). Other areas of the interpretation space will be coloured with intermediate colours (blended colours). A small deviation from the probabilities represented by a particular colour will be displayed with nearly that colour, so that a range of probabilities can easily be taken into account.
[0083] By assigning colour values representing class membership, in particular probabilistic class membership, to points in the attribute space, preferably covering all of the attribute space that is populated with actual attribute vectors, a two-dimensional colour map or table is defined. So the coloured attribute space represents a map or table that can be used as look-up reference for efficient display of the interpretation space.
[0084] This is relevant since data volumes handled in seismic processing are significant. Typically, only a small part of the actual data is displayed at any one time on a computer's screen, such as shown in FIG. 5 . With the map or table of display parameters obtained by the classification according to the present invention, changing the display of the interpretation space is merely a matter of a few lookup operations for each data point. For a given location in interpretation space 50 , the several attributes are determined, and the corresponding display parameters (e.g. red, green, blue, transparency values) are read and used for displaying. These are fast operations allowing an operator to browse quickly through the data, e.g. by moving one of the slices or planes 51 , 52 , 53 in FIG. 5 using a standard workstation. The desired part of the interpretation space is then displayed and events 55 e.g. representing layers in a subsurface formation are highlighted using the colour map. It shall be clear that also other parts of the interpretation space can be displayed, e.g. isosurfaces or particular events. Given this speed of data handling and display, the classification effectively happens on the fly and can be interactively refined by the analyst in real time, suitably displaying attribute space (e.g. such as in FIG. 4 b ) and at least part of the interpretation space (e.g. as in FIG. 4 a or 5 ) at the same time. Therefore, class definition (through attribute space) and display/interpretation (in interpretation space) are not separate, sequential steps anymore. Rather, these can be carried out simultaneously, by using the interactive manipulation of class membership parameters, e.g. through interactively changing the parameters of the probability density functions characterizing the classes.
[0085] The interpretation method of the present invention allows real-time interactivity in all operational aspects of the method, including the production of classified results, and thereby avoids the “black box” aspect of many state-of-the-art classification workflow.
[0086] Clearly, the same principles also allow effective handling of m=3 or more attributes, with colour cubes or hypercubes instead of two-dimensional colour maps. Such higher dimensional cubes can be created and handled principally in the same way as two-dimensional colour maps.
[0087] The interpretation according to the present invention can provide insight into the presence and properties of a subsurface formation. Sometimes it is possible to identify a region of the formation that contains a hydrocarbon reservoir, from which oil and/or natural gas can be produced, e.g. after drilling a well into the respective region of the subsurface.
[0088] The methods of the invention are suitably computer implemented, in particular by running a computer program product on a computer system. The computer program product comprises code suitable for carrying out the steps of the method. Clearly, this code can include prompting the user or operator of the method, such as a seismic interpreter, for input, such as for defining and/or updating classes, classification points and/or classification rules. When the classification is finalized, and/or at any intermediate stage, results (classification points, rules, class-membership attributes and/or display parameters) can be stored, displayed, outputted, or transmitted. | A method for interpreting a plurality of m-dimensional attribute vectors (m 2 ) assigned to a plurality of locations in an n-dimensional interpretation space (n 1 ), which method comprises arranging at least a subset of the attribute vectors as points in an m-dimensional attribute space; defining k classes (k 2 ) of attribute vectors by identifying for each class at least one classification point in attribute space; postulating a classification rule for points in attribute space; determining a class-membership attribute of a point in attribute space using the classification points and the classification rule to obtain a classified point; and assigning a display parameter to the classified point which is related to the class-membership attribute. In one embodiment the display parameter is a mixed display parameter derived from probabilistic membership values each representing a probability that the classified point belongs to a selected class. In another embodiment classified points are displayed in attribute space and in interpretation space at the same time. The method can be used in a method of producing hydrocarbons from a subsurface formation. Also provided are corresponding computer program products and computer systems. | 6 |
BACKGROUND OF THE INVENTION
The present invention pertains to the field of power supply systems for dental, surgical, and industrial handpieces and the like, and, in particular, to a portable, sterilizable, electric power supply which includes an independent power source.
Handpieces or hand tools are used by a variety of professionals, such as dentists, surgeons, technicians, etc. They operate by means of a "power supply" which may utilize electrical or pneumatic energy to drive or power the tool. When handpieces are required to be used in locations outside of normal offices, they may utilize a portable power supply. These outside locations include patient homes, nursing facilities, remote clinics, and other field locations, such as disaster sites or battlefields. Thus, portable power supplies for handpieces are desirable for use in situations where the doctor or technician does not have access to normal office equipment.
While some portable electric power supplies exist, most are pneumatic; although, both electric and pneumatic power supplies are rather large, noisy, and expensive. One example of a portable pneumatic power supply is described in U.S. Pat. No. 4,286,949 issued to Holt, Jr.. Electric power supplies are not typically sterilizable because their components are not sealed, and they are subject to lack of power and power failures because they rely on electrical lines at the site. Although the pneumatic power supplies are sterilizable, they also rely on electrical lines at the site, which may not be available, to power the pneumatic compressor. In addition, pneumatic power supplies require costly maintenance because of the lubricated components which comprise the compressor-motor assembly. Sterilization is highly desirable because of the often infectious environments in which the handpieces may be used. A noise suppression box may be used with these types of portable power supplies, however this only adds to the cumbersome nature and decreases portability.
Thus, a need exists for an improved portable power supply for handpieces that overcomes the problems associated with prior art devices.
SUMMARY OF THE INVENTION
The portable power supply system of the present invention overcomes those problems by including (i) a sealed, sterilizable electric motor assembly which is attachable to a variety of standardized handpieces or handheld tools, and (ii) detachable connection of the motor assembly to a variable voltage foot controller which is adaptable to either an AC/DC adaptor or a rechargeable battery. Thus, the power supply system of the present invention has a motor assembly that is readily autoclavable, is not dependent upon the availability of power at a remote site, is compact and economical, and may be used with any International Standard (ISO) 3954-1982E type handpiece or common laboratory tools.
The variable voltage controller is comprised of a standard foot controller, such as used for sewing machines, with connections for either the AC/DC adaptor or the battery. A conventional coaxial cable is used to communicate the DC voltage output from the foot controller to the electric motor, which is housed in a small, lightweight body with an International Standard male connection at one end. The body is completely sealed, thereby virtually eliminating maintenance requirements and allowing the motor assembly to be autoclaved or sterilized between uses.
The resulting power supply system of the present invention is more compact and quieter than existing systems, and the low voltage requirements of the motor assembly result in added economy. The elimination of the need to clean and replace lubricated parts, which is required in pneumatic systems, further results in ecological benefits, as well as cost savings to the user. The simple, compact structure of the motor assembly results in reduced manufacturing costs, and the use of conventional connections and a commercially available foot controller further adds to a less expensive system.
Further advantages and applications will become apparent to those skilled in the art from the following detailed description and the drawings referenced herein.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a pneumatic power supply system of the prior art.
FIG. 2 is a perspective view illustrating an embodiment of the portable power supply system of the present invention, wherein an electrical adaptor is used.
FIG. 2a is a perspective view illustrating an alternate embodiment of the portable power supply system, wherein a rechargeable battery unit is utilized.
FIG. 3 is a partially cross-section view of the motor assembly of the portable power supply system of the present invention as shown in FIG. 2.
FIG. 4 is a partially cross-section view of an alternate embodiment of the motor assembly of the portable power supply system of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
As illustrated in FIG. 1, the portable power supply systems of the prior art are relatively large and cumbersome, and are typically noisy. The pneumatic power supply system 10 shown in FIG. 1 further requires greater maintenance effort and expense due to its movable, working parts.
In contrast, the portable power supply system of the present invention, illustrated in FIG. 2 and indicated generally by the reference numeral 20, is compact, lightweight, quiet, and substantially maintenance-free. The basic components of the system include an access to an electrical power source and a variable voltage controller. The variable voltage controller controls the current from the higher voltage power source to a low voltage, direct current (DC) motor assembly attached to the proximal end of a handpiece.
In the embodiment illustrated in FIG. 2, the electrical power source is a typical alternating current (AC) outlet (not shown), and the access is provided by an AC/DC adaptor 22, of any conventional type well known to those skilled in the art. Since standard outlet voltage varies in different parts of the world, AC/DC adaptors appropriate to the local electrical supply may be used. Although, as shown in FIG. 2a, the reliance on working electricity in any part of the world can be eliminated by the use of a rechargeable battery unit 84 as the power source for the system 20 of the present invention.
Further, as shown in the prior art system 10 of FIG. 1, there are several types of handpieces available for use with a portable power supply. Accordingly, the handpiece 24 illustrated in FIG. 2 for the portable system 20 of the present invention serves merely as an illustration of the handpieces which may be accommodated.
Referring now in detail to the system 20 of the present invention illustrated in FIG. 2, it can be seen that the handpiece 24 is accommodated at its proximal end to the distal end of the motor assembly 26. The compact motor assembly 26, in turn, is connected at its proximal end to the foot controller 28 via a conventional coaxial cable 30. The foot controller 28 is of a standard type capable of varying the voltage from its power source and delivering a reduced voltage to the motor assembly 26. Pressure by a foot on the lever 32 activates the delivery of current through the controller 28, and increased pressure by the foot results in increased current or voltage. Thus, the doctor or operator has only to use one hand to maneuver the handpiece 24, while his foot operates the motor assembly 26 and the other hand is free to perform other tasks. It should be noted in FIG. 2 that a connecting cable 34 between the AC/DC adaptor 22 and foot controller 28 is of adequate length to allow the foot controller 28 to be located on the ground proximate the patient, away from the outlet, and the coaxial cable 30 is of a length adequate to allow the handpiece 24 to be held by the doctor when standing adjacent the patient.
As shown in FIG. 2, the lever 32 is hinged at its end closest to the connections. The lever 32 is of a rectangular shape covering substantially the entirety of the top of the body 82 of the controller 28. The construction and operation of the foot controller 28 are well-known to those skilled in the art.
The foot controller 28 has two connections in the supply system 20 of the present invention. One connector 74 is male and is inserted into the female connector 76 on the proximal end of the coaxial cable 30 which is attached to the motor assembly 26. The other connector 78 is female and receives the male connector 80 from the cable 34 attached to the AC/DC adaptor 22.
Alternately, as illustrated in FIG. 2a, the battery unit 84 has a connector 80' for mating with the foot controller 28 in lieu of the AC/DC adaptor 22. The use of the battery 84 allows the power supply system to be used in remote locations either not having access to electricity or having undependable electrical supply. The battery unit 84 is preferably of a rechargeable type for economy, although any battery type of adequate voltage having the appropriate connector 80' and cable 34' may be used.
Referring now to FIG. 3, the motor assembly 26 is illustrated (viewed right to left) with its retainer 36, housing 38, and end cap 40 shown in cross-section. The distal end of the assembly 26 comprises a male connector portion 42 of a type known as an International Standard male E-coupling. This connector 42 provides versatility in accommodating any of a variety of handpieces having the corresponding female connector portion (not shown) on its proximal end. The proximal end of the motor assembly 26 comprises a female connector 44 to receive a male connector (not shown) of the coaxial cable 30. When the handpiece 24 and the coaxial cable 30 are removed, the motor assembly 26 may be sterilized without harm to the DC electric motor 46 contained within the housing 38, since the housing 38 is well-sealed, as described below in connection with FIG. 3.
When the handpiece 24 is inserted over the standard ISO male connector 42 of the motor assembly 26, a cylindrical portion (not shown) located within the proximal end of the handpiece 24 is received into a passage 48 of the connector 42. A spring 50 located proximal the retainer 36 provides the tight fit necessary to affix the handpiece 24 onto the motor assembly 26. A driving pin 52 of the electric motor 46 extrudes into the passage 48 and provides the necessary rotary energy to drive the handpiece 24.
As shown in FIG. 3, the pin 52 is centrally located on a distal face 54 of the electric motor 46. The housing 38 encasing the pin 52 and motor 46 has a main body 56 with an inner diameter substantially the same as the diameter of the electric motor 46, thus ensuring a tight, sealing fit. A high temperature, preferably silicone, sealant is used on the distal face 54 of the motor 46 to provide additional sealing in the housing 38. A spring washer 58 is similarly sized to fit within the housing 38 and engages the proximal end of the motor 46. The spring washer 58 biases the motor 46 distally so that its distal face 54 is further provided with a secure seal. Connectors 60 extrude from the proximal end of the motor 46 through apertures (not shown) in the washer 58, and are received into a cavity 62 formed at the distal end of the end cap 40.
The distal end of the end cap 40 also has an outer diameter substantially the same as the inner diameter of the housing's main body 56, in which it is engaged. The exterior of the distal half of the end cap 40 is fluted, wherein the distal end has a reduced outer diameter adequate to receive the widest, distal portion of the connector 44. The connector 44 is hermetically sealed in the end cap 40. An O-ring 64 is located proximate the proximal end of the housing 38 to further provide sealing of the motor assembly 26. Thus, the sealant applied to the distal face 54, the spring washer 58, and the O-ring 64 components, along with other components and tolerances, hermetically seal the motor 46 within the housing 38.
Engagement of the end cap 40 onto the proximal end of the housing 38 is accomplished via springs 66 surrounding a passage 68 communicating the Cable connector 44 to the cavity 62. The springs 66 provide outward pressure on pins 70 which extend through holes 72 located on the periphery of the proximal end of the housing 38. Thus, the end cap 40 is removable by manually depressing the pins 70, if necessary for service or maintenance.
Wires (not shown) for the electrical connection between the connectors 60 and the connector 44 extend from the cavity 62 through the passage 68. Thus, the connector 44 comprises a "jack-type" electrical connector which receives the probe of the male connector on the distal end of the cable 30. The connector 44 has a distal portion of a reduced diameter comprising one electrode and a more proximal portion of a larger diameter comprising the other electrode of the opposite charge. These charges are provided by wires soldered to the connectors 60. Thus, the electrical connection between the cable 30 and connectors 60 is accomplished.
A motor assembly of the system 20 of the present invention is not only operable as an extension to a handpiece, but may also be used as a handle and power supply for small tools such as used in laboratories. That is, a chuck and collet configuration may be used in place of the male E-coupling to attach various tools or bits rather than ISO E-type handpieces, as illustrated in FIG. 4. Laboratory technicians and the like can thus use an alternate embodiment of the motor assembly to attach a tool 86 directly onto the distal end of the motor assembly 88, with the housing 90 of the assembly 88 comprising the handle necessary to grip and maneuver the tool 86.
As illustrated in FIG. 4, the DC motor 46 is contained within substantially the same casing as the previous motor assembly 26 of FIG. 3. Here, like numbers refer to like parts. The housing 90 includes a main body 92 having a slightly larger outer diameter than the housing 38. This larger diameter allows the pins 70 to be contained in recesses 93 formed on the inner circumference of the body 92. Thus, the pins 70 do not extrude to the exterior of the housing 90.
In the motor assembly of FIG. 4, the distal end is adapted to include a shaft 94 and nut 96 for attachment of the tool 86. The nut 96 is located on the distal end of the shaft 94, and the tool 86 is simply inserted and the nut releasably tightened. Thus, the exchange of tools is simple and quickly accomplished.
The shaft 94 has an outer diameter substantially the same as the passage 48 and extends to proximate the base of the driving pin 52. A nut 98 replaces the retainer 36 of the other motor assembly 26 and affixes the shaft 94 to the distal end of the housing 90. A smoothly contoured spacer 100 surrounds what was the male connector 42 of the other assembly 26, and together with a tapered outer surface of the end cap 102, provides a more uniform and better feeling exterior for handling by the technician.
Accordingly, the portable power supply 20 of the present invention provides a compact and multi-functional power source for doctors and others requiring same. The ISO compatible male connector 42 of the motor assembly 26 in one embodiment can accommodate a variety of handpieces, as likewise the shaft 94 and nut 96 of the motor assembly 88 in another embodiment can accommodate a variety of hand-held tools. An AC/DC adaptor 22 appropriate for the local electricity may be used, or a battery unit 84 may be substituted in remote or more hostile locations. Finally, the sealed casings of motor assemblies 26 and 88 significantly reduces the incumbent maintenance of the power supply 20, and further allows the motor assembly 26 or 88 to be sterilized as required along with the handpieces or tools.
Thus, the electric power supply system 20 of the present invention affords versatility, portability, and reliability heretofore unavailable. Other changes and modifications may be made from the embodiments presented herein by those skilled in the art without departure from the spirit and scope of the invention, as defined by the appended claims. | A portable power supply system utilizes a foot controller and a lightweight, sealed electric motor assembly which attaches to any International Standard E-Coupling handpiece. The foot controller is adaptable for use with either an AC/DC adaptor or a rechargeable battery. A coaxial cable connects the variable voltage supply from the foot controller to the low voltage, DC motor assembly. The motor assembly is sterilizable, lightweight, and quiet, making it ideal for use by dentists, oral or orthopedic surgeons, laboratory technicians, or anyone else desiring an economical, portable power supply for handpieces. | 8 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to sputter targets and sputter target assemblies having a uniform distribution of the magnetic leakage flux.
[0003] 2. Description of Related Art
[0004] Cathode sputter targets and target assemblies are widely utilized for the deposition of thin layer materials onto wafer substrates and subsequent circuit patterns laid thereon. The process requires a gas ion bombardment of a target having a surface formed of a material that is desired to be deposited onto a substrate. The target forms part of a cathode assembly that, together with the anode, is placed in an evacuated chamber filled with an inert gas, such as argon. A high voltage electrical field is applied across the cathode and the anode. The inert gas is ionized by electrons ejected from the cathode. Positively charged gas ions are attracted to the cathode, and upon impingement with the target surface, these ions dislodge the target material. The dislodged target material traverses the evacuated chamber and deposits as a thin film on the desired substrate, which is usually located in close proximity to the anode.
[0005] To further increase sputtering the concurrent application of an arch-shaped magnetic field superimposed over the electrical field has been utilized. This method is known as a magnetron sputtering method. The arch-shaped magnetic field traps electrons in an annular region adjacent to the target surface, thereby increasing the number of electron-gas atom collisions in the area to produce an increase in the number of positive gas ions (i.e., plasma) in the region that strike the target to dislodge the target material.
[0006] For magnetron sputter targets, the magnetic leakage flux (MLF), also known as magnetic pass through flux (PTF) at the target surface must be high enough to ignite and sustain the plasma. Under normal sputtering conditions, the higher the magnet strength, the higher the MLF. In the case of ferromagnetic materials, however, the strength of the high intrinsic permeability of the material effectively shields or shunts the magnetic field from the magnets behind the target and hence reduces the MLF on the target surface.
[0007] Considering the importance of the magnetic properties of sputter targets, manufacturers have relied upon various techniques to fabricate sputter targets with lower sputter target permeability and an increased PTF.
[0008] U.S. Pat. No. 4,401,546 discloses a planar ferromagnetic segmented target, where the segments are separated by gaps through which the magnetic field leaks to produce an MLF of 200 Gauss on the surface of the target.
[0009] U.S. Pat. No. 5,827,414 discloses a planar ferromagnetic target having a certain thickness due to the gaps in the target. The gaps in this configuration are radial gaps formed by slots in the target body that are perpendicular to the flux of the magnetron, thereby producing a more effective and homogeneous leakage magnetic field on and parallel to the surface of the target body so that the sputtering plasma density may be increased.
[0010] Other techniques developed include the hot or cold working of the sputter target blank to increase the PTF by manipulating the crystallographic structure. European Patent Document No. 799905 recognized that strain can manipulate a high-purity cobalt target's permeability. This patent publication discloses a process that relies upon either cold or warm rolling to reduce the target's initial permeability parallel to the target's surface to about 7. However, this process increases the permeability perpendicular to the target's surface.
[0011] U.S. Pat. No. 5,766,380 discloses a cryogenic method for fabricating aluminum alloy sputter targets. This method uses cryogenic processing with a final annealing step to recrystallize the grains into a desired texture. Similarly, U.S. Pat. No. 5,993,621 utilizes cryogenic working and annealing to manipulate and enhance crystallographic texture of titanium sputter targets.
[0012] Unfortunately, these processes have limited success with respect to the limited target thickness and control of the target's final magnetic properties, which in turn negatively affects the deposition rates and the film uniformity.
[0013] To meet the requirements of the semiconductor manufacturing industry and to overcome the disadvantages of the related art, it is an object of the present invention to provide a ferromagnetic sputter target and assembly with a uniform MLF.
[0014] It is also an object of the invention to provide a method of forming said ferromagnetic sputter target and assembly.
[0015] It is another object of the invention to provide an increased target thickness uniformity.
[0016] As a result of the invention, the target life is increased, and the cost of manufacturing the wafers is decreased. In addition, the film deposited onto the substrate has an increased uniformity.
[0017] Other objects and advantages of the present invention will become apparent to one of ordinary skill in the art upon review of the specification, drawings and claims appended hereto.
SUMMARY OF THE INVENTION
[0018] The foregoing objectives are met by the methods and sputter target assembly of the present invention. According to one aspect of the invention, a method of forming a ferromagnetic sputter target is provided. The method includes providing a ferromagnetic sputter workpiece and hot rolling the workpiece to a substantially circular configuration sputter target; machining a taper in a surface of the sputter target to have a thickness gradient of the sputter target, where the center of the sputter target is about 0.020 to about 0.005 inches thinner than the edge of said sputter target, and where the magnetic leakage flux across the sputter target is uniformly distributed.
[0019] According to a second aspect of the invention, a method of forming a sputter target assembly is provided. The method includes providing a ferromagnetic sputter target with a taper in a surface thereof, where the thickness gradient of the taper is such that the thickness at the center of the sputter target is about 0.020 to about 0.005 inches thinner than at the edge of the sputter target and where the magnetic leakage flux across the sputter target is uniformly distributed; applying a bond metal layer between the sputter target and a backing plate; pressing the sputter target and the backing plate; and forming a solid state bond therebetween to obtain the sputter target assembly.
[0020] According to another aspect of the invention, a ferromagnetic sputter target is provided. The target is a substantially circular target having a taper in a surface thereof and a target thickness gradient, where the thickness gradient at the center of the sputter target is about 0.020 to about 0.005 inches thinner than the edge of the sputter target, and wherein the magnetic leakage flux across the sputter target is uniformly distributed.
[0021] According to yet another aspect of the invention, a sputter target assembly is provided. The assembly includes a ferromagnetic sputter target with a taper in a surface thereof, where the thickness gradient of the taper is such that the thickness at the center of the sputter target is about 0.020 to about 0.005 inches thinner than at the edge of the sputter target and where the magnetic leakage flux across the sputter target is uniformly distributed; a backing plate with a matching recess therein having the ferromagnetic sputter target disposed therein and solid state bonded thereto to obtain the sputter target assembly.
BRIEF DESCRIPTION OF THE DRAWINGS
[0022] The objects and advantages of the invention will become apparent from the following detailed description of the preferred embodiments thereof in connection with the accompanying drawings wherein like numbers denote like feature and in which:
[0023] FIG. 1A illustrates a cross-sectional view of target in accordance with one of the embodiments of the invention;
[0024] FIG. 1B illustrates a perspective view of the bottom surface of the target;
[0025] FIG. 1C illustrates a cross-sectional view of the target having a parabolic bottom surface configuration;
[0026] FIG. 1D illustrates a cross-sectional view of the target having a linear bottom surface configuration;
[0027] FIG. 2 illustrates a cross-sectional view of the target and backing plate which form the target assembly; and
[0028] FIG. 3 illustrates a cross-sectional view of the target and backing plate, wherein the mating surface of the target has been treated.
DETAILED DESCRIPTION OF THE INVENTION
[0029] The present invention provides a planar single-piece ferromagnetic sputter target and assembly. In ferromagnetic sputter targets and assemblies the magnetic properties of the material are absolutely critical for the performance of the target in producing uniformly sputtered films on 300 mm wafers. The magnetic properties of the target may be controlled through the thermomechanical treatment of the blank metal workpiece, where uniformity is imposed by the microstructural evolution attained through either hot-working, cold-working, forging, or cryogenic treatment of the blank workpiece.
[0030] Modifying the target configuration, however, significantly affects the uniformity achieved. It has been shown that conventional sputter targets have a magnetic leakage flux which is higher at the edges than at the center of the target as the magnetic leakage flux flows around the edges of the target, while the ferromagnetic material at the center of the target shunts the flux.
[0031] In accordance with the principles of the present invention, a ferromagnetic material is formed into a solid, unitary sputter target configuration, such as a plate having an even permeability throughout the material. The sputter target has a thickness gradient, where the thicker target edge counteracts the edge effect of the flux. Ferromagnetic materials contemplated by the invention include, by way of example, pure nickel (Ni) and Ni-based alloys, such as NiFe and NiFeCo; pure iron (Fe) and Fe-based alloys, such as FeTa, FeCo and FeNi; pure cobalt (Co) and Co-based alloys, such as CoCr, CoCrPt; and other binary, ternary and higher degree of elemental alloys comprising Ni, Fe, Co and other elements having an intrinsic magnetic permeability greater than 1.0.
[0032] With reference to FIG. 1A , sputter target 10 is a substantially circular disc-shaped, high-purity ferromagnetic nickel or cobalt target. The ferromagnetic sputter target has a purity of at least about 99.99 weight percent. For purposes of this specification, all concentrations are in weight percent. Advantageously, sputter targets have a purity of at least 99.995 weight percent and more advantageously at least about 99.999 weight percent. While sputter target 10 , as depicted, is disc-shaped, it will be understood by those skilled in the art that other shape targets, such as oval, square, or rectangular may be utilized.
[0033] As aforementioned, target 10 can be manufactured from a blank workpiece, which is forged and hot worked or cold worked or cryogenically formed. Hot working reduces the residual stresses in the workpiece, but typically results in a higher magnetic permeability than cold working or cryogenic forming. The sputtering surface 12 is typically maintained planar to dislodge the material therefrom continuously and to place a uniform layer onto the substrate. Surface 14 of sputter target 10 is machined, forged, pressed, or cast to form a slight taper (exaggerated in the figure) extending radially from the center 16 to edge 18 of sputter target 10 . The taper causes a slight thickness gradient from the center 16 to the edge 18 , wherein the sputter target 10 is about 0.020 to about 0.003 inches thinner at the center 16 , and preferably about 0.020 to about 0.005 inches thinner at the center 16 , and most preferably about 0.010 to about 0.005 inches thinner at the center 16 .
[0034] The taper may be configured in any number of ways that would provide the thickness gradient. As shown in FIG. 1B , surface 14 has a number of concentric circles 19 , wherein the thickness decreases from the outermost to the innermost concentric circle. However, the thickness within each concentric circle is uniform. Among the exemplary configurations contemplated in the present invention, as illustrated in FIG. 1C , the taper can be parabolic extending from the edge to the center of the sputter target. Alternatively, as shown in FIG. 1D , the taper can be linear extending from the edge to the center of the target. As aforementioned, sputtering surface 12 is typically maintained planar. However, this sputtering surface may be modified in similar manner as discussed with reference to surface 14 , to contain a taper which is parabolic or linear (not shown). In this case, the taper should not exceed 0.010 inches. With reference to FIG. 2 , a target/backing plate assembly is illustrated. Target/backing assemblies provide the backing plate which secures the target in the sputtering apparatus and further reduce costs associated with the targets. Sputter target assembly 20 provides a backing plate 22 with a recess 24 machined therein which mates with the taper of target 10 inlaid therein. The overall height of sputter target assembly 20 maintains the industry accepted height dimension as shown in U.S. Pat. No. 6,073,830 which is incorporated by reference in its entirety. The metals utilized for the backing plate may be any number of metals and include aluminum (Al), titanium (Ti), copper (Cu), and alloys thereof. Preferably, the backing plate is made of a copper alloy.
[0035] The sputter target 10 is inserted into backing plate 22 and secured thereto via a strong bond. A number of bonding techniques have been developed and utilized to secure sputter targets to the backing plates. Acceptable bonding techniques include soldering, brazing, diffusion bonding, explosion bonding, mechanical fastening and epoxy bonding. However, depending on the materials chosen for the target and the backing plate, the bonding technique has to be carefully selected to avoid deleterious changes in the microstructure (e.g., grain growth) of the sputter target and to account for the difference in the coefficients of thermal expansion of the target and the backing plate. A mismatch in the coefficients of thermal expansion may simply result in deflection of the target or delamination of the two components, which would result in an unsatisfactory deposition onto the substrate and possible failure of the target assembly during use, respectively.
[0036] The most suitable bonding method depends on the target and backing plate materials. For example, high-purity nickel and nickel based targets often require bonding to copper backing plates at temperatures low enough to retain a fine microstructure and low magnetic permeability. For these types of materials a solid state bond is most advantageous, because this type of bonding uses low temperature processing and prevents changes of the microstructure or magnetic properties within the nickel-based target. Solid state bonding is disclosed in pending U.S. Ser. No. 10/153,660 which is hereby incorporated by reference in its entirety.
[0037] A bond metal layer 26 may be applied between sputter target 10 and backing plate 22 to form the solid state bond. Acceptable bond metals include the following precious metals: gold, silver, platinum, palladium, iridium, rhodium, ruthenium and osmium. For cost considerations, silver represents the most advantageous metal for forming solid state bonds. Acceptable techniques for coating with the bond metal layer include both foil utilization and electrodeposition processes. The electrodeposited bond layer has a thickness of at least 15 μm. Preferably, the solid state bond layer has total thickness of about 40 to about 100 μm.
[0038] Pressing sputter target 10 into backing plate 22 with bond metal layer 26 therebetween forms a solid state bond. The pressing occurs in a direction perpendicular to the sputter target's surface or face. Both hot uniaxial pressing and hot isostatic pressing are advantageous methods for forming solid state bonds between the target assembly components. Heating the bond metal to a temperature below the sputter target's grain growth temperature improves the solid state bond's integrity.
[0039] If the sputter target is nickel based and the backing plate is copper based, then the pressing advantageously occurs at pressures above about 70 MPa and at a temperature of about 260 to 320° C. Generally, increasing pressing temperature improves the bond's strength, but increases the likelihood of detrimental grain growth within the sputter target. Most preferably, the pressing occurs at a temperature between about 300 and about 320° C. and pressing occurs at a pressure of about 100 MPa. Under these conditions the microstructure of the target is unchanged and the taper is maintained.
[0040] As illustrated in FIG. 3 , the preparation of the bonding may consist of roughening the matching recessed surface 32 of backing plate 22 in assembly 30 . The bond interface may not lend itself to surface roughening of sputter target 10 , since it may change the overall dimensions of the sputter target thickness gradient. However, to improve the bond, a surface treatment step forms an uneven surface topology wherein the bond metal layer anchors. As a result, a lower bonding pressure and temperature can be utilized to form assembly 30 . Acceptable surface roughening techniques include, but are not limited to, particle blasting, shot peening and etching. Particles used in particle blasting can be selected from a group that may include, but is not limited to: grit, sand, glass beads and steel shot. This process causes subtle disruptions of the associated bonding surfaces when the components are heated and pressed. Most preferably, the process uses grit blasting to roughen the backing plate recess to promote the formation of desirable solid state bonding.
[0041] As shown in Table 1, the present invention decreased both the magnetic leakage flux (MLF) range and the MLF standard deviation of nickel targets by more than 30 percent compared to the related art, which contains planar surfaces 12 and 14 . For each of the four targets in Table 1, the MLF was measured in 25 points located in the target center and three concentric circles. All four targets had a nickel diameter of 17.2 inches and a nickel thickness of 0.1 inches. They were bonded to copper-chromium (C18200) backing plates having a thickness of 0.9 inches.
TABLE 1 Present Related Art Invention Property Target 1 Target 2 Target 3 Target 4 MLF Range 80 79 55 53 MLF Deviation 26 23 18 16
[0042] While the invention has been described in detail with reference to specific embodiments thereof, it will be apparent to those skilled in the art that various changes and modifications can be made, and equivalents employed, without departing from the scope of the appended claims. | Provided is a method of forming ferromagnetic sputter targets and sputter target assemblies having a uniform distribution of magnetic leakage flux. The method includes providing a ferromagnetic sputter workpiece and hot rolling the workpiece to a substantially circular configuration sputter target; machining a taper in a surface of the sputter target to have a thickness gradient of the sputter target, where the center of the sputter target is about 0.020 to about 0.005 inches thinner than the edge of the sputter target, and where the magnetic leakage flux across the sputter target is uniformly distributed. | 8 |
[0001] This application claims the benefit of U.S. Provisional Patent Application No. 61/335,939 filed Jan. 12, 2010.
FIELD OF THE INVENTION
[0002] The present invention relates generally to protection of electrical circuitry used in hardware components, and more specifically, to a system and methods that generates a physical unclonable function (“PUF”) security key for an integrated circuit (“IC”).
BACKGROUND OF THE INVENTION
[0003] An integrated circuit (“IC”), also known as a chip or a microchip, is a miniaturized electronic circuit used in electronic equipment such as computer, telephone, and digital applications. An IC is typically formed of semiconductor devices, such as silicon and germanium, as well as passive components such as capacitors, resistors, and diodes. Usually, an IC is manufactured on a thin substrate of semiconductor material. In recent years, cost in manufacturing of ICs, per transistor, has decreased. However, while lower cost increases the availability of manufacturing, considerable research is associated with IC development resulting in the creation of various intellectual property. Accordingly, ICs must be protected from threats such as cloning or copying as well as protected against misappropriation and unauthorized use. Threats may allow unauthorized access to encrypted data, replication of IC design including unauthorized use of intellectual property (“IP”) and hardware piracy or the illegal manufacturing of the ICs. Threats of cloning, misappropriation and unauthorized use of a security key are a problem, particularly in computer applications that use a security key in authentication protocols.
[0004] Many computer-based hardware security schemes exist to protect ICs from cloning and unauthorized use. These security schemes depend on accessibility to a security key or signature, such as a unique unclonable identifier derived from each IC. Security keys define the basis of computer-based hardware security mechanisms implemented at high levels of hardware security such as those mechanisms that perform encryption of data communication channels, or provide IP theft protection in computer-based logic devices including field-programmable gate arrays (“FPGAs”).
[0005] Conventional security keys are defined using digital data stored, for example, in a flash memory or read only memory (“ROM”) on the IC. From a security perspective, it is desirable that access to the security key is restricted to hardware circuits formed on the IC. Unfortunately, security keys stored using these conventional technologies are subject to invasive physical attacks which can allow an adversary to learn the secret key. If the secret key is learned by an adversary, then clones ICs can be created and security protocols can be compromised.
[0006] Various techniques have been proposed to protect ICs using physical unclonable function (“PUF”) implementations. Challenge-based IC authentication is one example. With challenge-based IC authentication, a secret key is embedded in the IC that enables the IC to generate a unique response to a challenge, which is valid only for that challenge. Thus, the key remains secret and the mechanism performing authentication is resistant to spoofing. Remote activation schemes are another example. Remote activation schemes enable IC designers to lock each IC at start-up and then enable it remotely, providing intellectual property protection and hardware metering. States are added to the finite state machine (“FSM”) of a design and control signals are added which are a function of the secret key. Therefore, the hardware locks up until receipt of a specific activation code. Other examples of PUF implementations include mismatched delay-lines, static random access memory (“SRAM”) power-on patterns, metal-oxide semiconductor (“MOS”) device mismatches and input dependent leakage patterns. However, each of these techniques has vulnerabilities related to misappropriation, cloning or unauthorized use of a security key for an IC.
[0007] There is a demand to improve the security of ICs, particularly mitigating the vulnerability of security keys to threats including cloning, misappropriation and unauthorized use. The present invention satisfies this demand.
SUMMARY OF THE INVENTION
[0008] According to the present invention, the vulnerability of an embedded security key stored on an IC is mitigated by deriving the security key from the physical characteristics of the IC. A physical unclonable function (“PUF”) circuit generates a silicon-variation-based security key. The PUF circuit includes a specialized electrical hardware circuit that is sensitive to process variations. The PUF further includes a mechanism to retrieve a unique set of responses from a variety of different challenges. A security key derived from a PUF circuit has properties such as volatility and non-replicability, which make it extremely difficult to clone, misappropriate or compromise the security key.
[0009] In one embodiment, a PUF may be implemented based on the variability in passive and active components or leakage current associated with the IC. In another embodiment, a PUF may be implemented based on variability in only passive components, for example, metal wires. A PUF circuit security key that is based on the variations in passive components of the IC is less susceptible (and therefore more robust) to environmental variations such as temperature and electrical circuit noise. While process variations in active components can be leveraged to create a diverse set of responses across ICs, the performance variations in active components are also subject to environmental variations. Therefore, these embodiments also necessitate calibration for environmental variations so that the response of the PUF circuit does not depend on the environmental conditions. However, calibration of the environmental conditions may complicate the design of the PUF circuit and make them less attractive for security applications.
[0010] Since the power grid is an existing and distributed resource in every design of an IC, the space required by a power grid-derived PUF is limited to the area available for the added challenge/response circuitry. Moreover, the distributed nature of the power grid makes it more prone to larger random and systematic process variation effects. Process variation effects introduce resistance variations whose magnitudes vary across different regions of the power grid thereby improving the security of an IC because it makes it less probable that the PUFs of two different ICs will produce the same response or security key.
[0011] Although the present invention is discussed herein with respect to power grids, it is contemplated that the present invention is applicable to deriving PUF responses from a ground grid. One embodiment of the invention includes a PUF circuit having a security key generated from the resistance variations in the power grids of ICs fabricated in a 65 nm technology. The PUF response may be defined in two ways. First, the response may be a set of voltage drops measured at a set of distinct locations on the power grid of the IC. Second, the response may be a corresponding set of equivalent resistances computed at the same set of distinct locations on the power grid of the IC. A PUF circuit enables a variety of challenges to be introduced to a power grid system, and measures the voltage drops or responses to those challenges.
[0012] PUF circuit security keys may be implemented in many applications including IC identification, enumeration in wireless sensor nodes, IC process quality control, hardware metering, challenge-based IC authentication, IP protection in FPGAs, cryptography, and remote service and feature activation.
[0013] In one embodiment, the invention is a security key generating system for an integrated circuit. The security key generating system includes a power grid with a plurality of power points, a voltage sense wire, and a plurality of intersecting striped layers. A voltage-measuring apparatus is connected to the voltage sense wire and at least one power supply is electrically connected to the plurality of power points. A ground grid is electrically connected to the power grid and at least one stimulus-measure circuit is disposed between the power supply and the ground grid. It is contemplated that the stimulus-measure circuit may include a shorting inverter, a voltage sense transistor, or a flip-flop. In certain embodiments, flip-flops may include an output connected to a shorting inverter. The shorting inverter may further comprise a first field-effect transistor having a source connected to a power supply and a drain connected to a source of a second field-effect transistor. The stimulus-measure circuit may further include a third flip-flop and a voltage sense field-effect transistor. Output of one flip-flop may be inputted to another third flip-flop, and the output of a flip-flop may be provided to a gate of the voltage sense field-effect transistor. A source of the voltage sense field-effect transistor is connected to a power supply, and a drain of the voltage sense field-effect transistor is connected to the voltage sense wire. It is also contemplated that the shorting inverter may comprise two connected field-effect transistors, with a first flip-flop providing an output to a gate of one of the two connected field-effect transistors, and a second flip-flop providing an output to a gate of the other of the two connected field-effect transistors.
[0014] The stimulus-measure circuit may include a first flip-flop, a second flip-flop connected to the first flip-flop, a third flip-flop connected to the second flip-flop, a shorting inverter connected to the first flip-flop, a first voltage sense field-effect transistor connected to the second flip-flop, and a second voltage sense field-effect transistor connected to the third flip-flop. A second voltage sense wire may also be connected to the stimulus-measure circuit with an operational amplifier having one input connected to the second voltage sense wire and another input connected to the other voltage sense wire and a key generator control connected to an output of the operational amplifier.
[0015] In another embodiment, the stimulus-measure circuit may include a plurality of flip-flops connected in series with a decoder connected to at least one of the plurality of flip-flops. The stimulus-measure circuit may also include one or more voltage sense field-effect transistors and a shorting inverter connected to the plurality of flip-flops. It is contemplated that the decoder is a 4 to 16 inverting decoder and one flip-flop is connected to a shorting inverter and at least two flip-flops are connected to the decoder. Outputs of the decoder may be connected to gates of one or more voltage sense field-effect transistors and the shorting inverter comprises a pair of connected field-effect transistors.
[0016] In another embodiment of the invention, a method of creating a physical unclonable function circuit security key includes the steps of providing a substrate and formulating a power grid on the substrate. The PUF is implemented such that the infrastructure that defines the security key does not consume a large area of the IC, since physical space on the semiconductor substrate is typically limited. The power grid includes one or more power ports. The power grid is connected to a power supply and one or more stimulus-measure circuits are inserted. Each of the one or more stimulus-measure circuits includes a shorting inverter, at least one voltage sense transistor, and at least one flip-flop. The security key is derived for the physical unclonable function circuit based on a measured stimulus and response between nodes of the power grid and the one or more stimulus-measure circuits. It is contemplated the security key may be a voltage drop security key or an equivalent resistance security key.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] The preferred embodiments of the invention will be described in conjunction with the appended drawing provided to illustrate and not to the limit the invention, where like designations denote like elements, and in which:
[0018] FIG. 1 is a schematic diagram of a power grid architecture according to an embodiment of the present invention;
[0019] FIG. 2 is a schematic diagram of an instrumentation setup including a global current source meter and a volt meter connected to the power grid architecture of FIG. 1 according to the present invention;
[0020] FIG. 3 is a schematic diagram of a stimulus/measure circuit (“SMC”) according to the present invention;
[0021] FIG. 4 is a schematic diagram of another embodiment of a SMC according to the present invention;
[0022] FIG. 5 is a schematic diagram of on-chip instrumentation for generating a security key according to the present invention;
[0023] FIG. 6 is a graph illustrating voltage drop signatures according to the present invention;
[0024] FIG. 7 is a graph illustrating resistance signatures according to the present invention;
[0025] FIG. 8 is a graph illustrating a gamma function fit of a chip equivalent resistance histogram according to the present invention;
[0026] FIG. 9 is a graph illustrating a gamma function fit of a noise equivalent resistance histogram according to the present invention;
[0027] FIG. 10 is a schematic diagram of another embodiment of a SMC with multiple sense transistors according to the present invention; and
[0028] FIG. 11 is a schematic diagram of another embodiment of on-chip instrumentation for generating a security key according to the present invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0029] As described herein, a power grid system having a physical unclonable function circuit for generation of a security key is provided. The system is based on the measured equivalent resistance variations in the power distribution system (“PDS”) of an IC. Although the present invention is discussed herein with respect to a power grid system, it is contemplated that the present invention is applicable to deriving PUF responses from a ground grid system.
[0030] A schematic representation of a power grid system is shown generally as 20 in FIG. 1 . The power grid system 20 includes a power grid 22 which has adjacent metal striped layers 24 and 26 that intersect each other at right angles in a mesh configuration. The adjacent metal layers 24 , 26 include vias 28 placed at the intersections of the layers. A ground grid 30 partially shown in dashed lines can be interleaved with the adjacent metal layers 24 , 26 and routed in a similar manner. It is contemplated that the structure of the ground grid 30 is similar to the structure of the power grid 22 . For example, both grids 22 and 30 can be routed across 10 metal layers available in the 65 nm IC forming process. The width of the wires and the granularity of the mesh of the power grid 22 vary across the metal layers 24 and 26 . For example, the widths of the lower metal wires in the metal layers 24 and 26 can be smaller and the granularity can be finer than the widths and granularity of the metal wires in the upper layers of the metal layers 24 and 26 .
[0031] The power grid 22 may be connected to a set of six controlled collapse chip connections (C4s) or power ports (PPs) 32 in a top metal layer 34 . The PPs 32 are labeled in a matrix notation as PP 00 through PP 12 . The PPs 32 allow the power grid 22 to be connected to a power supply 36 , for example through a membrane style probe card during wafer probe or through the package wiring. The finite resistances 38 of power port connections are represented as series resistances Rp xy in FIG. 1 .
[0032] A test jig indicated generally as 50 is shown in FIG. 2 . The PPs 32 are connected via wires 52 to a power source, such as a global current source meter (“GCSM”) 54 . The GCSM 54 provides a voltage, for example 0.9 V, to the power grid 22 and preferably can measure electrical current at a resolution of approximately 300 nA. In addition to measuring the global electric currents to each of the PPs 32 , measurements of on-chip voltage also occur. The on-chip voltage, in certain embodiments, can be measured using an off-chip pin that is connected internally to a globally routed voltage sense wire 54 . A voltage measuring apparatus, such as voltmeter 56 can be connected via dashed line 58 to the off-chip pin, as shown in FIG. 2 . A stimulus-measure circuit (SMC) 60 is inserted under each of the PPs 32 . Each SMC 60 is formed on a semiconductor substrate 62 , which can be formed of, for example, silicon or silicon-germanium. In alternative embodiments, it is envisioned that the SMC 60 may be connected to the ground grid 30 in a similar manner as the SMC is connected to the power grid 22 in order to sense electrical current variations in the ground grid.
[0033] The SMC 60 is shown in more detail in FIGS. 3( a ) and 3 ( b ). FIG. 3( a ) shows a top view of FIG. 2 with the metal layers 24 and 26 removed. In this embodiment, the PPs 32 are organized in a rectangular arrangement. A lateral distance 62 between PP 02 and PP 12 is 558 μm, and a width distance 64 between PP 02 and PP 00 is 380 μm. An SMC 60 is located under each of the PPs 32 .
[0034] Turning now to FIG. 3( b ), a more detailed view of one preferred embodiment of a SMC 60 connected to the power grid system 20 is shown. The SMC 60 includes a shorting inverter having a lower transistor 70 that has a drain connected to the ground grid 30 , a voltage sense transistor 72 that has a drain connected to the voltage sense wire 54 , and a set of three flip-flops FF 1 , FF 2 , and FF 3 . In the present embodiment, the transistors are field-effect transistors and the flip-flops are scan flip-flops. The volt meter 56 is also connected to the voltage sense wire 54 and measures the voltage at this node of the SMC circuit 60 . The flip-flop FF 1 receives a scan chain input 74 . The flip-flop FF 1 provides an output 76 to the flip-flop FF 2 and an inverter 78 .
[0035] Output from the inverter 78 is provided to the gate of the lower transistor 70 of the shorting inverter. The flip-flop FF 2 has an output 80 provided to flip-flop FF 3 and also a gate of an upper transistor 82 of the shorting inverter.
[0036] The drain of the upper transistor 82 is connected to the source of the lower transistor 70 . The source of the voltage sense transistor 72 connects via one of M 1 to M 10 metal layers 84 to the power supply 36 . Output from the flip-flop FF 3 is provided to the gate of the voltage sense transistor 72 and other flip-flops of SMCs 60 . The shorting inverter lower transistor 70 provides a controlled stimulus, i.e., an electrical short between the power supply 36 and ground grid 30 , when the states of flip-flop FF 1 and flip-flop FF 2 are set to 0 (low). The voltage on the power grid is measured using the voltage sense transistor 72 , enabled with a 0 (low) in flip-flop FF 3 .
[0037] A security key can be derived using two strategies, one that is based on voltage drops and another that is based on equivalent resistances at different nodes of the system power grid. In either strategy, the security key associated with the IC is composed of six quantities, each corresponding to one of the six SMCs 60 . The security key for a given IC under the voltage drop strategy can be constructed by enabling (high logic state) the shorting inverter transistors 70 in the SMCs 60 , one at a time, and then measuring the voltage at the source of the shorting inverter transistor using the voltage sense transistor. A voltage drop is computed by subtracting the measured voltage from the power supply 36 , which is shown in the exemplary embodiment as 0.9V. The process of measuring a voltage at a source of an exemplary shorting inverter field-effect transistor and computing a voltage drop is repeated for each of the other five SMCs 60 . The resulting set of six computed voltages defines the security key.
[0038] The values of the voltages defining the security key are affected by the magnitude of the electrical current passing through each shorting inverter. Accordingly, the variations in the magnitude of the electrical current passing through each shorting inverter transistor add to the randomness of the security key. In this embodiment the PUF circuit may be sensitive to environmental conditions and require some fine tuning or controlled environmental conditions to generate the same security key.
[0039] In another embodiment using an equivalent resistance (“ER”) strategy, the sensitivity of the PUF circuit to environmental conditions may be reduced. The sensitivity may be reduced by dividing the computed voltage drops by the associated global measured electrical currents passing through the shorting inverter.
[0040] In other examples, it is possible that hundreds of SMCs 60 can be inserted into commercial power grids, which would greatly expand the complexity of the security key over that shown in the six PPs example above. Inserting a large number of SMCs in a power grid architecture is feasible because the amount of on-chip space of the SMC is small. For example, using a total of 100 SMCs, each SMC having an area of 50 μm 2 yields a space requirement of 5000 μm 2 . However, this is only 0.02% of the 25,000,000 μm 2 area available in a 5 mm×5 mm IC chip.
[0041] In another embodiment of the invention shown generally as 90 in FIG. 4( a ), a modification of the SMC 60 is provided. The SMC 60 shown in FIG. 3( b ) is modified to form a SMC 92 which incorporates more than one voltage sense transistor. FIG. 4( a ) shows a first voltage sense transistor 94 and an added second voltage sense transistor 96 . The second voltage sense transistor 96 enables a voltage to be measured in a metal layer 98 located underneath the power port PP 00 . A shorting inverter having a lower transistor 100 and an upper transistor 102 is connected to the PP 00 power port. The second voltage sense transistor 96 may be used to measure the voltage drops between metal layers M 1 and M 10 (see FIG. 4( b )) at different places on a power grid 104 . The present embodiment of the SMC increases the number of stimulus/response pairs capable of being measured and computed. The use of a larger number of stimulus/response pairs causes the security key to be more complex since more voltage drops are now computed between any pairing of the first voltage sense transistor 94 and second voltage sense transistor 96 across the array of SMCs 92 .
[0042] FIG. 4( b ) further illustrates the embodiment 90 having the modified SMC 92 , and has like components of FIG. 3( b ) identified with similar references numbers. The SMC 90 includes a shorting inverter having a lower transistor 100 that has a drain connected to the ground grid 30 , a first voltage sense transistor 94 that has a drain connected to the voltage sense wire 54 , and a set of three scan flip-flops FF 1 , FF 2 , and FF 3 . The volt meter 56 is connected to the voltage sense wire 54 and measures the voltage at this node of the SMC circuit 90 . The flip-flop FF 1 receives a scan chain input 74 . The flip-flop FF 1 further provides an output 76 to the flip-flop FF 2 and an inverter 78 . Output from the inverter 78 is provided to the gate of the lower transistor 100 of the shorting inverter. Output from the flip-flop FF 1 is also provided via line 106 to the gate of the upper transistor 102 of the shorting inverter. The flip-flop FF 2 has an output 80 provided to flip-flop FF 3 and also a gate of the first voltage sense transistor 94 .
[0043] The drain of the upper transistor 102 is connected to the source of the lower transistor 100 . The source of the first voltage sense transistor 94 connects via metal layers M 1 or M 10 84 to the power supply 36 . Output from the flip-flop FF 3 is provided to the gate of the second voltage sense transistor 96 via line 108 and other flip-flops of SMCs 90 .
[0044] FIG. 4( b ) has an additional flip-flop FF 3 used to control the second sense transistor 96 . In this embodiment, it is possible to replace the shorting inverter with a single positive channel field-effect transistor (“PFET”). However, the stacked devices of the shorting inverter are more robust to defects and provide a fault tolerant strategy to prevent yield loss that might result if a defect caused the stimulus transistor to remain in an ON state.
[0045] In another embodiment 110 of the present invention shown in FIG. 5 , an increase in the number of stimulus/response pairs is provided, which allows the stimulus to be applied from more than one SMC. In this embodiment 110 , multiple shorting inverters are enabled simultaneously at different locations and the voltage drops are measured using different combinations of transistor pairs each connected to one of a first voltage sense wire 112 or a second voltage sense wire 114 . The present application refers to these scenarios as “multiple-on” scenarios and the former embodiments 60 and 90 as “single-on” scenarios. Since the power grid is a linear system, superposition applies. Therefore, to make the IC more resilient to attack, where an attacker systematically deduces the voltage drops that would occur under a multiple-on scenario by measuring the voltage drops under all single-on scenarios, the present embodiment can include an obfuscation of the scan chain control bits. Under obfuscation, the number and position of the enabled shorting inverters are deterministically (or randomly) scrambled for a given scan chain control sequence, making it difficult or impossible to systematically apply single-on tests at known locations on the chip. For chip-specific random scrambling, a subset of the SMCs 116 can be used during initialization to define the state of a selector that controls the scan chain scrambling configuration.
[0046] The present embodiment requires the use of external instrumentation to measure the voltages and global electrical currents required to compute the IC's security key. Although this embodiment is applicable to chip authentication applications, e.g., where the objective is to periodically check the authenticity of a chip or set of chips to circumvent attempts to replace the chips with counterfeits, it is not amenable to cryptology applications that use the security key in hardware implemented encryption/decryption algorithms. In order to serve this latter application, the security key generation process preferably uses on-chip instrumentation.
[0047] As shown in FIG. 5 , a key generator control unit 118 drives the scan-in, scan-out and scan-clock signals of the SMCs with a specific pattern. The specific pattern enables one or more of the shorting inverters in the array of SMCs. This embodiment uses the original SMC 60 ( FIG. 3 ) modified to include a second voltage sense transistor connected between metal layer M 1 and the second voltage sense wire 114 . The scan pattern also enables two voltage sense transistors, one for each of the two voltage sense wires 112 and 114 . The two voltage sense wires 112 and 114 are routed to respective inputs 120 and 122 of a differential operational amplifier or Op Amp 124 . The Op Amp 124 outputs a logic low ‘0’ or a high ‘1’ at line 126 depending on whether the voltage on voltage sense wire 112 is larger or smaller than the voltage on voltage sense wire 114 , respectively. The 1-bit output on line 126 is sent to the key generation control unit 118 and the process is repeated until a sufficient number of bits are generated to realize the security key. This implementation of the present invention may be more sensitive to environmental variations because it makes use of voltages instead of equivalent resistances, as described earlier. Therefore, the response for a given chip under a given sequence of scan patterns may differ over time unless temperature and power supply noise are monitored and controlled. In other examples, more noise tolerant architectures are possible but such architectures will increase the required on-chip area associated with the generation of the security key.
[0048] The following describes the results from experiments to evaluate certain embodiments of the present invention specifically with respect to the diversity in the voltage drops and equivalent resistances in a set of thirty-six chips. Also described are the results from an additional set of experiments which evaluate the stability of the PUF circuit.
[0049] The PUF circuit stability experiments were performed on one of the chips in the set. To evaluate stability, the process was repeated for the security key generation/measurement process seventy-two times. No temperature control or specialized low noise test apparatus was used. The variation across the set of security keys from these experiments is due to environmental noise and temperature variations. The stability experiments assist in determining the probability of security key aliasing, i.e., the probability that two chips from the population generate the same security key. Data from the stability experiments was used as control data.
[0050] The experimental results for twelve of the chips from the set of thirty-six are shown in FIGS. 6 and 7 , using the voltage drops and equivalent resistances, respectively. The left half of the figures lists the chip number along the abscissa or x-axis. The right half of the figures along the abscissa axis lists twelve PUF circuit stability data for one chip. The six data points defining the chip security key are displayed vertically above the chip identifier. The ordinate or y-axis in the figures indicates the voltage drop and equivalent resistance in FIGS. 6 and 7 , respectively.
[0051] The diversity among the security keys in the twelve chips shown on the left side of FIGS. 6 and 7 is evident in both plots. In addition to the different patterns of dispersion in the security keys, the ordering of the data points from top to bottom is also distinct across all chips. The ordering is in reference to the SMCs that each data point corresponds to as shown in the figures. For example, SMC 00 in FIG. 3( a ) is assigned 0, SMC 01 is assigned 1, and SMC 12 is assigned 5. In FIG. 6 , the ordering for chip 1 is 5, 1, 2, 0, 4, and 3, while the ordering for chip twelve is 3, 0, 5, 1, 2, and 4. Therefore, the diversity among the security keys due to dispersion is actually larger because of the differences in the orderings. It is also clear from the experiments that in some embodiments environmental variations may have an impact on a security key and therefore, may need to be taken into account.
[0052] In some examples, there may be differences in the dispersion and ordering of the data points for the same chip across the voltage drop and equivalent resistance analyses. This is expected because the equivalent resistance eliminates an element of the diversity introduced by variations in the magnitude of the shorting electric currents. In order to quantitate the dispersion among the chip security keys, the Euclidean distance between the data points is computed and their variance is analyzed.
[0053] For a security key having six data points, the six data points in each security key can be interpreted as a single point in a six-dimensional space.
[0000] Dist=√[( x 1 −y 1 )+( x 2 −y 2 )+ . . . +( x 6 −y 6 )] Eq. 1.
[0000] The Euclidean distance between two security keys for chips x and y is given by Equation 1. The Euclidean distance is computed between all possible pairing of chips, i.e., (36*35)/2=630 combinations. The same procedure is carried out using the control data in which (72*71)/2=2556 combinations are analyzed.
[0054] In order to compute the probability of two chips having the same security key given the uncertainty associated with the voltage or equivalent resistance measurements, a histogram that tabulates the number of Euclidean distances partitioned into a set of bins for the chip and noise data sets separately is computed. The bins in each histogram are equal in width, with each equal to 1/25th of the total span that defines the range of Euclidean distances among the 630 and 2556 combinations of chip and noise data pairings, respectively. The histograms were then fit to gamma probability density functions (“PDF”). The histograms and the gamma PDFs are shown superimposed in FIG. 8 (chip) and FIG. 9 (noise) for the equivalent resistance analysis. In both cases, the gamma functions are a good fit to the histograms. The range of values found among the 630 chip pairings is between 0.45 and 5.0, as indicated by the abscissa axis, while the range for the noise analysis in the abscissa axis is between 0.01 and 0.12. Therefore, the largest value in the noise data is approximately four times smaller than the smallest value in the chip data.
[0055] The probability of aliasing was computed by first determining the Euclidean distance in the noise data that bounds 99.7% (3 sigma) of the area under the PDF. This particular Euclidean distance is the upper bound for the worst case noise and is equal to 0.099 for the data shown in FIG. 9 . Then, a computation is taken of the cumulative distribution function (“CDF”) of the chip data and is used as a worst case noise value to determine the probability of aliasing by looking up the ordinate or y-axis number of occurrences value on the chip CDF associated with this x-value. This gives the probability that the Euclidean distance between any pairing of two chips is less than or equal to the worst case Euclidean distance among the control data.
[0056] The results for the equivalent resistance and voltage analyses are given in Table 1. Using equivalent resistances, the probability of aliasing is 6.9e −8 or approximately 1 chance in 15 million. For the voltage analysis, the probability increases to approximately 1 chance in 28 billion. Given that the number of SMCs used to define the security key in these experiments is only six, it can be expected, based on these results that the probability would vastly improve in a design that included a larger number of SMCs.
[0000]
TABLE 1
Probability of aliasing
Analysis Type
Voltage
Equivalent Resistance
Prob Eucl. Dist. Of chips <
3.5e−11
6.9e−8
99.7% of all noise Eucl. dist.
[0057] The experiments and results described above on the power grid PUF circuit demonstrate feasibility of the embodiments described herein. Given the high degree of randomness provided by the single-on scenarios, in combination with the limited increase in randomness provided by multi-on scenarios, expanding single-on scenarios generates a security key that is difficult for unauthorized users to clone or determine. This approach to generating a security key further indicates that excellent single bit probabilities (the probability that a response bit is ‘0’ is nearly 50%) under an actual use scenario using data from the single-on PUF circuit is present. The actual use scenario involves comparing voltage drops or equivalent resistances between pairing of transistors on the same IC.
[0058] Another embodiment 130 of the present invention may provide an increase in the number of single-on scenarios, as shown in FIG. 10 . The embodiment 130 can include additional voltage sense transistors 132 that connect to each of the metal layers, e.g., M 1 through M 10 , in a vertical fashion. This allows 10 voltage drops and equivalent resistances based on the number of metal layers to be measured from each SMC. Flip-flops FF 2 through FF 5 drive the inputs from a respective flip-flop and provide outputs 134 - 140 , respectively, to a 4-to-16 inverting decoder 142 which functions to produce a single low logic ‘0’ on one of the voltage sense transistors when driven with a specific bit pattern. The inverting decoder 142 can be designed such that an input bit pattern of all high logic ‘1’s disables all voltage sense transistors.
[0059] Decoding logic can be added to minimize the additional hardware required for the SMC design in this embodiment. Even if these modifications triple the size of the PUF circuit to 150 mm, this embodiment still only represents an area of 0.06% on a 5 mm×5 mm chip that includes 100 copies of the SMC. Also, SMC leakage current in this embodiment is negligible because the stacked transistors in the shorting inverter are both off, and there is no voltage drop across the voltage sense transistors, when the SMCs are not being used. Furthermore, each SMC may be able to provide up to 10 times the number of response bits compared to the embodiment 60 of FIG. 3( b ), and therefore fewer copies will be needed to achieve a specific size for the response bit space.
[0060] The SMC embodiment of FIG. 10 permits any pairing of voltage drops or equivalent resistances from two different PUF circuits to be compared. However, the actual use scenario must be constrained such that only same layer voltage drops or equivalent resistances are compared. This restriction is necessary because voltage drops or equivalent resistances increase monotonically across the vertical dimension of the power grid. This restriction avoids adding bias to the single-bit probabilities that would otherwise occur if any arbitrary pairing was allowed.
[0061] The PUF circuit as described in FIG. 10 requires the use of external instrumentation to measure the voltages and global electrical currents needed to compute the PUF circuit responses. Although this embodiment serves the chip authentication application well, e.g., where the objective is to periodically check the authenticity of chips to circumvent attempts to replace the chips with counterfeits, it is not amenable to cryptography applications that use the PUF responses as the security key in encryption/decryption algorithms. In order to serve this latter application, the PUF responses can be computed using on-chip instrumentation.
[0062] An exemplary embodiment 150 using on-chip instrumentation is shown in FIG. 11 . A key generator control unit 152 drives the scan-in, scan-out and scan-clock signals of the SMCs 154 with a specific pattern to enable one or more of the shorting inverters in the array of SMCs. The scan pattern also enables two voltage sense transistors, one for each of the first voltage sense wire 156 and second voltage sense wire 158 , respectively. The two voltage sense wires 156 and 158 are routed to the inputs 160 and 162 , respectively, of a differential Op Amp 164 . The Op Amp 164 outputs a logic value ‘0’ or a ‘1’ along line 166 depending on whether the voltage on the first voltage sense wire 156 is larger or smaller than the voltage on the second voltage sense wire 158 . The 1-bit response is sent via line 166 to the key generation control unit 152 and the process is repeated until a sufficient number of bits are generated to realize the security key. This embodiment may be sensitive to environmental variations because it makes use of voltages instead of equivalent resistances. Other more temperature and noise tolerant embodiments are possible as discussed above, but such designs may increase the on-chip area needed to generate the security key. While a power grid 22 is illustrated as being connected to the SMC's 154 , it is contemplated that in an alternative embodiment a ground grid may be connected to the SMC's.
[0063] While the present invention and what is considered presently to be the best modes thereof have been described in a manner that establishes possession thereof by the inventors and that enables those of ordinary skill in the art to make and use the inventions, it will be understood and appreciated that there are many equivalents to the exemplary embodiments disclosed herein and that myriad modifications and variations may be made thereto without departing from the scope and spirit of the invention, which is to be limited not by the exemplary embodiments but by the appended claims. | A system and methods that generates a physical unclonable function (“PUF”) security key for an integrated circuit (“IC”) through use of equivalent resistance variations in the power distribution system (“PDS”) to mitigate the vulnerability of security keys to threats including cloning, misappropriation and unauthorized use. | 8 |
This application claims priority from German patent application serial no. 10 2012 204 839.1 filed Mar. 27, 2012.
FIELD OF THE INVENTION
The invention concerns a method for actuating a shifting element with three shift positions and a device according to the invention.
BACKGROUND OF THE INVENTION
Shifting elements for torque transmission, for example in the form of shifting clutches or claws, have long been known in geared mechanical transmissions such as countershaft transmissions. Countershaft transmissions are usually made with gearwheels, so-termed loose wheels, mounted rotatably, on a shaft, which mesh with gearwheels connected in a rotationally fixed manner to other shafts so that they form so-termed gear pairs. By alternately connecting the gearwheels mounted rotatably on the shaft to the shaft in a rotationally fixed manner, the gear pairs can be connected into the force flow of a countershaft transmission by means of appropriate shifting elements such as synchronizers, claws or frictional elements in order to obtain various gear steps. As a rule this requires an actuating element in the form of a manual actuator, an electric actuator or a piston/shifting-cylinder arrangement that can be actuated hydraulically or pneumatically. In such piston/shifting-cylinder arrangements a piston is arranged and able to move axially in a shifting cylinder. The piston can move actively to at least one shift position and in its thrust direction is directly or indirectly connected fixed to the shifting element. In this case the actuating element can actuate the shifting elements mechanically, hydraulically, pneumatically or magnetically in relation to the shaft on which the rotatably mounted gearwheels are arranged.
A shifting element usually belongs to a shifting group of a geared mechanical transmission. In such a case a shifting group is preferably formed of two rotatably mounted gearwheels arranged next to one another in the transmission, which can alternately be engaged in the torque transmission by means of a shifting element. As is known, for example from the document DE 197 56 639 A1 by the present applicant, in such cases for each shifting group of a geared transmission, one shifting element with a cylinder that acts on both sides, having a piston which is moved by a fluid, can be used.
Depending on the design, it can also be necessary to maintain a central position in a shifting group, this as a rule being the neutral position. In the central or neutral position it is important that no part of the shifting element engages with any loose wheel. Thus, for example the central position constitutes the passive position of the actuating element. In that case the actuating element is held in the central position for example by springs, and has to be pushed actively to the other two shifts positions. For this, in pneumatic or hydraulic control systems two working lines and two piston faces are needed. Without such holding in the central position by spring action there is a risk that the central position will not be able to be approached, set and maintained exactly so that parts of a shifting element are at least partially engaged with a loose wheel.
The problem of a safe approach to the central position can also be solved by mechanical systems without the central position being held by springs. One solution is described, for example, in the document DE 40 38 170 A1. A shifting cylinder is considered, which has a two-sided controllable piston coupled to a shifting element, the piston being acted upon with a pressure medium by way of control elements such as displacement valves. The piston consists of two double pistons that act in opposition, which can move within a common cylinder housing, such that in the cylinder housing a respective pressure space with a pressure medium connection is associated with each of the two double pistons. The first piston of each double piston is rigidly connected to move with a shifting element and the second piston of each double piston is connected to a first piston so that it can move freely. When the pressure is equalized on both sides, the two double pistons are held in the neutral position with their freely movable, second pistons against a stop in the cylinder housing, and in each case when acted upon alternatively by pressure on one side or the other, they are pushed out of the neutral position to the shifting position, in such manner that the unpressurized double piston with its two pistons has its shifting displacement imparted to it by the pressurized double piston.
However, for example due to lack of fitting space or even by virtue of a component identity approach or platform concept, it can be in part not possible, or only so with difficulty, to realize a shifting cylinder that can be actuated to both sides with two working lines and with a corresponding control system.
SUMMARY OF THE INVENTION
Accordingly, with a hydraulically or pneumatically controlled actuating element in the form of a shifting cylinder with one working line, the purpose of the invention is to ensure reliable movement to three shift positions of a shifting element for the shifting of a shifting packet. In this, the central position in particular should be secure so that in this position there can be no contact between parts of the loose wheels and the shifting element.
The basic concept of the invention is that to move a piston in a cylinder against a force, a certain fluid pressure is needed as the displacing force. If, from a particular point along the control path, the opposing force increases abruptly from one shift position to the next, that point in the control path can be recognized and maintained by not increasing the fluid pressure and hence the displacing force any further. To move the piston farther, the fluid pressure in the pressure space of the cylinder has to be increased until a displacing force is built up which is larger than the opposing force acting on the piston.
The invention solves the problem in that a shifting element is pushed by a spring element to a first end position. To bring about a shift, the shifting element must be actuated hydraulically or pneumatically to move it along the control path against the force of the spring element. To recognize the central, or neutral position precisely, when the central position is reached the lever arm is made shorter by virtue of a special contour on the area contacted by the spring element. The area contacted by the spring element is understood to be the elements that are in contact with the spring element, such as pressure elements for transmitting the force to the spring element, buttress elements or supports that hold the spring element. This produces an abrupt increase of the displacement force required in order to move the shifting element farther and reach the third shift position at the second end position of the piston. In a fluid-actuated system this abrupt force increase enables a specific pressure to be set. For this, cup springs or membrane springs of various designs are used as spring elements. The cup spring can be designed such that it exerts a spring force that remains almost constant over the control path. To move farther along the control path no pressure increase of the actuating element is needed, since the spring element presses the shifting element back with its spring force.
An abrupt increase of the displacement force as required by the invention can also be produced by a combination of at least two spring elements. In this case a first spring element exerts a first force on the shifting element in opposition to its movement direction and, beyond a particular position along the control path, this first opposing force is supplemented by a second opposing force produced by a second spring element. This also produces an abrupt increase of the displacement force required. In this variant according to the invention torsion springs are used as the spring elements. Of course, the different spring forces can also be produced by a plurality of spring elements.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention and its embodiment variants will now be described in greater detail with reference to the following drawings, which show:
FIG. 1 : Diagram of the hydraulic actuation of a claw (as in the prior art)
FIGS. 2 and 2A : Diagram of a lever arm shortened according to the invention, and associated characteristic curves
FIG. 3 : Diagram of the actuation of a pressure element with a combination of two springs
FIG. 4 : Method according to the invention, with a contour on the buttress element
FIG. 5 : Method analogous to FIG. 4 with a contour on the pressure element and on the buttress element
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In FIG. 1 (showing the prior art) the three shift positions A, B, C will be explained briefly. The figure shows three shifting groups 2 , 4 , 6 each with an actuating element 8 , 12 , 16 respectively, in the form of a controlled cylinders with a piston, and a shifting element 10 , 14 , 18 respectively which is connected directly to the piston. Each of the shifting groups 2 , 4 , 6 is pictured in one of the three shift positions A, B, C. The first shifting group 2 is in the shift position A in which the piston of the actuating element 8 is in its first end position. In that shifting position the shifting element 10 is engaged with the gearwheel closest to the actuating element 8 . The second shifting group 4 is shown in the second shifting position B, namely the central or neutral position. The piston of the actuating element 12 of the shifting group 4 is in the central position and the shifting element 14 is then not engaged with either of the gearwheels of the shifting group 4 . The third shifting group 6 is shown with the piston of the actuating element 16 and thus also the shifting element 18 in the third shifting position C. In this third shifting position C, the shifting element 18 is engaged with the gearwheel of the shifting group 6 which is farthest away from the actuating element 16 , and the piston has reached its second end position.
FIGS. 2 and 2A show the diagram of a lever shortened according to the invention and the associated characteristic curves in the shift positions A, B, C already described. FIG. 2A shows a device according to the invention with a pressure element 20 , which is connected to an actuating element (not shown here) and which is in contact with a cup spring 22 on one side. The pressure element 20 is part of a shifting element. Radially on the inside and on its side facing away from the pressure element 20 the cup spring 22 is in contrast with a mounting support 24 . The pressure element 20 serves to transmit the actuating pressure, starting from the actuating element, by way of the pressure element 20 , to the cup spring 22 , whereas the cup spring 22 with its spring force is already prestressed in shift position A and presses against the pressure element 20 . The pressure element 20 does not rest against the cup spring over a flat area, but is provided with a special contour. In this example according to the invention this takes the form of two contours elements 26 , 28 shaped as pointed elevations on the side of the pressure element 20 that faces toward the cup spring 22 . The contour element 26 is radially farther away from the axis of the cup spring 22 than is the contour element 28 . In the first shift position A the pressure element 20 contacts the cup spring 22 only at the contour element 26 . In order to reach the central position, i.e. shift position B, the actuating element has to move the pressure element 20 and the cup spring 22 against the force of the cup spring 22 . During this the pressure transmission takes place via the contour element 26 until the second shift position B is reached and the cup spring 22 adopts a position in which both contour elements 26 and 28 are in contact with the cup spring 22 . From then on, with further actuation of the shifting element toward the third shift position C, the pressure transmission is taken over by the contour element 28 . The distance of the contour element 28 away from the point where the cup spring 22 is in contact with the mounting support 24 is smaller than that of the contour element 26 . Thus, the lever for transmitting the force of the actuating element is shorter, and a larger force must therefore be applied in order to move the pressure element 20 farther in the direction toward shift position C. As a result different pressures are needed in order to move to shift position C, starting from shift position A, so that for each shift position A, B, C specific actuating pressures can be defined. Hence the actuating pressure can be adjusted in such manner that all the shift positions A, B, C can reliably be achieved.
The performance graphs 30 show the actuating element pressures at each shift position A, B, C, at the respectively associated points S A , S B , S C along the control path. At the first shift position A a certain actuating pressure p 1 is required in order for the contour element 26 to move the cup spring 22 in the direction toward shift position B. At shift position B there is an abrupt increase of the actuating pressure and a pressure p 2 is needed to move the cup spring farther to the third shift position C. In the initial shift position A no pressure has to be applied, since there the actuating element is in its end position.
The performance graphs 32 show the functions of the contour elements 26 , 28 along the control path S A , S B , S C . As far as shift position B the pressure is transmitted by way of the contour element 26 . From the time, in the second shift position B, when both contour elements 26 , 28 are in contact, during any further movement in the direction toward the third shift position C, the force is transmitted by the contour element 28 .
The performance graphs 34 show the overlap or engagement of the shifting element with the gearwheels of the shifting group along the control path S A , S B , S C . In the first shift position A the shifting element is engaged with the claws of a first gearwheel Z 1 of the shifting group. In the third shift position C the shifting element is engaged with the claws of a second gearwheel Z 2 of the shifting group. In the second shift position B, the neutral position, according to the stated objective no part of the shifting element must be in contact with a gearwheel Z 1 , Z 2 . The diagram shows that before reaching the second shift position B the connection of the shifting element with the first gearwheel Z 1 is broken, and only on the way from the second shift position B to the third shift position C does the shifting element engage with the second gearwheel Z 2 .
The performance graph 36 shows the variation of the spring force over the control path S A , S B , S C . As already described, a cup spring 22 can be used so that the actuating force remains almost constant over a control distance. In this example the cup spring 22 has been prestressed until it exerts approximately the force F 1 . This corresponds to the prestressing force with which the piston of the actuating element is loaded in its initial position A. To move it from the first shift position A to the second shift position B, an actuating pressure must be applied which is greater than the spring force F 1 . From the second shift position B onward the spring force curve rises. To move from the second shift position B to the third shift position C, namely to the second end position of the piston of the actuating element, it is thus necessary for the actuating element to apply a force at least larger than F 2 . The force increase of the cup spring 22 from the second shift position B onward, indicated by the spring characteristic curve, can additionally support the abrupt pressure increase for the recognition of the central position.
As already described, the abrupt pressure increase can be produced not only by means of a defined contour on the contact area of a cup spring, but also by actuating a pressure element in combination with spiral springs. This is illustrated in FIG. 3 . In this case the pressure element 20 is not provided with a special contour, but is connected to one end of a first spiral spring 38 . At its opposite end in the direction of the shifting path S, the spring is attached to a spatially fixed buttress element 40 . In the initial position the first spiral spring 38 is already acted upon with pressure by the pressure element 20 . The pressure element 20 is part of the shifting element and is connected to an actuating element (not shown). On the buttress element 40 , a second spiral spring 42 is attached to the same surface to which the first spiral spring 38 is attached. The second spiral spring 42 is inserted under compression between the buttress element 40 and a first inner side of a U-shaped holding element 44 . The second inner side of the U-shaped holding element 44 is in contact with the side of the buttress element 40 facing away from the pressure element 20 . The first spiral spring 38 acts upon the pressure element 20 with a force F 3 in the direction of the control path. The control path is the distance to be covered by the actuating element or by the pressure element 20 in order to move from the first shift position A to the second shift position B and then to the third shift position C. In FIG. 3 the shifting element is shown in all three shift positions. In the initial shift position A, the spring force F 3 of the first spiral spring 38 pushes against the pressure element 20 . To move to the second shift position B, the spring force F 3 of the first spiral spring 38 must therefore be overcome. When the pressure element 20 reaches the outside of the U-shaped holding element 44 , shift position B has been reached. At this point an abrupt pressure increase is produced since, to move farther to the third shift position C, in addition to the spring force F 3 of the first spiral spring 38 , the spring force F 4 of the second spiral spring 42 is also now being applied. In this case the U-shaped holding element 44 serves to ensure exact positioning of the second shift position B and of the abrupt pressure increase produced by virtue of the second spiral spring 42 . To be able to move to the third shift position C, from the second shift position B onward both of the spring forces F 3 ,and F 4 have to be overcome. If now the pressure element moves farther to the third shift position C, not only are the two spiral springs 38 , 42 compressed but also the U-shaped holding element 44 is pushed in the direction along the control path.
FIG. 4 illustrates a method according to the invention in which there is a contour on the buttress element. The contour for changing the effective lever length does not necessarily have to be formed on a pressure element or on the side of the actuating element. The contour can also be formed on a separate buttress element positioned adjacent to the cup spring 22 on the side facing away from the pressure element 20 , or as illustrated in this case, it can be provided by the design of the holder 24 itself, in which the contour is formed directly. Again, there are two contour elements 46 and 48 . The first contour element 46 is directly at the contact point of the cup spring 22 on the holder 24 . Again, the shifting element is shown in all three shift positions A, B, C. In the first shift position A, namely the first end position of the piston of the actuating cylinder, a force is exerted by the pressure element 20 on the cup spring 22 so that the cup spring 22 is pre-stressed. The cup spring 22 is in contact only with the contour element 46 on the holder 24 . If now the actuating element is moved along the control path in the direction toward the third shift position C, then when the second shift position B is reached the second contour element 48 too comes in contact with the cup spring 22 . The effective lever of the pressure element 20 on the cup spring 22 is thereby shortened and an abrupt pressure increase takes place. In order to move farther to the third shift position C, a larger force or a higher pressure must be exerted on the pressure element 20 and the cup spring 22 . Thus, the second shift position B can be clearly distinguished.
A more pronounced pressure increase can also be produced if a corresponding contour can be formed on different elements of the shifting group. In FIG. 5 , for example, contours are formed on the pressure element 20 and on the holder 24 . FIG. 5 also shows that the contour for lever shortening can be designed differently. In this case there are no sharply projecting individual contour elements, but instead contour surfaces 50 and 52 . Other contour designs that have the same effect are possible. To illustrate the shift sequence the shifting element is shown in all three shift positions A, B, C. In the initial position A the pressure element 20 , which is part of the shifting element, presses against the pre-stressed cup spring 22 . The cup spring 22 rests against the holder 24 radially inside at the corner of the contour surface 52 . The pressure element 20 contacts the cup spring 22 only with the radially outer edge of the contour surface 50 located toward the edge of the cup spring 22 . If now the pressure element 20 is pushed in the control path direction to the second shift position B, the actuating element must overcome at least the force of the cup spring 22 to be able to move. When the second shift position B is reached the surfaces 50 and 52 are both in contact with the cup spring 22 . During subsequent movement from the second shift position B to the third shift position C, according to the invention a lever shortening takes place. On moving in the control path direction the cup spring 22 is in contact with the edge of the surface 50 closest to the holder 24 and with the edge of the surface 52 next to the pressure element 20 . The lever length of the cup spring 22 is accordingly shorter and correspondingly a larger force has to be applied in order to shift from the second shift position B to the third shift position C. The abrupt pressure increase required according to the invention is therefore brought about.
In present-day hybrid transmissions, already present proportional pressure regulators can be used to produce the pressure jump. In a proportional pressure regulator a specific pressure corresponds to a specific current. No further regulators have to be built in.
INDEXES
2 Shifting group
4 Shifting group
6 Shifting group
8 Actuating element
10 Shifting element
12 Actuating element
14 Shifting element
16 Actuating element
18 Shifting element
20 Pressure element
22 Cup spring
24 Holder
26 Contour element
28 Contour element
30 Actuating pressure performance graph
32 Contour element performance graph
34 Gearwheel engagement performance graph
36 Spring performance graph
38 First spiral spring
40 Buttress element
42 Second spiral spring
44 U-shaped holder
46 Contour element
48 Contour element
50 Contour surface on the pressure element
52 Contour surface on the holder
A First shift position, first end position
B second shift position, neutral position
C Third shift position, second end position
S A Position along the control path at shift position A
S B Position along the control path at shift position B
S C Position along the control path at shift position C
p 1 , p 2 , p 3 Actuating pressure
Z 1 First gearwheel
Z 2 Second gearwheel
F 1 , F 2 , F 3 , F 4 Spring force | A method of actuating a shifting element with three shift positions, having a simply controlled shifting cylinder as the actuating element, a shifting element for shifting to the three shift positions and a pressure regulator, such that the shifting cylinder is designed as a cylinder with one working line and the shifting element is pushed by the spring force of at least one spring element to an end position and moved to the other shift positions in opposition to the spring force. The central position is recognized in that, when the correct shifting element position is reached, the force for moving the shifting element in opposition to the spring force abruptly increases and, because of this, a specific pressure can be set by a pressure regulator for the central position. | 5 |
CROSS-REFERENCE TO RELATED U.S. APPLICATIONS
This application is a National Stage of International Application No. PCT/US2010/000417, filed Feb. 12, 2010, and entitled “Methods and Apparatus for Sample Temperature Control in NMR Spectrometers,” which claims the benefit of U.S. Provisional Application No. 61/152,619, filed Feb. 13, 2009, and entitled “Method and Apparatus for Accurate and Precise Stabilization of the Sample Temperature in NMR Spectrometers with Automated Compensation of Radio-Frequency Induced Heating,” each of which is hereby incorporated by reference in its entirety.
FEDERALLY SPONSORED RESEARCH
This invention was made with government support under GM 47467 awarded by the National Institute of Health. The government has certain rights in the invention.
FIELD OF THE DISCLOSURE
The technology described herein relates generally to control and stabilization of the temperature of samples inside nuclear magnetic resonance (NMR) spectrometers in an automated fashion with a high level of accuracy and precision. In certain embodiments, the temperature is automatically maintained during consecutive NMR experiments, in particular if their radio-frequency pulse schemes cause sample heating.
BACKGROUND
Control and stabilization of the sample temperature are important criteria for high-resolution NMR experiments, because the measured chemical shift is a physical property that can be sensitive to small temperature changes. NMR experiments employ radio frequency (RF)-pulses that induce sample heating due to dielectric absorption. Differential sample heating among a series of experiments causes difficulties for the analysis of the resulting spectra. For example, for protein structure determination, the side chain protons of proteins are often assigned using TOCSY-type experiments with many RF-pulses and strong sample heating. In contrast, NOESY experiments used to provide distance information feature only a few RF-pulses and cause thus little sample heating. The calculation of protein structures from these experiments depends on the correlation of the chemical shifts in both types of experiments and a high correspondence and control of the sample temperatures in these different experiments can be important in determining accurately protein structures.
Due to these reasons, it is important to control and stabilize the NMR sample temperature with accuracy and precision of the order of 0.1 K. The terms accuracy and precision are used here in their canonical definitions. The accuracy of temperature stabilization refers to the difference between a desired temperature and the actual average sample temperature. Temperature control and stabilization is accurate, if the apparatus creates and maintains the sample temperature at a value desired by the user. The precision of temperature stabilization refers to the standard deviation of the sample temperature. Temperature control and stabilization is precise, if the remaining temperature fluctuations are small, irrespective of whether the temperature is accurate.
In conventional NMR probes, the sample temperature control is achieved with a thermocouple located in the air stream that forms the temperature reservoir for the sample. A measurement of the air stream temperature with accuracy and precision of 0.1 K or below is typical in such conventional setups. However, these external measurements of the air stream do not detect the true sample temperature. RF-induced sample heating, often as large as five degrees K, is not detected and thus not corrected. Thus, despite a precision of 0.1 K, the accuracy of sample temperature stability is 5 K or larger in conventional systems.
An interactive method to correct differential RF-heating in a series of experiments is manual adjustment of the temperature control, by comparing one-dimensional (1D) traces of the spectrum of interest to a reference spectrum. Such a procedure is however error-prone, cumbersome and time-consuming and forbids itself for automated or high-throughput setups. Modern automated setups require that several different experiments on the same sample or the same experiment on different samples are consistently recorded and automatically analyzed. These demands cannot be fulfilled with an interactive method.
Highly accurate and precise measurements of the sample temperature can be achieved in a non-invasive way by using the temperature-dependence of the chemical shift of suitable nuclei as thermometers (e.g. van Geet, A. L., Calibration of methanol nuclear magnetic resonance thermometer at low temperature, Anal. Chem. 42, 679-680 (1970). This is being used in many practical NMR applications, in particular to calibrate the temperature unit of the NMR probe upon installation. However, only if these measurements are carried out in samples with an exactly defined composition, often containing the pure thermometer substance in bulk, the measured chemical shifts can be interpreted as temperatures. Such methods are thus not applicable on samples with a non-standard chemical composition.
A method for using direct NMR measurements to improve the temperature stabilization has been disclosed by H. Keiichiro, Japanese Patent 3-156394 (1991). The disclosed method uses a conventional field-frequency lock unit to extract a second frequency component besides the field-frequency lock signal, calculates the chemical shift difference of these two resonances, and compares the result with values from a reference table for the desired temperature. The outcome of this temperature measurement is then directly used to control the sample heater, either replacing the conventional thermocouple measurements or by adding the two values together. However, since chemical shifts are not only dependent on the temperature, but also on other sample parameters, like the pH value, the salt concentration, etc., the use of this method would require temperature reference tables for each of the infinite number of possible sample compositions. Since these tables are not available, the accuracy achieved by this method is as high as 10 K. Due to this drawback, the temperature controller as described in Japanese Patent 3-156394 is not practicable and has not become widely used.
SUMMARY
According to some aspects, a method is described that achieves accurate and precise stabilization of the NMR sample temperature by a combination of (i) repeatedly measuring the resonance frequency or chemical shift of a suitable inert thermometer substance, e.g., using either one-dimensional Fourier transform (1D FT) NMR combined with automated peak picking or frequency sweeping, (ii) using the measured data to generate dynamic temperature values for the control of the heater system, (iii) using a thermocouple measurement in the air stream to achieve precision, (iv) employing the automated procedure “MET” for a combined management of the experiments of interest and the generation of the temperature control signals. MET stands for “Management of Experiments and Temperature.” By using inter-experimental periods of variable length, the steady state is established individually for each experiment in a series of experiments and the temperature can thus be kept at the same reference value for one or several different experiments in an automated fashion. The precision of the method disclosed here can be on the order of 0.1 K or less. The accuracy can be on the order of 0.1 K or less, which represents a 20-100 fold improvement over previous and conventional methods.
The systems and methods described herein may be referred to as “temperature-lock” in reference to the field-frequency lock that is commonly used to stabilize the static magnetic field of an NMR magnet against field drift or other disturbances, even though the technical details of the present technology differ from those of a field-frequency lock system.
Thus, it should be appreciated that according to some aspects, accurate and precise temperature control may be achieved by monitoring a sample temperature during the acquisition of NMR experiments. Such experiments may induce heating within a sample in some embodiments, and aspects of the technology described herein accurately and precisely compensate for such sample heating by monitoring changes in an NMR resonance frequency or chemical shift of a thermometer substance during experimentation, and adjusting an air temperature within the sample chamber during the experiments. According to some non-limiting embodiments, a trigger signal to start an NMR experiment is generated in response to comparing a monitored resonance frequency value or chemical shift value of a thermometer substance to a reference value. In certain embodiments, the reference value is previously acquired.
In some embodiments, the temperature-lock method is used in conjunction with a field-frequency lock. If a field-frequency lock is used, the resonance frequency of the field-frequency lock nucleus can serve as a reference value to define the chemical shift scale for all nuclei via indirect referencing. The nucleus for the field-frequency lock can differ from the nucleus used for the temperature-lock. In some embodiments, the nucleus used for the field-frequency lock is the same as the nucleus used for the temperature-lock. If the present invention is used without field-frequency lock, the chemical shift measurements of the temperature-lock substance can be referenced relative to an absolute standard. In such an embodiment, possible fluctuations or drifts of the static magnetic field can decrease the temperature lock precision.
According to one aspect, a nuclear magnetic resonance (NMR) system is provided. The NMR systems comprises a sample chamber, an adjustable heater to adjust an air temperature within the sample chamber, a thermocouple to provide a thermocouple signal representing the air temperature within the sample chamber, and a sensor to monitor a frequency response of a thermometer substance within a sample in the sample chamber and to provide a varying output signal indicative of the frequency response of the thermometer substance as a sample temperature of the thermometer substance varies. The NMR system further comprises a processor coupled to the sensor to receive the varying output signal of the sensor and to generate a compensation signal indicative of a target value of the air temperature. The NMR system further comprises a controller to compare the thermocouple signal and the compensation signal and to produce a feedback control signal, based on the comparison, for adjusting the adjustable heater.
According to another aspect, a method of operating a nuclear magnetic resonance (NMR) system is provided. The method comprises detecting an air temperature of a sample chamber of the NMR system, monitoring a frequency response of a thermometer substance in a sample within the sample chamber during an NMR experiment, and determining an experimental resonance frequency value from the frequency response. The method further comprises comparing the experimental resonance frequency value to a reference resonance frequency value, and, in response to comparing the experimental resonance frequency value to the reference resonance frequency value, iteratively generating a compensation signal indicative of a target value of the air temperature to make the experimental resonance frequency value approximately equal to the reference resonance frequency value. The method further comprises comparing the target value of the air temperature to the detected air temperature.
According to another aspect, at least one computer-readable storage medium is provided that is encoded with computer-executable instructions that, when executed, cause at least one computer to perform a method for use in a nuclear magnetic resonance (NMR) system. The method comprises detecting an air temperature of a sample chamber of the NMR system, monitoring a frequency response of a thermometer substance in a sample within the sample chamber during an NMR experiment, and determining an experimental resonance frequency value from the frequency response. The method further comprises comparing the experimental resonance frequency value to a reference resonance frequency value, and, in response to comparing the experimental resonance frequency value to the reference resonance frequency value, generating a compensation signal indicative of a target value of the air temperature to make the experimental resonance frequency value approximately equal to the reference resonance frequency value. The method further comprises comparing the target value of the air temperature to the detected air temperature.
According to another aspect, a method of controlling a temperature of a sample in a nuclear magnetic resonance (NMR) system is provided. The method comprises controlling an air temperature of a sample chamber of the NMR system to provide a first sample temperature for the sample, the sample being at least partially disposed in the sample chamber. The method further comprises measuring a resonance frequency reference value of a thermometer substance within the sample at the first sample temperature. The method further comprises applying a first radio frequency (RF) excitation sequence to the sample to induce heating within the sample. The method further comprises measuring a resonance frequency experimental value of the thermometer substance during application of the first RF excitation sequence. The method further comprises comparing the resonance frequency experimental value to the resonance frequency reference value, and generating a compensation signal indicative of an amount by which to alter the air temperature of the sample chamber to make the resonance frequency reference value and the resonance frequency experimental value approximately equal.
According to another aspect, at least one computer-readable storage medium is provided that is encoded with computer-executable instructions that, when executed, cause at least one computer to perform a method for controlling a temperature of a sample in a nuclear magnetic resonance (NMR) system. The method comprises controlling an air temperature of a sample chamber of the NMR system to provide a first sample temperature for the sample, the sample being at least partially disposed in the sample chamber. The method further comprises measuring a resonance frequency reference value of a thermometer substance within the sample at the first sample temperature. The method further comprises applying a first radio frequency (RF) excitation sequence to the sample to induce heating within the sample. The method further comprises measuring a resonance frequency experimental value of the thermometer substance during application of the first RF excitation sequence. The method further comprises comparing the resonance frequency experimental value to the resonance frequency reference value. The method further comprises generating a compensation signal indicative of an amount by which to alter the air temperature of the sample chamber to make the resonance frequency reference value and the resonance frequency experimental value approximately equal.
In the various aspects and embodiments summarized above, it will be appreciated that the NMR system may further comprise a field-frequency lock subsystem for stabilizing the static magnetic field of the NMR system. In some embodiments, the field-frequency lock subsystem operates using the same nuclei of an atomic species that are used for the temperature lock. In some embodiments, the field-frequency lock subsystem operates using different nuclei of an atomic species than are used for the temperature lock.
It should be appreciated that all combinations of the foregoing concepts and additional concepts discussed in greater detail below (provided such concepts are not mutually inconsistent) are contemplated as being part of the inventive subject matter disclosed herein. In particular, all combinations of claimed subject matter appearing at the end of this disclosure are contemplated as being part of the inventive subject matter disclosed herein. It should also be appreciated that terminology explicitly employed herein that also may appear in any disclosure incorporated by reference should be accorded a meaning most consistent with the particular concepts disclosed herein.
BRIEF DESCRIPTION OF THE DRAWINGS
The skilled artisan will understand that the figures, described herein, are for illustration purposes only. It is to be understood that in some instances various aspects of the invention may be shown exaggerated or enlarged to facilitate an understanding of the invention. In the drawings, like reference characters generally refer to like features, functionally similar and/or structurally similar elements throughout the various figures. The drawings are not necessarily to scale, emphasis instead being placed upon illustrating the principles of the teachings. The drawings are not intended to limit the scope of the present teachings in any way.
FIG. 1 is a block diagram of one embodiment of a temperature-lock NMR system.
FIG. 2 is an embodiment of a management of experiments and temperature (MET) procedure.
FIG. 3 represents one embodiment of the MET procedure.
FIG. 4 depicts functional aspects of one embodiment of the temperature-lock method.
FIG. 5 depicts various embodiments for nuclear magnetic resonance frequency measurements without and with temperature-locking.
FIG. 6 shows chemical shift measurements for three temperature-lock nuclei in aqueous solution, measured at 500 MHz field strength.
FIG. 7 depicts the application and effect of temperature locking in an NMR spectroscopy experiment.
FIG. 8 illustrates a conventional NMR setup.
The features and advantages of the present invention will become more apparent from the detailed description set forth below when taken in conjunction with the drawings.
DETAILED DESCRIPTION
Following below are more detailed descriptions of various concepts related to, and embodiments of, inventive systems, methods and apparatus for sample temperature control in NMR spectrometers. It should be appreciated that various concepts introduced above and discussed in greater detail below may be implemented in any of numerous ways, as the disclosed concepts are not limited to any particular manner of implementation. Examples of specific implementations and applications are provided primarily for illustrative purposes.
In various embodiments of the present invention, apparatus and methods for nuclear magnetic resonance (NMR) spectroscopy are described herein, which in exemplary implementations can stabilize the sample temperature in an NMR spectrometer with a precision and an accuracy of about 0.1 K or less. This sample temperature stabilization technique is referred to herein as “temperature-lock.” In certain embodiments, the temperature-lock method automatically maintains the sample at the same reference temperature over the course of different NMR experiments.
By way of introduction and for purposes of understanding, certain aspects of a conventional NMR spectrometer are first reviewed. FIG. 8 depicts an embodiment of a conventional NMR spectroscopy system, which comprises a sample tube 1 , feedback controller 2 , temperature sensor 3 , temperature controller 4 , RF coils 6 , an NMR spectrometer 7 , a main computer or processor 10 , a field-frequency lock spectrometer 11 , and static magnetic field B 0 coils 12 . A portion of the sample tube 1 can be located inside the NMR magnetic coils 6 , 12 and provide for the introduction of a sample into the NMR system. The sample tube can extend to a region outside the magnetic coils for access by a system user. The feedback controller 2 can provide a signal to the temperature controller 4 based on the temperature measured by the temperature sensor 3 and a user-defined temperature setting T set . The temperature sensor 3 can comprise a thermistor, thermocouple or other conventional temperature measurement device. The temperature controller 4 can comprise a heating and cooling or a heating device. For the embodiment shown, an air stream 5 is provided by an air supply apparatus and is heated by heater 4 . The air stream can flow as shown by the dashed arrows and bathe a portion of the sample tube 1 in which the sample of interest is located. The RF coils 6 can be one or multiple coils configured to be excited at various RF frequencies to produce RF magnetic fields in a region containing the sample. The NMR spectrometer 7 can comprise a spectrometer that provides one or more channels for one or several different nuclei. In various embodiments, the main computer 10 provides for overall control of the NMR spectrometer system.
For the conventional system shown in FIG. 8 , the feedback controller 2 , temperature sensor 3 , temperature controller 4 , and air stream 5 can be used to provide a thermal bath for a sample within the sample tube 1 and to control the sample temperature. For example, thermocouple 3 measures the air stream temperature and feedback controller 2 regulates the heater 4 so that the detected temperature (represented by a voltage in an analog system or by a digital signal) matches the user-defined temperature T set . In operation, these elements providing a thermal bath for the sample operate independently from the spectrometer 7 in the conventional setup. The NMR spectrometer 7 can include one or several channels for the nuclei of interest, e.g., the three channels 1 H, 13 C and 15 N for biological triple resonance experiments. The field-frequency lock spectrometer 11 and static field coils 12 can maintain the static B 0 field constant over the course of a measurement by using a signal from a suitable field-frequency lock nucleus. The field-frequency lock can operate independently of the acquisition of the experiments and of the temperature unit. (Exceptions are implementations which require usage of the field-frequency lock channel for some pulses. In those implementations, the field-frequency lock channel can be alternatingly switched between the two demands.) In some embodiments, the chemical shift scale for all nuclei is defined by arbitrarily setting the field-frequency resonance to a user-defined fixed value at all temperatures, e.g., 4.7 ppm for D 2 O, and then referencing all other nuclei indirectly to this fixed point by their relative gyromagnetic ratios. This scheme of chemical shift referencing is also used in some non-limiting embodiments of the present invention.
The setup of one non-limiting embodiment of the technology described herein is shown in FIG. 1 . In the figure, 1 represents the sample tube, sitting inside the NMR magnet. An air stream 5 is provided by an air supply and can be heated and/or cooled by temperature controller 4 . The air stream follows the way of the dashed arrows. 3 represents a thermocouple or other conventional temperature measurement device. 10 depicts the main computer. Feedback controller 2 can provide a signal for the temperature controller 4 based on the temperature measured by temperature sensor 3 and the dynamic temperature control value T dyn (which in some embodiments may correspond to a target air temperature value) provided by processor 10 . This temperature signal is represented either by a voltage in analog systems, or by a digital signal. RF coil 6 comprises one or multiple coils tunable to the resonance frequencies of all required nuclei. Spectrometer 7 comprises an NMR spectrometer that contains channels for one or several different nuclei. Block element 8 represents an optional additional channel of the NMR spectrometer. 11 represents the channel for the field-frequency lock that controls the static field coils 12 to maintain the global B 0 field at the reference value. It should be appreciated that additional connections between the main computer 10 and field-frequency lock channel 11 and static field coils 12 may exist in some embodiments, but are not shown in the drawing for purposes of illustration.
Compared to the conventional setup, the NMR sample of interest now contains an additional inert thermometer substance, the temperature-lock substance Z with the temperature-lock nucleus L. In various embodiments, the inert thermometer substance does not chemically react with a substance being studied in the NMR experiment, or is biocompatible with the substance being studied in the experiment. An embodiment for aqueous samples comprises Z=H 2 O and L= 17 O, but many other choices are possible as discussed below. If the nucleus L is not covered by the existing channels of the conventional NMR spectrometer setup, an additional channel 8 for the nucleus L is added. In this case, the coils 6 are adapted to be tunable to this nucleus. The resonance frequency of the nucleus L in the compound Z is continuously measured by channels of the NMR spectrometer 7 or via channel 8 using either 1D FT-NMR or frequency sweeping as described below. The detected chemical shift of the temperature-lock nucleus, δ(L Z ), or the detected resonance frequency, can be continuously or semi-continuously handed over to the main spectrometer computer 10 which stores and analyses these data. Computer or system processor 10 can employ a management of experiments and temperature (MET) procedure, which derives a dynamic temperature control signal, T dyn , for the negative feedback controller 2 and simultaneously manages the execution of dummy scans and acquisition of the experiments. The controller 2 in some embodiments may comprise a comparator, a PID controller, and a driver. Other types of controllers are also possible. As mentioned, in some non-limiting embodiments, T dyn represents a target, or desired, air temperature value.
A simplified embodiment for the MET procedure is shown in FIG. 2 . The depicted embodiment comprises three main phases R, D and E standing for reference, dummy scans and experiment, respectively. The index i corresponds to the experiment number in a series of experiments. The dashed lines represent the borders between the operational phases. In phase R, which can be initially executed once, a reference value for the chemical shift of nucleus L in compound Z in the sample is recorded. Phases D and E are then executed once for each of multiple experiments. During phase D, the dummy scans are executed. These dummy scans execute the full RF pulse scheme, leading to sample heating. During the continuous execution of these dummy scans, T dyn is adjusted until the sample temperature has reached a steady state and the chemical shift readings match the reference acquired in phase R. Then, in phase E, the actual experiment is recorded. Typical lengths are 10-40 seconds for phase R, 10-500 seconds for phase D, and 10 minutes-10 days for phase E.
One embodiment of the MET procedure is shown in FIG. 3 . In the embodiment depicted, the procedure starts at the top and follows the arrows. Boxes denote action steps and rhombs denote decision steps. The procedure ends at the bottom after all experiments have been measured. The letters R, D, E correspond to the three main phases of the procedure as outlined in FIG. 2 , the index i corresponds to the experiment number in a series of experiments. The dashed lines indicate the borders between the phases.
For the embodiment of FIG. 3 , after the sample has been inserted, phase R starts and the chemical shift reference value δ ref is acquired with the heater control set to T set , the desired sample temperature chosen by the user. In the absence of experiments and thus in the absence of strong RF-heating, the sample temperature is substantially equal to the air stream temperature, which is accurately and precisely controlled by the thermocouple. For example, the sample temperature is within about ±0.1 K of the air stream temperature. The setting T dyn =T set can yield the desired sample temperature, since the sample heating caused by the pulses used to acquire δ ref can be neglected. In the embodiment with 1D FT NMR, the δ ref is acquired by a single scan of δ(L Z ) or, to improve the accuracy, the average of n scans, where n is a user-defined value. Phase R is completed and phase D 1 begins by starting the dummy scans of experiment 1. The dummy scans employ the full radio-frequency scheme of the real experiment and simultaneously measure δ(L Z ) ( FIG. 5 ). Thus, the dummy scans induce the same amount of radio-frequency heating and thus change sample temperature by the same amount as the real experiment. The average of m measurements of δ(L Z ) during the dummy scans, δ ss , can be calculated and compared with the reference value δ ref , where m is a user-defined value. If δ ss and δ ref differ by not more than a user-defined tolerance value Δδ max , the steady state has been reached. If they do differ by a larger amount, the temperature reference value T dyn for the controller is changed by an amount ΔT dyn . The value of ΔT dyn can be a user-defined fixed value, or it can be made dependent on the difference δ ss −δ ref according to a predefined schedule. Since the temperature change coefficient of the nucleus L relative to the lock is known or can be determined from trial experiments, the sign of ΔT dyn can directly be determined from the sign of δ ss −δ ref . After changing the value of T dyn , a new value for δ ss is measured. Optionally, several dummy scans are executed, before this new measurement takes place. Once the steady-state condition |δ ss −δ ref |<Δδ max is reached, phase D 1 , the execution of the dummy scans, is terminated and phase E 1 , the regular acquisition of the experiment, is started. This transition is preferably executed without an interruption of the pulse rhythm. The T dyn value is no longer changed during the phase E 1 . δ(L Z ) is not recorded during E 1 . If another experiment is scheduled, phases D 2 and then E 2 follow E 1 . This is iterated until all scheduled experiments have been recorded. As an illustration of the performance of the MET procedure, the time-course of δ(L Z ) and T dyn during two experiments is shown in FIG. 4 .
Although the embodiment above is described with reference to chemical shift δ(L Z ), it will be appreciated that nuclear magnetic resonance frequency values, e.g., ω r (L Z ), of the temperature-lock nucleus L can be measured, tracked, and used in some embodiments the feedback method. For example, ω r (L Z ) can be measured prior to the application of RF pulses to determine a reference value ω ref , and ω r (L Z ) can be measured during dummy scans to determine a shifted resonance frequency value ω ss due to heating of the sample by the RF pulses. The magnitude of the difference |ω ss −ω ref | can then be examined to determine whether it is with a user defined tolerance value Δω max , and whether T dyn should be adjusted. In some embodiments, the chemical shift or nuclear magnetic resonance frequency is measured with respect to a standard, e.g., with respect to a nuclear magnetic resonance frequency of a selected nucleus. The selected nucleus can be a nucleus used for field lock of the NMR apparatus in some embodiments, or can be a nucleus not used for the field lock. In some embodiments, the selected nucleus has a resonance frequency dependent upon sample temperature. In certain embodiments, the selected nucleus has a resonance frequency substantially independent of temperature, e.g., less than about 5 ppm/K, less than about 2 ppm/K, less than about 1 ppm/K, less than about 0.5 ppm/K, and yet less than about 0.1 ppm/K in some embodiments.
FIG. 4 depicts functional aspects of one embodiment of the temperature-lock method. Time is depicted by the horizontal axis as increasing from left to right. Vertical dotted lines mark equal time points. The phases R, D, E of the MET procedure, as defined in FIG. 2 are represented by the boxes in FIG. 4A . FIG. 4B represents the measured chemical shift of the temperature-lock nucleus, δ(L Z ). The dashed horizontal line indicates the value of δ ref . FIG. 4C represents dynamic temperature control settings, T dyn , resulting from the MET procedure are shown. The dashed horizontal line is the temperature setting T set desired by the user.
In some embodiments, δ(L Z ) is acquired during E 1 in an interleaved fashion with the experiment, but without disturbing its pulse scheme ( FIG. 5 ). These measurements and possible T dyn adjustments may be used to compensate possible failures or fluctuations of the air stream or to compensate pulse sequences that change their rf-heating during the course of the experiment.
FIG. 5A represents an experimental scheme used for a main NMR experiment in the absence of the temperature-lock. The RF-pulse sequence is shown as open boxes. Recording of free induction decays (FID) is shown as open triangles. t r denotes the repetition time of the experiment. This repetition time is used in all panels of this figure. L represents the temperature-lock channel. M represents all other channels. The grey boxes denote pulse segments on nucleus L when the nucleus L is used for the main experiment.
FIG. 5B represents an embodiment of an NMR experiment employing temperature-lock with 1D FT-NMR. The letters R, D, E denote the three phases of the MET procedure as defined in FIG. 2 . R: Measurement of the reference value in the absence of any other experiment. A 90° pulse (vertical bar) excites the steady-state magnetization of L with subsequent recording of an FID (triangle). D: Pulse scheme during the dummy scans. The FID recordings on channel M (dashed triangles) are optional and are otherwise replaced by equivalent delays. E: Recording of the experiment. The acquisition of the temperature-lock frequency on channel L (dashed) is optional in this phase.
FIG. 5C depicts an embodiment of an NMR experiment employing temperature-lock with frequency sweeping. The letters R, D, E denote the three phases of the MET procedure. R: Measurement of the reference value in the absence of any other experiment. The frequency sweeping is indicated by wavy lines. D, E: Pulse scheme during the dummy scans and the experiment. Frequency sweeping is switched off during pulses on the nucleus L that might also be used for the main experiment.
According to one aspect of the present invention, an absolute calibration of the chemical shift dependence on temperature for the lock nucleus L is not required. After the reference signal is acquired, all the temperature-lock has to do is bring the resonance back to this reference value by changing the temperature setting T dyn . Thus, in some embodiments, not even a linear temperature dependence of the temperature-lock nucleus is a requirement. In some embodiments, it is sufficient if the dependence is strictly monotonic.
For the detection of the resonance frequency or chemical shift of the nucleus L by the spectrometer, two implementations can be used as depicted in FIG. 5 : 1D FT-NMR and frequency-sweeping NMR. One implementation comprises acquisition of a 1D FT-NMR spectrum of nucleus L and subsequent automated peak-picking ( FIG. 5B ). In another implementation with frequency sweep NMR, the resonance frequency or chemical shift of L is detected by frequency scanning ( FIG. 5C ), using the same or a similar scanning technology that is used for conventional field-frequency-locks. In the implementation with 1D FT-NMR, a possible embodiment for the automated peak picking routine used for the identification of the peak maximum in the frequency spectrum is described in: Hiller, S. et al. J. Biomol. NMR 42, 179-195 (2008). In this peak-picking routine, the global maximum of the spectrum is identified and the position of the peak maximum is interpolated by a symmetrization procedure involving the intensities of the two neighboring data points in each dimension. Alternative peak picking routines can be applied, or the routines can be modified to recognize certain features of the spectrum.
The choice of a suitable lock compound is guided by the following considerations. The main NMR experiment should not be impacted by the presence of the temperature-lock nuclei, and thus the nucleus L should be different to the nucleus, whose steady-state magnetization is used for the experiment of interest. In certain embodiments, L is contained in the molecule Z, which is a small molecule with sharp resonance lines. In some embodiments, Z is chosen to be a substance that is already part of the desired sample preparation, so that no change in the chemical composition of the sample is required, for example, a nucleus from the solvent, such as 17 O-water or 13 C-labelled organic solvents; or buffer components, such as 31 P-phosphate, salts, organic buffer compounds, detergents or other additive molecules. For protein samples in aqueous solution, 13 C-labelled and perdeuterated amino acids, or 13 C-labelled 2,2-Dimethyl-2-silapentane-5-sulfonic acid (DSS) may also be the temperature-lock compound of choice. For biomolecular NMR, the use of 13 C has the advantage that no channel needs to be added to conventional triple-resonance probe heads to implement the temperature-lock. 17 O has the strong advantage of universal applicability on aqueous samples, however, it may require an additional channel over those in triple-resonance probes in some embodiments.
Since the chemical shift referencing is based on the field-frequency lock, the effectively observed temperature shifts can comprise a combination of the temperature shifts of the field-lock resonance and the nucleus L in the substance Z. Thus, even nuclei that intrinsically have a weak or no temperature dependence can be suitable temperature-lock substances, if the field-frequency lock substance has sufficiently strong temperature dependence.
FIG. 6 shows temperature traces for the three different compounds 13 C-alanine, 31 P-phosphate and 17 O-water based on 1D FT NMR and automated peak picking. The temperature traces are as follows: 13 C-alanine ( FIG. 6A ), 17 O-water ( FIG. 6B ), and 31 P-phosphate ( FIG. 6C ). The absolute temperatures are indicated next to each data set. Each scan was taken in a 1D FT-NMR experiment followed by automated peak picking. In FIG. 6A the individual scans (thin lines) are shown in addition to the gliding average of the last 40 scans (bold lines). In FIGS. 6B-C , the gliding averages of 40 scans are shown. Temperature intervals of 0.1 K could be unambiguously distinguished in each case and are thus an upper limit to the obtainable accuracy, the amount of the lock substance and the number of averaged scans. Effective chemical shift changes relative to the D 2 O resonance are about 20 ppb/K for 13 C-alanine, 10 ppb/K and 31 P-phosphate, and −10 ppb/K for 17 O-water on their respective ppm scales. These results show that an embodiment of the temperature-lock is feasible with each of these three nuclei.
FIG. 7 shows as an example the application of 13 C-alanine as temperature-lock compound in a 2D [ 1 H, 1 H]-TOCSY experiment with strong RF-heating. FIG. 7A depicts chemical shift data based on the resonance frequency of the temperature-lock nucleus 13 C in the compound alanine. Trace (a) shows the chemical shift of the temperature-lock nucleus at a reference temperature of about T set =25° C. The average of 40 of these reference scans serves as the temperature lock reference value δ ref (dashed horizontal line). Trace (b) shows chemical shift measurements of the temperature-lock nucleus during 500 dummy scans of a 2D [ 1 H, 1 H]-TOCSY experiment with temperature adjustments by the MET procedure. Trace (c) shows chemical shift measurements of the temperature-lock nucleus during 500 dummy scans of a 2D [ 1 H, 1 H]-TOCSY experiment without temperature adjustments by the MET procedure. FIG. 7B depicts NMR spectra of the same sample in the same experimental situation. (a): 1D 1 H-NMR spectrum at the reference temperature of about T set =25° C. (b)/(c): First scan of a 2D [ 1 H, 1 H]-TOCSY experiment with/without using the temperature lock techniques. The NMR spectra for (b) and (c) were recorded directly after the corresponding dummy scans for each case.
The experiment of FIG. 7 shows that the RF pulse sequences increase the effective sample temperature by about 2.3 K, inducing large chemical shift changes of the resonance frequency of the temperature-lock nucleus. By a comparison of the resonance positions of the first scan of the 2D [ 1 H, 1 H]-TOCSY experiment with the 1D 1 H-NMR reference spectrum at the reference temperature, which were virtually identical ( FIG. 7B ), shows that the temperature calibration obtained using the temperature lock to be functional and highly accurate.
The experimental details for the acquisition of the data in FIGS. 6 and 7 were as follows. For 13 C as temperature-lock nucleus, a sample of 50 mM [U— 13 C]-Alanine was used. Measurements with 17 O and 31 P as temperature-lock substance were made with a sample of 50 mM phosphate buffer in [5% 17 O, 7% 2 H]—H 2 O. The 1D NMR spectra were recorded with a 90° excitation pulse followed by FID acquisition. 256, 11270, 1024 complex points were recorded in 400 ms, 1000 ms, 61 ms for 13 C, 31 P, 17 O, respectively. This interscan delay was adjusted to result in a repetition time of 1 s. The signal was zero-filled to 32 k complex points, multiplied with a cosine window function and Fourier transformed. From the 1D spectrum of 13 C-alanine, one resonance line from the multiplett of the C β atom at about 19 ppm was selected. The position of the peak maximum was interpolated from the intensity of the maximum and its two neighboring points. The 1D spectra of 17 O-water and 31 P-phosphate featured exactly one resonance line each and in these experiments the global maximum was picked without interpolation. The peak positions were stored continuously. Averages were calculated from 40 consecutive measurements. However, the parameters described here represent only one possible non-limiting embodiment, as many alternative choices are possible.
In addition to stabilization of the temperature, the proposed method allows the transfer of the temperature calibration of a given sample to another spectrometer, since the same resonance frequency relative to the static field lock (in ppm) must be observed at the same temperature. This condition is true as long as the chemical composition of the sample is not changed and the parameters for the temperature lock have been adjusted in a way to reproduce the same results. Thus, for studies of the same sample on different spectrometers, the temperature lock can be used to have identical temperature calibrations on all fields at all experiments.
According to one aspect of the present invention, the sample temperature is measured as the sample average, disregarding possible temperature gradients along the sample, which are known to occur in different size depending on the probe geometry and other factors.
According to some embodiments, the dynamic implementation of the dummy scans is used, and in some non-limiting embodiments the experiment always starts only when the steady state has been reached. However, not all embodiments are limited in this manner. For example, other implementations are also possible, such as using a fixed number of scans, a combination of a dynamic value with a fixed upper limit, or other possible implementations.
Some aspects of the technology described herein may exhibit one or more of the following advantages compared to conventional systems and methods: (a) 20-100 fold improvement of the accuracy when compared to existing non-interactive methods (b) full or nearly complete automation when compared to interactive methods (c) the experiments in some embodiments may start only when the steady state is truly reached (d) direct transferability of a calibration on the same sample between different spectrometers.
All literature and similar material cited in this application, including, but not limited to, patents, patent applications, articles, books, treatises, and web pages, regardless of the format of such literature and similar materials, are expressly incorporated by reference in their entirety. In the event that one or more of the incorporated literature and similar materials differs from or contradicts this application, including but not limited to defined terms, term usage, described techniques, or the like, this application controls.
While the present teachings have been described in conjunction with various embodiments and examples, it is not intended that the present teachings be limited to such embodiments or examples. On the contrary, the present teachings encompass various alternatives, modifications, and equivalents, as will be appreciated by those of skill in the art.
While various inventive embodiments have been described and illustrated herein, those of ordinary skill in the art will readily envision a variety of other means and/or structures for performing the function and/or obtaining the results and/or one or more of the advantages described herein, and each of such variations and/or modifications is deemed to be within the scope of the inventive embodiments described herein. More generally, those skilled in the art will readily appreciate that all parameters, dimensions, materials, and configurations described herein are meant to be exemplary and that the actual parameters, dimensions, materials, and/or configurations will depend upon the specific application or applications for which the inventive teachings is/are used. Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific inventive embodiments described herein. It is, therefore, to be understood that the foregoing embodiments are presented by way of example only and that, within the scope of the appended claims and equivalents thereto, inventive embodiments may be practiced otherwise than as specifically described and claimed. Inventive embodiments of the present disclosure are directed to each individual feature, system, article, material, kit, and/or method described herein. In addition, any combination of two or more such features, systems, articles, materials, kits, and/or methods, if such features, systems, articles, materials, kits, and/or methods are not mutually inconsistent, is included within the inventive scope of the present disclosure.
The above-described embodiments can be implemented in any of numerous ways. For example, the embodiments may be implemented using hardware, software or a combination thereof. When implemented in software, the software code can be executed on any suitable processor or collection of processors, whether provided in a single computer or distributed among multiple computers.
Further, it should be appreciated that a computer may be embodied in any of a number of forms, such as a rack-mounted computer, a desktop computer, a laptop computer, or a tablet computer. Additionally, a computer may be embedded in a device not generally regarded as a computer but with suitable processing capabilities, including a Personal Digital Assistant (PDA), a smart phone or any other suitable portable or fixed electronic device.
Also, a computer may have one or more input and output devices. These devices can be used, among other things, to present a user interface. Examples of output devices that can be used to provide a user interface include printers or display screens for visual presentation of output and speakers or other sound generating devices for audible presentation of output. Examples of input devices that can be used for a user interface include keyboards, and pointing devices, such as mice, touch pads, and digitizing tablets. As another example, a computer may receive input information through speech recognition or in other audible format.
Such computers may be interconnected by one or more networks in any suitable form, including a local area network or a wide area network, such as an enterprise network, and intelligent network (IN) or the Internet. Such networks may be based on any suitable technology and may operate according to any suitable protocol and may include wireless networks, wired networks or fiber optic networks.
Any computing device or computer configured to implement the various functionality described herein may comprise a memory, one or more processing units (also referred to herein simply as “processors”), one or more communication interfaces, one or more display units, and one or more user input devices. The memory may comprise any computer-readable media, and may store computer instructions (also referred to herein as “processor-executable instructions”) for implementing the various functionalities described herein. The processing unit(s) may be used to execute the instructions. The communication interface(s) may be coupled to a wired or wireless network, bus, or other communication means and may therefore allow the computer to transmit communications to and/or receive communications from other devices. The display unit(s) may be provided, for example, to allow a user to view various information in connection with execution of the instructions. The user input device(s) may be provided, for example, to allow the user to make manual adjustments, make selections, enter data or various other information, and/or interact in any of a variety of manners with the processor during execution of the instructions.
The various methods or processes outlined herein may be coded as software that is executable on one or more processors that employ any one of a variety of operating systems or platforms. Additionally, such software may be written using any of a number of suitable programming languages and/or programming or scripting tools, and also may be compiled as executable machine language code or intermediate code that is executed on a framework or virtual machine.
In this respect, various inventive concepts may be embodied as a computer readable storage medium (or multiple computer readable storage media) (e.g., a computer memory, one or more floppy discs, compact discs, optical discs, magnetic tapes, flash memories, circuit configurations in Field Programmable Gate Arrays or other semiconductor devices, or other non-transitory medium or tangible computer storage medium) encoded with one or more programs that, when executed on one or more computers or other processors, perform methods that implement the various embodiments of the invention discussed above. The computer readable medium or media can be transportable, such that the program or programs stored thereon can be loaded onto one or more different computers or other processors to implement various aspects of the present invention as discussed above.
The terms “program” or “software” are used herein in a generic sense to refer to any type of computer code or set of computer-executable instructions that can be employed to program a computer or other processor to implement various aspects of embodiments as discussed above. Additionally, it should be appreciated that according to one aspect, one or more computer programs that when executed perform methods of the present invention need not reside on a single computer or processor, but may be distributed in a modular fashion amongst a number of different computers or processors to implement various aspects of the present invention.
Computer-executable instructions may be in many forms, such as program modules, executed by one or more computers or other devices. Generally, program modules include routines, programs, objects, components, data structures, etc. that perform particular tasks or implement particular abstract data types. Typically the functionality of the program modules may be combined or distributed as desired in various embodiments.
Also, data structures may be stored in computer-readable media in any suitable form. For simplicity of illustration, data structures may be shown to have fields that are related through location in the data structure. Such relationships may likewise be achieved by assigning storage for the fields with locations in a computer-readable medium that convey relationship between the fields. However, any suitable mechanism may be used to establish a relationship between information in fields of a data structure, including through the use of pointers, tags or other mechanisms that establish relationship between data elements.
Also, various inventive concepts may be embodied as one or more methods, of which an example has been provided. The acts performed as part of the method may be ordered in any suitable way. Accordingly, embodiments may be constructed in which acts are performed in an order different than illustrated, which may include performing some acts simultaneously, even though shown as sequential acts in illustrative embodiments.
All definitions, as defined and used herein, should be understood to control over dictionary definitions, definitions in documents incorporated by reference, and/or ordinary meanings of the defined terms.
The indefinite articles “a” and “an,” as used herein in the specification and in the claims, unless clearly indicated to the contrary, should be understood to mean “at least one.”
The phrase “and/or,” as used herein in the specification and in the claims, should be understood to mean “either or both” of the elements so conjoined, i.e., elements that are conjunctively present in some cases and disjunctively present in other cases. Multiple elements listed with “and/or” should be construed in the same fashion, i.e., “one or more” of the elements so conjoined. Other elements may optionally be present other than the elements specifically identified by the “and/or” clause, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, a reference to “A and/or B”, when used in conjunction with open-ended language such as “comprising” can refer, in one embodiment, to A only (optionally including elements other than B); in another embodiment, to B only (optionally including elements other than A); in yet another embodiment, to both A and B (optionally including other elements); etc.
As used herein in the specification and in the claims, “or” should be understood to have the same meaning as “and/or” as defined above. For example, when separating items in a list, “or” or “and/or” shall be interpreted as being inclusive, i.e., the inclusion of at least one, but also including more than one, of a number or list of elements, and, optionally, additional unlisted items. Only terms clearly indicated to the contrary, such as “only one of” or “exactly one of,” or, when used in the claims, “consisting of,” will refer to the inclusion of exactly one element of a number or list of elements. In general, the term “or” as used herein shall only be interpreted as indicating exclusive alternatives (i.e. “one or the other but not both”) when preceded by terms of exclusivity, such as “either,” “one of,” “only one of,” or “exactly one of.” “Consisting essentially of,” when used in the claims, shall have its ordinary meaning as used in the field of patent law.
As used herein in the specification and in the claims, the phrase “at least one,” in reference to a list of one or more elements, should be understood to mean at least one element selected from any one or more of the elements in the list of elements, but not necessarily including at least one of each and every element specifically listed within the list of elements and not excluding any combinations of elements in the list of elements. This definition also allows that elements may optionally be present other than the elements specifically identified within the list of elements to which the phrase “at least one” refers, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, “at least one of A and B” (or, equivalently, “at least one of A or B,” or, equivalently “at least one of A and/or B”) can refer, in one embodiment, to at least one, optionally including more than one, A, with no B present (and optionally including elements other than B); in another embodiment, to at least one, optionally including more than one, B, with no A present (and optionally including elements other than A); in yet another embodiment, to at least one, optionally including more than one, A, and at least one, optionally including more than one, B (and optionally including other elements); etc.
In the claims, as well as in the specification above, all transitional phrases such as “comprising,” “including,” “carrying,” “having,” “containing,” “involving,” “holding,” “composed of,” and the like are to be understood to be open-ended, i.e., to mean including but not limited to. Only the transitional phrases “consisting of” and “consisting essentially of” shall be closed or semi-closed transitional phrases, respectively, as set forth in the United States Patent Office Manual of Patent Examining Procedures, Section 2111.03. | Described are methods and apparatus, referred to as “temperature-lock,” which can control and stabilize the sample temperature in an NMR spectrometer, in some instances with a precision and an accuracy of below about 0.1 K. In conventional setups, sample heating caused by experiments with high-power radio frequency pulses is not readily detected and is corrected by a cumbersome manual procedure. In contrast, the temperature-lock disclosed herein automatically maintains the sample at the same reference temperature over the course of different NMR experiments. The temperature-lock can work by continuous or non-continuous measurement of the resonance frequency of a suitable temperature-lock nucleus and simultaneous adaptation of a temperature control signal to stabilize the sample at a reference temperature value. Inter-scan periods with variable length can be used to maintain the sample at thermal equilibrium over the full length of an experiment. | 6 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention generally relates to a shelter structure and more particularly to a novel and unique module, support pedestal structure associated therewith, connector means between adjacent modules and procedures for setting up and assembling the modules on site to facilitate the construction of a shelter structure.
2. Description of the Prior Art
Shelter structures or buildings constructed from modules consisting of generally triangular panels connected and associated in particular manners are generally well known which enables the panels to be prefabricated in a manufacturing plant and delivered to the construction site in a disassembled or partially assembled condition to facilitate the construction of the shelter. Applicant's prior U.S. Pat. Nos. 3,474,804, 3,533,202, and 3,534,514 disclose prior developments in this field of endeavor with these patents disclosing the basic concept of curved edges of generally triangular panels being secured together with the opposite apices of the panels being spread apart to form a lobe or module. Other patents disclosing developments in this field of endeavor include U.S. Pat. Nos. 3,562,975; 3,636,676; 3,461,626; 3,470,659; 3,534,513; 3,139,958; 3.714,749; 3,332,178; 3,445,970; 3,016,115; 2,716,993; and 3,759,277.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a shelter structure constructed from a plurality of interconnected modules or lobes each of which includes a framework system of rafters which ar hingedly joined and opened in a manner to generate a pair of intersecting conic sections which permits skins which may be either flexible, semi-rigid or rigid to be attached to the rafters either before or after they are pulled apart to transform the single plane of the skins into three-dimensional, cone-shaped sections.
Another object of the invention is to provide a shelter structure in which the conic sections are all identical which permits additional lobes or modules to be added on after original construction as needed.
A further object of the invention is to provide a shelter structure in accordance with the preceding objects in which the conic sections have their apices spread apart and supported in elevated relation to a supporting surface by a pedestal support connected to the rafters in a novel manner which permits the lobe or module to be oriented at a desired elevation above ground level with the pedestal support arrangement enabling the lobe or modules to be joined to each other thereby providing unique stability and resistance to overturning moment both during erection and thereafter.
Still another object of the invention is to provide a shelter structure constructed of a plurality of lobes or modules in accordance with the preceding objects in which a unique procedure of assembly is employed which permits the lobes to be raised from a deck or other supporting surface which is inaccessible to conventional cranes and the like thus enabling on-site assembly of the lobes or modules without requiring elaborate assembly mechanisms although a lifting device is most conveniently employed to elevate the assembled lobes for support from the pedestal supports.
Yet another important feature of the present invention is to provide a shelter structure in accordance with the preceding objects which is relatively inexpensive to manufacture and assemble, adaptable for various assembly arrangements to vary the shelter structure, stable in construction, capable of expansion by adding modules after installation and employing conventional structural components.
These together with other objects and advantages which will become subsequently apparent reside in the details of construction and operation as more fully hereinafter described and claimed, reference being had to the accompanying drawings forming a part hereof, wherein like numerals refer to like parts throughout.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a shelter unit constructed in accordance with the present invention.
FIG. 2 is a plan view of the structure of FIG. 2.
FIG. 3 is a side elevational view of the construction of FIG. 1 with the side walls removed illustrating the pedestal supports and rafter framework.
FIGS. 4-7 are schematic views illustrating various arrangements in which the modules or lobes may be assembled.
FIG. 8 is a vertical sectional view, on an enlarged scale, taken substantially upon a plane passing along section line 8--8 of FIG. 2 illustrating the rafter array, connectors therebetween and pedestal supports therefor.
FIG. 9 is an enlarged side elevational view of one of the pedestal supports and the lower apices of two connected conic sections.
FIG. 10 is an elevational view interiorly of the pedestal and rafter array of FIG. 9.
FIG. 11 is a fragmental elevational view of the connection between the upper ends of the rafters defining the curved edges of the triangular panels.
FIG. 12 is a perspective view of the structure of FIG. 11 illustrating the orientation of the rafters and connector prior to the apices of the triangular panels being spread apart.
FIG. 13 is a sectional view, on an enlarged scale, taken along section line 13--13 illustrating the connecting assembly between adjacent modules or lobes.
FIGS. 14-21 illustrate schematically the sequential steps to be followed in assembling a plurality of modules into a shelter unit.
FIG. 22 illustrates the angular extent of the circular sector of each lobe face prior to the triangular panels being spread apart.
FIG. 23 is a view similar to FIG. 22 but illustrating the circular sector of each lobe face after the triangular panels have been spread apart.
FIGS. 24-27 illustrate the procedural sequence followed in setting up a modified embodiment of the shelter structure in which the upper ends of the rafters are connected hingedly and a flexible skin is connected to the rafters.
FIG. 28 illustrates the mitered construction of the upper end of the rafters and the connector therebetween.
FIG. 29 illustrates an accordion hinge structure connecting the lower ends of the rafters in the embodiment of the invention illustrated in FIGS. 24-27.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now specifically to the drawings, a shelter structure constructed in accordance with the present invention is illustrated in FIGS. 1 and 2 and is generally designated by reference numeral 30 with the shelter structure being supported on any suitable supporting surface which may be the groung surface or a deck 32 of concrete, wood or the like depending upon the requirements of each individual installation or depending upon the characteristics of each site or the desires of the builder or owner. As illustrated, three lobes or modules are employed in the shelter structure which are designated generally by reference numerals 34, 36 and 38 and labeled in the plan view in FIG. 2.
Each lobe includes a pair of indentical triangular panels 40 and 42 formed by a skin 44 and a rafter array 46 which includes edge rafter A, intermediate rafter B, two central rafters C, an intermediate rafter D, and an edge rafter E, as illustrated in FIG. 10, with all of these rafters having their upper ends 48 cut diagonally at a 45° angle and being interconnected by hinge brackets 50 of angular construction having hinge bolts 52 extending through and connecting pivotally the upper ends of corresponding rafters in the connected edges between the triangular panels 40 and 42. A pair of bolts 54 extend through the legs of the connector brackets and the corresponding rafters in longitudinally spaced relation to the pivot bolts 52 in order to retain the rafters in their spread apart condition. FIG. 12 illustrates a pair of edge rafters A in their generally parallel, unspread condition while FIG. 11 illustrates the same pair of rafters A in their spread apart condition with the bolts 54 in assembled relation. When the triangular panels 40 and 42 are connected and the apices 56 and 58 spread apart to form the module 34, the juncture between the panels 40 and 42 becomes a curved arcuate line 60 defining a ridge line between the panels 40 and 42 with each of the lobes 34, 36 and 38 including an arcuate ridge line so that each of the triangular panels 40 and 42 is changed from a substantially planar member to a conic section when the apices 56 and 58 are spread apart. As illustrated in FIG. 1, vertical wall members 62 may be connected to the free edges of the lobes to form a shelter structure. When it is desired to extend the shelter structure by making it larger, additional lobes may be incorporated therein or lobes may be removed if desired.
The structure for connecting adjacent lobes is illustrated in FIG. 13 in which the edge rafters E in FIG. 10 are joined by a connecting member 64 in the form of a square structural element connected to the rafters E by bolts 66 or similar fastening elements. FIGS. 9 and 10 illustrate the structure for supporting the lobes which is in the form of a pedestal generally designated by numeral 68 with the pedestals 68 supporting the apices 56 and 58 of the triangular panels 40 and 42 as well as the corresponding apices on adjacent lobes as illustrated in FIG. 3. Thus, depending upon the arrangement of the lobes, the pedestals 68 will support a single apex of a lobe or the connected apices of two lobes. FIGS. 4-7 illustrate various lobe arrangements with each lobe including two triangular panels. FIGS. 4 and 5 illustrate the capability of employing half lobes when desired which are illustrated by the broken lines in FIGS. 4 and 5. In certain instances, introduction of half lobe sections produces certain efficiencies. For example, the external wall area may actually be reduced while affording a larger floor area when using a half lobe section.
The pedestal assembly 68 includes a pair of structural members 70 secured to the supporting platform or base 32 by angle iron brackets 72 or the like with the upper end of the member 70 being provided with a notch 74 therein receiving the lower ends of the rafters E with the notch 74 having a generally right-angular configuration as illustrated in FIG. 9. For supporting the outer edge rafters A in the lobe, a pair of corbel plates 76 are attached to the pedestal member 70 by fastening bolts 78 with the upper edges of the corbel plates 76 being beveled as at 80 to abuttingly engage the lower ends of the edge rafters A. An angulated splice plate 82 is fastened to the outer surfaces of the corbel plates 76 by the bolts 78 and the upper end portion of each of the splice plates 82 is angulated outwardly and is disposed along the outer surface of the outer edge rafters A and are secured thereto by bolts 84. The upper outer corner of the splice plate 82 is beveled as at 86 to conform with the inclination of the upper edge of the rafters A and the roof skin thereon.
In the assembly, rafter B is trapped between rafters A and C and rafter D is trapped between rafters E and C and the two rafters C are trapped between rafters A and E. The rafters, except for E have a 45° diagonal or bevel cut at their lower ends so that they will be properly trapped and supported due to their relationship to each other and due to the conical section being formed when the apices of adjacent panels are spread apart. The skin 44 may be a plurality of triangular panels of laminated wood such as plywood or the like or any other suitable material with roofing material of any various type applied to the shelter structure. FIG. 22 illustrates a plan view of an array of rafters prior to spreading illustrating an arcuate segment of approximately 50° having dimensional characteristics A and C while FIG. 23 illustrates the array of rafters after spreading having an arcuate extent of approximately 70° and dimemsional characteristics B and D in which dimensional characteristic C in FIG. 22 is greater than dimensional characteristic B in FIG. 23 and the dimemsional characteristic B in FIG. 23 is .707 A with FIG. 22 depicting the undeveloped cone or planar arrangement and FIG. 23 depicting the developed cone or conic section which curves when the apices are apread apart.
When the apices are spread apart, the included angle between the rafters E is 90° and the distance between the apices is 1.414 A.
FIGS. 14-21 illustrate a procedure of assembly in which FIG. 14 discloses a central section of one of the triangular panels including rafters E, D and C with a skin 44 attached thereto and FIG. 15 illustrates the assembly of an outside section to the central section with rafters C, B and A added thereto. FIG. 16 illustrates half of the triangular panels joined at their curved edge while FIG. 17 illustrates the manner in which the second half of each of the triangular panels are secured together thus forming a lobe as illustrated in FIG. 18. The apices of the lobe are spread apart as illustrated by the arrows in FIG. 18 and retained in this position by a bracing member 90. A lifting crane 92 ia then employed to elevate the lobe 34 and to orient it with the two apices 56 and 58 downwardly which is accomplished by the flexible lift line or cable 94 being attached to a bridle 96 connected at its ends to the brace member 90. The crane structure 92 may be mounted on any suitable base 98 and is only schematically illustrated. In this arrangement, when the top edge of the lobe 34 is elevated to a position above the crane boom or the like, the fact that the point of attachment of the lift cable 94 is above the center of gravity of the lobe 34, the lobe 34 will be automatically oriented in the full line position illustrated in FIG. 20 with the apices 56 and 58 disposed downwardly so that the pedestal support 68 may then be installed.
FIGS. 24-29 illustrate a series of rafters 100 which are hinged together by the gusset hinge 102 which enables the rafters 100 to be oriented in parallel relation to each other as illustrated in FIG. 4 with the gusset hinges being illustrated in FIG. 28 in which the rafters are locked in angular relation. The ends of the rafters 100 are mitered as at 104 so that when they are in their angular orientation, the mitered edges engage each other. The lower ends of the rafters 100 are connected together by an accordion hinge assembly 106 which enables the mirror image rafters 100 to be pivoted apart to form a lobe with the apices of the lobes at the lower ends thereof also being spreadable.
With the rafters in their collapsed position as illustrated in FIG. 24, the assembly may be towed to a site by the use of a suitable towing vehicle 108 and a trailering connection 110 to a supporting trailer or attachable wheels 112. The trailer and hitch may be self-contained or the wheel assembly may be attached directly to the rafters and the hitch 110 attached to the forward end of the collapsed rafter assembly. Upon reaching a site, the rafters 100 are spread apart in the manner illustrated in FIG. 25 and rigidly secured in this position by inserting the upper bolts through the gusset plates 102. An upstanding mast, pole or other vertical support 114 having a pulley 116 at the upper end thereof and an elongated cable 118 may be employed for fanning the rafters 100 into an upright position to form a lobe as illustrated in FIG. 26. The cable 118 may be pulled manually or with any suitable manual or powered winch mechanism so that the array of rafters forms itself into a framework of a pair of intersecting conic sections. The rafters 100 are interconnected by a flexible tension member or members 120 at their upper extremities so that as each set of rafters is pulled away from its position parallel to the ground, that tension member becomes fully extended and finally exerts force on the next set of rafters in its turn so that a shelter framework is formed. The framework may be covered with a flexible covering, a semi-rigid covering or a series of rigid sections. The flexible covering may be applied before or after fanning and stressing or anchoring, the semi-rigid covering may be applied after fanning but before or after stressing and the rigid covering may be applied after stressing between adjacent rafters.
The circular sector or each lobe face is approximately 50° as illustrated in FIG. 22 before it is hinged and deformed by stretching into a conic section. When hinged and stretched, the angle included becomes 90° or someother angle approximately 90° included between the panels at the connected curved edges depending upon choice and requirement. When stretched to have an included angle of 90°, the angle reduces to approximately 49° and the distance between the apices of the two lobe faces is 1.414 times the radius of the lobe. However, in elevation, the angle of the lobe face is deformed and foreshortened to 70° 32 minutes which is the dihedral angle of a right tetrahedron so that in plan view the two lobe faces form a pair of equilateral triangles having a 60° apex angle as seen in FIG. 2. FIG. 13 illustrates adjacent lobes being joined together by means of the long square cross section member bolted to the outside rafter members underneath the joining valley.
The gusset plates 50 also serve as hinge plates and all of the rafters except the rafters E are cut at 45° at their lower ends so that when the rafters move from a circular array into a conical array, the face formed by the 45° cut is parallel to the central axis of the intersecting cones. It is pointed out that other hinging systems may be employed to preserve the symmetry of the rafters in lieu of the gusset hinge plates 50 with it being essential that the rafters be hingedly connected but secured in a stable angular orientation. The lower ends of the rafters are so arranged that when they are orientated in their conic array, the 45° edge cut comes in to contact along its full length with adjacent rafters with the rafters A being bolted to the splice plate 82.
While multiple lobes have been primarily disclosed, it is pointed out that a single lobe and a half lobe are useful structures by themselves or in any combination with other lobes. Also, while a conic section or configuration of each panel has been illustrated and described, the princple is equally applicable to parabolic, elliptical, free-form and compound curve sections.
The foregoing is considered as illustrative only of the principles of the invention. Further, since numerous modifications and changes will readily occur to those skilled in the art, it is not desired to limit the invention to the exact construction and operation shown and described, and accordingly all suitable modifications and equivalents may be resorted to, falling within the scope of the invention. | A shelter structure constructed of a plurality of modules or lobes each of which includes a pair of triangular panels having curved edges connected together with the apices thereof spread apart and supported by pedestals in elevated relation to a supporting surface. Adjacent edges of the lobes or modules are secured together by a connector and the pedestals are secured to the lower apices of the modules by splice plate assemblies. The lobes or modules are assembled into a building or shelter structure by a unique manipulative procedure to facilitate the construction of a shelter on site thus enabling the modules to be conveyed to the site in a partially assembled condition and then expeditiously set-up and assembled into a shelter structure. | 4 |
This application is a division of application Ser. No. 07/779,219, filed Oct. 18, 1991, U.S. Pat. No. 5,598,508.
BACKGROUND OF THE INVENTION
1. Technical Field
This invention relates to waveform analysis and more particularly to a system for performing real-time waveform analysis using artificial neural networks.
2. Discussion
Accurate waveform analysis plays a crucial role in many fields. That is, many technical areas involve problems in analyzing an incoming signal having a characteristic waveform which must be interpreted and classified. Some examples of such signals include the analysis of audio, sonar, and electromagnetic waves from various sources. For example, detailed analysis and classification of speech signals is required to perform automated speech recognition. Another example occurs in analysis of seismographic signals. Numerous waveform analysis applications exist in the medical field. Examples of physiologic waveforms which are subject to analysis include respiratory wave analysis including pressure and gas concentrations, vascular pressure waves (arterial, etc.), airway pressure waves; electrocardiograms; electroencephalograms; pressure wave analysis in a cardiopulmonary bypass machine circuit, plethysmograms and bioimpedance waves.
Some of the more difficult tasks involved in analyzing such signals include front end (preprocessing) steps, including waveform segmentation; classification of waveforms into predetermined classes; and interpreting of ambiguous data such as ambiguous classification results. Difficulties in performing tasks such as these are compounded because of wide variations in such waveforms due to countless factors causing the signal to deviate in frequency, amplitude, shape, etc. from expected norms. Because of these variations, the task of developing algorithms and writing software to automatically perform waveform analysis frequently becomes a daunting, monumental task. This "software bottleneck" has slowed the development of systems in this area. Even when large sums of time and money are spent to develop such software algorithms, results in many areas are still not satisfactory.
A further problem with conventional approaches is that they are frequently computationally expensive which either necessitates enormous computing power, or simply precludes their use in systems which must perform in real-time. For example, in the analysis of physiological waveforms, real time performance is often essential to achieve results fast enough to take corrective responses to abnormalities in a patient's physiological functioning.
A promising alternative to conventional symbolic sequential computing techniques is offered by artificial neural network systems. Neural network architectures, which are loosely based on knowledge of the neuroanatomy of the brain, have been shown to perform well at tasks such as classification of waveforms having subtle differences--tasks which heretofore have been limited to performance by humans. In addition to their robust ability to recognize characteristic waveforms which vary widely from predicted shapes, neural networks also promise to offer a solution to the "software bottleneck" discussed above. This is because explicit algorithms need not be developed for neural networks to recognize waveforms. Instead, these systems, trained with exemplars, they converge to an acceptable solution. In addition, once trained, a neural network can generally perform a recognition task rapidly due to its inherent parallelism. See R. P. Lippmann "An Introduction to Computing with Neural Networks" IEEE ASSP Magazine, April 1987, page 4 for a discussion of the better-known neural network architectures and techniques. Despite the promising outlook, many difficult remain to be solved in such areas as preprocessing data to make it suitable for processing by the neural network, optimizing the architectures and learning paradigms for the recognition process, as well as postprocessing and interpretation of ambiguous results.
Thus it would be desirable to provide a system and method to perform waveform analysis which overcomes some or all of these shortcomings. It would be desirable to have a system which can perform accurate analysis and classification of waveforms without requiring extensive algorithm and software development time. Further, it would be desirable to provide such a system which can perform waveform analysis in real-time with readily available and reasonably priced hardware. It would further be desirable to provide a waveform analysis system which can readily analyze and classify waveforms which deviate substantially from predicted patterns. Further, it would be desirable to provide a waveform analysis system which makes use of the advantages of neural network architectures and also resolves inherent preprocessing, analysis and postprocessing difficulties.
SUMMARY OF THE INVENTION
Pursuant to the present invention, a method of analyzing waveforms having characteristic features in a signal using neural networks is provided. Initially, a first portion of the signal is transmitted to a neural network so that AN consecutive samples of said signal are transmitted to N input nodes of the neural network, so that the transfer causes the neural network nodes to receive data from buffer locations having the same index number. An output is then generated by the neural network which is a representation of the index number of the input node receiving the starting point of the waveform, since the neural network has been previously trained to recognize starting and end points of the characteristic waveforms respectively. In accordance with another aspect of the present invention, a third neural network then receives the contents of the buffer between the identified starting points and ending points. This neural network has been trained to produce an output which serves to classify the waveforms. In accordance with another aspect of the present invention, a fourth neural network is then trained to resolve any ambiguities in the third neural network output using additional information.
In accordance with another aspect of the present invention, a system is provided for analyzing a characteristic waveform in a signal using neural networks in the manner described above.
BRIEF DESCRIPTION OF THE DRAWINGS
The various advantages of the present invention will become apparent to one skilled in the art by reading the following specification and by reference to the following drawings in which:
FIG. 1 is a diagram of the main components of a preferred embodiment of the present invention for use in automated capnogram waveform analysis;
FIG. 2 is a diagram showing normal and abnormal capnogram waveforms to be identified by the present invention;
FIG. 3 is a diagram of a neural network configured to produce an output which identifies the waveform's starting point or end point;
FIG. 4 is a diagram showing the progression of a signal containing a waveform into the input buffer of the present invention;
FIG. 5 is a diagram illustrating a sampling of a signal containing a partial waveform;
FIG. 6 is a diagram illustrating the setting of buffer value to 0 for incomplete waveforms;
FIG. 7 is a diagram illustrating a technique for insuring that sufficient lead and lag portions of a waveform are sampled;
FIG. 8 is a diagram illustrating the time normalization of a waveform;
FIG. 9 is a diagram illustrating additional details of the time normalization shown in FIG. 8;
FIG. 10 is an illustration of the amplitude normalization process in accordance with the present invention;
FIG. 11 is an illustration of additional details of the amplitude normalization process;
FIG. 12 is a diagram of the lead and lag normalization of a waveform in accordance with the present invention;
FIG. 13 is a diagram of addition details of the lead and lag normalization process;
FIG. 14 is an example of a waveform from arterial pressure waves in accordance with an additional embodiment of the present invention;
FIG. 15 is another diagram of lead and lag normalization performed on arterial pressure waves in accordance with an alternative embodiment of the present invention;
FIG. 16 illustrates several partial waves to be identified by the present invention;
FIG. 17 illustrates the output classifications produced by neural network 3 in accordance with the present invention;
FIG. 18 is an example of the output of neural network 3 for an exemplary waveform;
FIG. 19 is an example of an ambiguous output from neural network 3 requiring arbitration;
FIG. 20 is a table of the outputs of neural network 4 for performing arbitration; and
FIG. 21 is an overall diagram of the processes performed by the present invention in neural networks 1-4.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention provides the system and method for analyzing waveforms which may originate in numerous applications as discussed above. To illustrate the use of the techniques of the present invention, a non-limiting example will be described in accordance with a preferred embodiment involving physiologic respiratory signals. In particular, the preferred embodiment involves analysis of capnograms, which are measurements of carbon dioxide concentration in inhaled and exhaled breath during respiration over time. The carbon dioxide concentration measurement is usually performed by a measurement of absorption of infrared light in a sample of a subjects exhaled breath, although other techniques such as mass spectroscopy can also be used to measure CO2 concentration.
The goal when analyzing physiologic signals such as capnograms, (as well as many other types of waveforms) is to locate and separate each event in a time series of data for a subsequent pattern identification. In the capnogram, the event of interest is the portion of the signal produced during expiration. Once each individual event is isolated by the system, it is then analyzed by the pattern recognition portion of the system and a diagnosis is displayed. A pattern classification of each individual capnogram permits the diagnosis of normal and various abnormal capnograms.
Referring now to FIG. 1, the main components of the preferred embodiment of the present invention are shown. A subject or patient 10 undergoing anesthesia has a breathing tube 12 (endotracheal tube) inserted into his trachea. The breathing tube is connected to an anesthesia machine and breathing circuit 14 in a conventional manner which is connected to an inspiratory valve (not shown) in the intake 16 segment of the tube and an expiratory valve (not shown) connected to the expiratory portion 18 of the breathing circuit 14. In operation, a bellows (not shown) will force air into the subject's lungs through the breathing tube 12 and the subject will exhale unassisted forcing CO2-rich gas to pass out of the breathing tube 12 and into the expiratory portion of the breathing circuit 18. A gas sampling catheter 20 is attached to the breathing tube 12 at point 22. The gas sampling catheter is fed to a respiratory gas monitor which may comprise an Ohmeda Model 5250 respiratory gas monitor manufactured by Ohmeda Corporation of Louiseville, Colo. The respiratory gas monitor 24 analyzes the CO2 content of the gas in the sampling catheter 20 and produces a capnogram signal 26 which contains characteristic waveforms 28 which represent elevated CO2 levels during expiration.
Ordinarily, the capnogram signal 26 is monitored by operating room personnel to insure that a normal signal is present. Various kinds of abnormalities in the capnogram are indicative of a variety of abnormal conditions and will generally require immediate corrective action. While some automatic waveform analysis techniques have been employed previously to detect such abnormalities, the performance of such systems has had several drawbacks limiting their usefulness as discussed above.
In accordance with the present invention, the capnogram 26 is analyzed using an artificial neural network-based system to perform preprocessing, classification, and postprocessing of individual capnograms. In more detail, the waveform analysis system 30 of the present invention employs an input line 32 which carries an analog capnogram signal 26. This analog signal is converted to a digital signal by an analog to digital converter 34 which may comprise a Model DASH-16F analog to digital converter manufactured by Metrabyte Corporation of Taunton, Mass. This analog to digital converter 34 includes direct memory access (DMA) control and is used to convert and store the CO2 capnograph signal 32 into computer memory without using CPU time.
In particular, the analog to digital converter 34 output is fed to a host computer 36 which, for example, may comprise a PC computer employing a 486, 33 megahertz chip. The analog to digital conversion is performed at 20 hertz which is sufficiently fast to capture all the features of the capnogram 26 with a minimum amount superfluous data. A waveform analysis program 38 in accordance with the present invention is stored in the PC 36 memory and performs the steps of waveform analysis as described hereinafter.
In particular, a memory storage area in the program 36 comprises a circular input buffer 40 which temporarily stores the capnogram signal 26 before transferring it to a pair of neural networks, designated neural network No. 1, 42 and neural network No. 2, 44. These neural networks are trained to locate the start point and end point of an individual capnogram 28. Once the start point and end point are defined by neural network No. 1, 42 and No. 2, 44 outputs, the capnogram waveform 28 defined by these points is transmitted to neural network No. 3, 46 which has been trained to recognize specific abnormal waveform features. For example, referring now to FIG. 2, a normal capnogram 54 is shown along with a capnogram 56 illustrating an inspiratory valve defect, and one having a cleft in the plateau 58 and another capnogram 60 indicating an expiratory valve defect having an elevated base line. The present invention thus is able to recognize these and other characteristic waveform shapes automatically in real-time to permit corrective action to be taken.
In cases where neural network 346 produces an output which is ambiguous, that is, not clearly one category or another, neural network No. 48 is used to perform arbitration using additional information about the physiologic state of the patient 10 to account for atypical waveforms. The output of neural network No. 48 is a representation of the classification of the normal or abnormal waveform 28 which may then be displayed in various ways by a display unit 50. For example, abnormal waveforms may trigger an alarm to alert operating room personnel to the condition, or may further be processed by subsequent systems which may then specify corrective measures to be taken.
The software 38 contains control logic 52 which directs the flow and decisions of the program as discussed in more detail below.
In more detail, the circular input buffer 40 is over-sized so that about two minutes of data can be stored. Nevertheless, the goal of the preferred embodiment is to be able to recognize a capnogram 28 observation in 15 seconds or less. Data is sampled at 20 hertz and fed to neural networks one and two, each having 300 input nodes. Thus, since there is a one to one correspondence of collected data points to input nodes a maximum of 300 data points or (300+20) equals 15 seconds can be analyzed. A given location in the buffer 40 is defined as an index point.
Referring now to FIG. 3 a representation of a neural network 62 having 300 input nodes 64 and one output node 66 is shown. Each of the 300 input nodes receive data from the capnogram signal 26 contained in the input buffer 40 where data in each corresponding index number in the buffer is transmitted to one of the 300 input nodes having a corresponding index number. It will be appreciated by those skilled in the art that neural network 62 may comprise a conventional three-layer back-prop neural network having 300 input hidden nodes 70 which may optimally include 15 to 45 hidden nodes and synaptic connections 72 between each node in neighboring layers. That is, in accordance with conventional multilayer perceptron, each node 64 is connected to each hidden node 70 and likewise each hidden node 70 is connected to the output node 66.
Further details of multilayer perceptrons may be found in the above referenced paper by Lippmann, entitled "Introduction to Computing Using Neural Network". In addition, a software package sold by Ward Systems Group of Frederick, Md. known as NeuroShell is available to implement neural networks 1-4 in software in accordance with the present invention. Further, a code generation module available from Ward Systems Group facilitates in development of the control logic for controlling the over all system. Further, a hardware training board available from NeuroShell may be advantageously employed in permitting rapid training of the neural networks as described below. Alternatively, it will be appreciated that the neural networks may be implemented in hardware using, for example, a neural network chip such as the ETANN chips manufactured by Intel. Corp. of Sunnyvale, Calif.
Returning to FIG. 3, while the input signal 26 is shown as filling all 300 index points, in practice, it is not desirable to wait 15 seconds in order to fill the data buffer with 300 points before analysis is performed. This is because if a given wave was, for example, 10 seconds long, 5 seconds would be wasted for the buffer to fill and little time would be left to complete the analysis before another wave was generated. Thus, it is desirable to analyze a partially filled buffer. As shown in FIG. 4 the buffer is filled gradually until a complete waveform has been received. Thus, the first waveform 74 in FIG. 4 is rejected because it is not complete, likewise the waveform 76 is rejected and finally waveform 78 is accepted by the system. This is accomplished as follows.
Referring to FIG. 5, a waveform 80 is shown after part of the wave has been collected. It should be noted that index point 0 would contain the digitized value of the amplitude of the waveform (capnogram) at time 0. Index point 20 would contain the value measured 20 points (1 second) later. Initially, a few, five for example, data points are collected and sent to neural networks 1 and 2. The neural networks 1 and 2 would receive 300 numbers from the buffer. Since some signal must be passed to the input nodes of these neural networks, the empty buffer locations, which were assigned values of -1, are given the value of zero for analysis. Thus, the first five data points would contain actual wave amplitude values and the remaining 295 input nodes would be 0. As shown in FIG. 5 sometime later the waveform amplitude values contained in 100 index points of wave 80 are transmitted to neural networks 1 and 2 and the remaining 200 points are empty places from the buffer which are padded with zeros before transfer to the network as illustrated in FIG. 6.
Each time data is transmitted to neural network 1 or 2, output node 66, shown in FIG. 3, will produce an output which in the case of neural network 1 will represent the index number of the starting point of the wave; in the case of neural network 2, output node 66 will assume a state having a numerical value representing the index number of the end point of the wave. For example, as shown in FIG. 3 the starting point occurs at index point 80 in the buffer as well as input node 80 in neural network 1. This will cause the neural network 62 to produce a value at output node 66 of 80. Likewise, in the case of neural network 2, since the end point occurs at index point 175 the output node will produce a value of 175. It will be appreciated that by training neural networks 1 and 2, in accordance with conventional back prop techniques, using training sets of input data similar to conventional capnograms, the weights of synaptic connection 72 will converge to solution producing output values in the output node 66 corresponding to the index number of the wave starting point or ending point. Also, using two different neural networks permits independent training and testing sets, and a different number of hidden nodes for each network. It will also be appreciated that neural networks 1 and 2 could be combined into a single network having two output nodes, one designating the starting point and one output node designating the end point. However, it has been found that a number of advantages are achieved by separating this function into two separate neural networks as illustrated herein.
Referring again to FIG. 6, it will be appreciated that at this stage a correct starting point may be identified by neural network 1 but that index point 100, for example, will incorrectly be identified by neural network 2 as an ending point. In order to recognize that this is not a valid end point, the present invention compares the index of the end point determined by neural network 2 with the index of the last collected real data point. Real data must exist at the end point index for the wave to be considered captured. Thus, referring again to FIG. 4 the end point identified by neural network 2 will be rejected in the case of the waveform at stages 74 and 76, but will finally be accepted at stage 78. Thus, by repeatedly sampling data to determine the location of the end of the waveform it is not necessary to wait for a buffer to fill before passing its contents to the neural networks 1 and 2 for analysis. Also, it will be appreciated that the use of the analog to digital converter with direct memory access hardware permits data to continue being collected into the buffer in a background process while neural networks 1 and 2 attempt to locate the starting point and end point.
Another situation which must be accounted for occurs if the waves are arriving at a relatively low frequency, and the buffer is partially filled with zeros waiting for a wave to begin. This situation is illustrated in the curve 82 shown in FIG. 7. If this happens, the end point determined by neural network 2 will never fall after the last collected data point. For example, they both may be at data point 300. Further, any time the end point is found in the last 20 nodes, it will be desirable to collect additional data. This will permit neural network 2 to get a good look at the terminal portion of the wave. To handle both these situations, the earliest 20 points 84 are deleted from the buffer so that the wave is "slid" to the left to make room for additional data collection. Deletion is performed by moving the 0 index value 20 points later, (to the right), and changing the 20 data point valves to -1. This will result in the wave 86 shown in FIG. 7. The assumption is that if no valid end point has yet been identified, (or if it found in the last 20 nodes), it is unlikely that the earliest data points are part of a valid wave and can be removed. Note that the number of neural network input points was chosen to be significantly larger than the anticipated maximum wave duration. Further, this shifting procedure insures that neural network 3 will have sufficient information about the terminal portion of the wave to make accurate classifications. This is because it is desired that neural network 3 use as much information about the waveform including the lead and lag portion for recognizing and classifying waveforms, in much the same way that a human observer would use this information to recognize characteristic waveforms.
The software control program 52 continues in the above described fashion--collecting a few data points, sending them to neural networks 1 and 2, and analyzing the outputs of the neural networks--until both start and end points are plausible. Once this happens, the contents of the buffer between the start and end points is extracted and sent to neural network 3 for pattern recognition. The buffer will continue to collect new data so that no waves are missed. That is, subsequent processing is performed at a rate considerably faster than the rate at which new data enters the buffer. This is an important consideration which permits the present invention to be utilized in real-time.
Once neural networks 1 and 2 locate valid start and end points of the wave, the values of the amplitude of the wave between the start and end points are sent to neural network 3. If further analysis (discussed below) by neural network 3 confirms that we have a valid wave, the buffer will be cleared almost up to the end point index. As mentioned above, the buffer is cleared up to about 5 points earlier than the end point. Thus, when newly collected data is analyzed a few old data points are presented to neural networks 1 and 2 along with the new data. This technique increases the likelihood that neural network 1 will see enough of the starting region of the wave to identify it. This technique underscores an important principle of the present invention. That is, to try to mimic the way a human would identify starting points and end points. A human must see a bit of the wave before the start point and after the end point to be certain that those points are valid.
Neural network 3, 46 is a three layer perceptron having 50 number of input nodes, so that it is sufficiently wide to accept the expected waves between start points and end points. In accordance with the preferred embodiment, neural network 3 has an output corresponding to each unique classification, such as the classifications 54-60 shown in FIG. 2. Thus, if a normal wave such as wave 54 in FIG. 2 is presented to neural network 3, the output corresponding to normal should be 1.0 and the outputs corresponding to the other classes of abnormal waves should all be zero or close to it.
However, before presentation to neural network 3 the wave must be normalized or scaled. This insures that all waves have an arbitrary maximum value of 100 and approximately the same length of lead and lag segments. This step facilitates identification by neural network 3 because it reduces the wide variation in amplitude and duration that such waves can have. For example, a wave of amplitude 6 and duration 9, and a wave of amplitude 4 and duration 8 may both be completely normal and recognized as such based on their shape. There are a number of ways to normalize this data. These may be summarized as follows:
1. Time normalization--this technique is necessary when n data points must be mapped to x input nodes.
2. Amplitude normalization--this is used to emphasize certain morphologic features (and de-emphasize others) to improve network performance and efficiency.
3. Lead and lag normalization--this refers to aligning the rising and falling segments of each wave with respect to the input nodes of neural network 3, in order to reduce the translational variability of the input vector.
Time normalization is used to calculate the inputs to neural network 3. The time series of data delineated in the buffer by the start point and end point consists of a variable number of data points (analog-digital samples.) This time series must be expanded or reduced in time so that it may be mapped to the 50 input nodes of neural network 3. The process by which the data is arranged into 50 equally spaced points is as follows: each new data point is calculated by finding the two original data points which most closely approximate the desired data point in time. Then, the amplitude of the wave corresponding to the desired point in time is calculated by literally interpolating between those two nearest original data points. For example, referring to FIGS. 8 and 9 suppose that 16 data points in curve 88 comprise the wave delineated by the start point and end points, and neural network 3 required 10 data points. (As opposed to 50 required in the preferred embodiment) Thus, it is desired to translate curve 88 having 16 data points into curve 90 having only 10 data points. Since no collected data points exist, at the exact points of the desired time arrival (point x1 and x2 in FIG. 9) the amplitude for x1 is interpolated from A and B on curve 88 and the amplitude for x2 is interpolated from points C and D on curve 88.
Amplitude normalization techniques may be tailored to the specific pattern recognition paths employed by the present invention. In capnogram analysis, the capnogram's morphology is the primary determinant of capnogram classification. However, the only difference between an entirely normal capnogram and one produced as a result of an expiratory valve leak is the base line off-set of the wave. Therefore, the maximum amplitude of each wave is normalized so that all capnograms passed to neural network 3 have identical peak values. Importantly, the minimum values of each wave are preserved as a ratio of the maximum amplitude. This transformation is performed as illustrated in FIG. 10. In particular, wave 92 has a minimum value of wave amplitude b at point 94 and a maximum value wave amplitude of a at point 96. The amplitude of each data point is then scaled by 100/a. Thus, as illustrated in curve 98, the new wave maximum amplitude is 100 (a×100/a). The new wave minimum amplitude is equal to b×100/a.
Lead and lag normalization is performed to align morphologically similar segments of the capnogram in the input nodes of neural network 3. While neural network 3 could classify capnograms which are shifted earlier or later in the input layer, this translational variability reduces the classification accuracy and complicates training. If not for lead and lag normalization, capnogram alignment in the input node vector of neural network 3 would be dependant upon the performance of neural networks 1 and 2. Therefore, if neural networks 1 and 2 are performing well one would not expect significant variability in wave alignment. However, it is possible that neural networks 1 and 2 will need modification and that the modified networks will pick slightly different staring point and end points while neural network 3 remains fixed (not retrained). Thus, if all new starting points were slightly earlier and all new ending points slightly earlier, all new capnograms passed to neural network 3 would be shifted later in the input layer. As a result, neural network 3 might not still perform optimally. Therefore, by performing lead and lag normalization, we isolate the performance and training of neural networks 1 and 2 from the training of neural network 3. This greatly simplifies the task of training and permits refinements and customization of the system to be performed in a modular fashion where changes in one section do not require retraining or reconfiguration of another module.
Referring now to FIG. 12 lead and lag normalization is performed by locating the point of half-maximum capnogram amplitude on the rising and falling segments of the wave (A 1/2RISE 100 and A 1/2FALL 102), respectively) Next, the wave duration D between these two points is measured. Then, the amplitude of the wave at the points 1/3 earlier than A 1/2RISE 100 and 1/3 D later than A 1/2FALL , are measured. Lines 104 and 106 are then extended from those points to produce new lead and lag segments as shown in FIG. 13.
Waveforms other than capnograms may require different techniques for normalization. For example, arterial pressure wave should be normalized for maximum and minimum values but not for lead and lag segments. In this case, it might be desirable to append a first derivative of a waveform for input to for input to neural network number 3. Thus, where the raw waveform appears as shown in curve 108 of FIG. 14, the normalized waveform 110 is shown in FIG. 15 with the first derivative appended. This addition to the waveform is used for the purpose of improving Neural Network No. 3's ability to classify subtle feature differences.
Normalization is usually performed in the following order: (1) amplitude; (2) lead-leg; (3) time. The normalized waves are then fed directly to the 50 input nodes of neural network 3. Neural network 3, has been previously trained to recognize and classify the wave's morphology as for example, one of the wave classes shown in FIG. 2.
Every output node of neural network 3 corresponds to a different classification. However, output node number 1 is different. It works in conjunction with neural networks 1 and 2 to validate the acquisition of an acceptable wave. Referring now to FIG. 16 partially collected waves, noise and other spurious data such as those shown in this figure are actively identified.
Referring now to FIG. 17 a table of six output nodes of neural network 3 in accordance with a preferred embodiment of the present invention is shown. It is seen that this network has been trained to recognize partial waves by producing an output in output exceeds some threshold (usually 0.3), no further analysis of the data is performed. Instead, additional data is collected and appended to the data already in the buffer and presented again to neural networks numbers 1 and 2. It is possible to append data because the buffer is not cleared until a valid wave is identified by neural network number 3. Thus, neural network number 3 performs two functions: One, validity checking of the captured (putative) wave. Two, preliminary classification of the waves morphology.
Referring now to FIG. 18, an example of a wave 110 is shown. The outputs of four of the output nodes of neural network number 3 are also shown. Each of the output nodes will have an output value which ranges from 0 to 1, representing a different classification. The greater the value associated with an output node, the more strongly the network believes this wave belongs to that class. In the case shown in FIG. 18 the partial wave node value of 0.1 indicates that the wave is not a partial wave. The normal value of 0.8 indicates that the wave 110 can be accepted as being normal and the output can then be transmitted to the display unit 54 for utilization by operating room personnel, or subsequent processing equipment.
In some cases, however, the outputs of neural network 3 will be in conflict (such as "normal" in combination with any class of abnormal), or when no obvious winner exists. In this case, further analysis of the data by neural network number 4, called the arbitration network, is used. The arbitration network number 4 analyzes the outputs of neural network number 3 in the context of other information about the wave.
For example, if the output of neural network number 3 is as shown in FIG. 19, in this case, it is not clearly a normal wave since the normal value is only 0.6 and the expiratory value is 0.5. A human expert analyzing wave 112 in FIG. 19 would possibly be able to recognize that the capnogram wave 112 is slightly above the baseline because the patient is breathing at a high respiratory rate. In this case the baseline elevation is due to monitor response time characteristics and not necessarily to a valve abnormality. The neural network number 3 is technically correct in identifying an expiratory valve defect because of the elevated baseline. Refer to curve 60 in FIG. 2. Furthermore, the neural network's confusion (normal and exp valve is understandable because the wave appears close to normal and the elevation is very slight.
To resolve this ambiguity neural network number 4 is supplied with the same information that permits the human expert to correctly classify the wave. Thus, neural network number 4 receives as inputs the outputs of neural network number 3 and additional data such as respiratory rate, peak and minimum CO 2 values. For example, neural network number 4 inputs may comprise the following: normal-0.6, cleft 0.1, expiratory valve defect 0.5, respiratory rate 26, peak CO 2 6%, minimum CO 2 0.5%. (The partial wave category used in neural network 3 is no longer needed for neural network number 4).
The outputs of five output nodes of neural network number 4 are shown in FIG. 20. In this example, neural network number 4 outputs may be as follows: normal 0.9, cleft 0.0, inspiratory valve 0.0, exp valve 0.1, unknown 0.0. During system development, when neural network number 3 classification is ambiguous, an expert can examine the outputs of neural network number 3 and use his expertise to train neural network number 4. Although in accordance with the preferred embodiment, neural network 4 is given additional contextual data, it is also possible to omit the additional data and simply train neural network number 4 to interpret patterns in neural network number 3's outputs to produce the correct outputs. Neural network number 4 like neural network number 3 is a three layer perceptron containing six to ten input nodes and five output nodes and may have between 4 and 8 hidden nodes of course these values may vary widely on the application.
Referring now to FIG. 21, a summary of the steps performed by the waveform analysis system 30 are shown. In the first step 114 the entire contents of the buffer 40 at an arbitrary point in time is shown. To the left of the vertical dotted line the wave which was last identified is shown and is about to be discarded from the buffer. To the right of the vertical dotted line is the newly collected raw data which is to be transmitted to the inputs of neural networks number 1 and number 2.
In step 116 neural network number 1 locates a starting point SP at index point 10 in the buffer, (which corresponds to the tenth input node of neural network number 1). Likewise, neural network number 2 locates the end point EP at index point 120 in the buffer corresponding to the index node number 120. Data between index points 10 and 120 are then normalized in step 118. This normalization as discussed above includes time normalization, amplitude normalization and lead and lag normalization. Thus, the incoming curve 120 is transformed into the normalized curve 122. Regardless of the original wave duration, all the waves are normalized to 50 data points as discussed above before transmitting to the 50 input nodes of neural network number 3 in step 124. Neural network number 3 then produces output signals in its output nodes which classify the incoming wave. Should an ambiguity exist in this classification the information from neural network number 3 is transmitted to neural network number 4 in step 126 along with additional information such as respiratory rate, peak CO 2 and minimum CO 2 . Neural network number 4 outputs then remove the ambiguity and correctly identify the wave as normal.
Training the neural networks 1-4 may be performed using training data devised from actual patient data or using data generated using an artificial lung attached to the breathing apparatus and capnogram monitor 24. Training in the preferred embodiment was in accordance with the back propagation procedure which is fully explained in the Ward System Group NeuroShell Manual published by Ward's Systems Group of Frederick, Md. and incorporated herein by reference. Neural networks 1-4 each required tens of thousands training cycles to train. The number of training cycles can vary widely depending on the application and the criteria for acceptable results. Using the NeuroShell hardware training board this was accomplished in approximately 8 hours. It will be appreciated that other neural network architectures besides back prop may also be successfully employed utilizing the techniques of the present invention.
The output of neural network number 4 may be used in a number of ways. For example, display 50 may simply display the classification indicated by neural network number 4 output, or may also include an alarm to alert operating room personnel to an abnormal condition. Further, display 50 may be coupled to other processing systems. For example, the display 50 may be coupled to an interactive system which permits the user to receive explanations of the detected abnormalities and to also receive instructions as to corrective measures which should be taken. Besides the operating room application, the waveform analysis system 30 of the present invention may be used as an intelligent input into a comprehensive patient monitoring system. Also this system design could be applied to many signals acquired simultaneously from one patient to perform intelligent diagnostics.
From the foregoing, it can be seen that the present invention provides a waveform analysis system that is capable of analyzing physiologic as well as non-physiologic waveforms and effectively segmenting the waveform, classifying the waveform and resolving ambiguities in classifications. This system avoids costly algorithm development, works rapidly enough for real-time deployment, and can be implemented at a reasonable cost. Furthermore, the modular construction of the waveform analysis system 30 in accordance with the present invention permits individual neural networks to be retrained and modified independently of the others. Furthermore, once the neural networks 1-4 are trained to a satisfactory degree, the internal synaptic weights derived by training may be set to fixed values and embodied in fixed weight hardware for inexpensive mass production. Those skilled in the art can appreciate that other advantages can be obtained from the use of this invention and that modification may be made without departing from the true spirit of the invention after studying the specification, drawings and following claims. | A real-time waveform analysis system utilizes neural networks to perform various stages of the analysis. The signal containing the waveform is first stored in a buffer and the buffer contents transmitted to a first and second neural network which have been previously trained to recognize the start point and the end point of the waveform respectively. A third neural network receives the signal occurring between the start and end points and classifies that waveform as comprising either an incomplete waveform, a normal waveform or one of a variety of predetermined characteristic classifications. Ambiguities in the output of the third neural network are arbitrated by a fourth neural network which may be given additional information which serves to resolve these ambiguities. In accordance with the preferred embodiment, the present invention is applied to a system analyzing respiratory waveforms of a patient undergoing anesthesia and the classifications of the waveform correspond to normal or various categories of abnormal features functioning in the respiratory signal. The system performs the analysis rapidly enough to be used in real-time systems and can be operated with relatively low cost hardware and with minimal software development required. | 0 |
RELATED U.S. APPLICATION DATA
This is a file-wrapper continuation of application Ser. No. 08/095,791, filed Jul. 22, 1993 now abandoned which is a Continuation-In-Part of application Ser. No. 07/796,007 filed Nov. 22, 1991, abandoned.
BACKGROUND OF THE INVENTION
The present invention relates generally to coating compositions, and more particularly, to polyorganosiloxane compositions forming mar-resistant coatings on substrates.
A variety of substrates, including those made of glass, plastic, metal, or concrete, are usefully coated with protective films. It is generally desirable that protective film coatings have good weathering properties, adhesion, and resistance to thermal and mechanical shock, heat, humidity, and common chemicals. It is also desirable that the film coatings be practical to apply, dry, and cure. These properties are more difficult to achieve when the protective film coating is applied to plastic substrates than when applied to many other substrates.
Some plastics substrates are desirable substitutes for glass due to a lighter weight than glass, economically advantageous fabrications, and breakage resistance. However, commercially available plastic substrates tend to have a reduced resistance to abrasion, marring, and scratching when compared to glass. Thus, protective film coatings for plastic substrates are of particular interest.
Several technical approaches have been attempted in an effort to coat plastic substrates in order to improve resistance to abrasion, marring and scratching of the plastic substrates. In particular, work has been carried out to develop coatings of polyorganosiloxanes cross-linked by a condensation of silanol groups.
The Mayasumi patent, U.S. Pat. No. 3,837,876, described a reaction of aminosilane with epoxysilane to produce a substance dissolvable in a solvent. Once dissolved, the substance was applied to various substrates to coat the substrates.
The Ender patent, U.S. Pat. No. 3,166,527, described mixing epoxysilane with aminosilane to make an unpolymerized mixture and a polymerized mixture. Each of the mixtures was applied to a surface to coat the surface. The coating made by each mixture was cured either by standing at room temperature or by heating.
The Koda patent, U.S. Pat. No. 3,961,977, described a use of aminoalkoxysilane hydrolyzed within a range of 10-40% of hydroxyl groups and epoxyalkoxysilane to make a coating mixture. The hydrolyzed aminoalkoxysilane and epoxyalkoxysilane were dissolved in a solvent. Solvents described included a ketone.
The Treadway et al. patent, U.S. Pat. No. 4,378,250, described a use of ketones or aldehydes in making a coating. In particular, the Treadway et al. patent described increasing the hydrolysis of at least two different silane materials to above 40% to make a reaction mixture. The Treadway et al. patent also described adding the ketone to the reaction mixture to form a ketimine.
SUMMARY OF THE INVENTION
The present invention includes an abrasion-resistant coating that adheres well to the substrate and is clear, transparent, colorless, and free of visible specs. The coating is also highly tintable and is strongly adherent to the substrate even after tinting or exposure to heat and humidity.
The coating composition includes a solvent, an epoxy prepolymer, and a partially hydrolyzed aminosilane that is effectively blocked from reacting with the epoxy prepolymer at ambient temperature. The coating composition is applied to the substrate and then treated to remove the block from the hydrolyzable aminosilane such that the aminosilane and the epoxy prepolymer react to form an abrasion-resistant coating.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention includes a coating composition that includes a solvent, a nonsilane epoxy prepolymer that undergoes epoxy polymerization, and a partially hydrolyzable aminosilane that is effectively blocked from reacting with the epoxy prepolymer at ambient temperature to provide an exceptionally durable coating that is cross-linked by silanol condensation. The present invention also includes a method for making a coating cross-linked by silanol condensation that includes partially hydrolyzing an aminosilane to a degree that is greater than 10% of complete molar reaction, mixing the partially hydrolyzed aminosilane with an agent blocking epoxy polymerization such as a ketone or an aldehyde to form a ketimine thereby blocking later epoxy polymerization until desired by heating, adding a non-silane epoxy prepolymer to the ketimine to form a mixture, partially polymerizing the mixture by heating to provide body to the mixture, adding a solvent to provide to the polymerized mixture a proper viscosity for coating, and adding a surfactant to provide uniform coating characteristics.
The coating composition of the present invention is suitable for coating plastic substrates such as ophthalmic lenses. In particular, the coating composition provides an abrasion-resistant and mar-resistant coating for polycarbonate ophthalmic lenses.
The coating composition of the present invention is tintable. The coating composition may be used to formulate a coating for a substrate such as an ophthalmic lens which tints many times darker than coatings with compositions having two or more different silanes. A presence of two different silanes is believed to render the composition of the coating ponderous. Also, the composition having two or more different silanes has a limited dye tintability range obtainable by varying the ratio of epoxy to amino groups within the bounds of allowable abrasion resistance.
The method of the present invention is usable to provide a tintable coating for substrates such as ophthalmic lenses. In particular, the method may further include steps of coating a substrate with the coating composition and contacting the coating with a dye to impart a tint to the coating. The method has an increased versatility and efficiency for tinting lenses over methods presently available. A wide range of tint values and shorter tinting times with tinting baths may be produced by suitable variations of the proportions of epoxy and aminosilane components of the composition of the present invention.
Suitable epoxies usable in the composition of the present invention include compounds of the general formula: ##STR1## where R 1 and R 2 include hydrogen, alkyl, aryl, alkoxy, alkoxyalkyl, alkoxyaryl, or other relatively stable organic moieties. Diepoxy, triepoxy, or polyepoxy compounds with the epoxies separated by alkyl, etheric, or alkyletheric linkages may also be used.
Suitable aminosilanes include compounds having the general formula: ##STR2## where the R can be any stable mix or combination at the various positions of alkyl, alkoxy, alkyl ether, alkylamino or other combination of carbon and hetero atoms. One particularly preferred component, due to availability and price, is gamma-aminopropyltriethoxysilane.
Suitable solvents in the coating composition include alcohols, aldehydes, ketones, glycol ethers, and esters. One preferred solvent is a mixture of methyl ethyl ketones and ethyl alcohol. The particular step at which solvent is added in the method of making the composition is not critical. It is convenient, however, to add a chilled solvent to quench the prepolymerization reaction.
In one embodiment, the composition preferably also includes a surfactant, used as a flow-controlling agent for regulating film thickness and enhancing the cosmetic appearance of the coated article. One commonly available surfactant is FLUORAD FC-430®, available from 3M Corporation of St. Paul, Minn.
When the coating is applied to a substrate, the coating can be polymerized and hardened in an oven which has access to normally humid air. The heat and moisture remove the blocking agent so that epoxy polymerization which is catalyzed by the amine can take place.
The examples set forth below are intended for illustrative purposes and should not be construed as limiting the invention in any way.
EXAMPLE 1
1,000 grams of gamma-propylaminotriethoxysilane was added to 150 grams of water (H 2 O) to form a mixture which was heated to 35° C. and stirred for an hour. The temperature of the mixture reached approximately 80° C. The resultant solution was allowed to stand for at least two hours. This will be called Solution A.
A quantity of cyclohexane dimethanol diglycidyl ether was set aside and will be called Solution B.
A quantity of 100 grams of FC-430® surfactant, manufactured by 3M of St. Paul, Minn., were dissolved in 900 grams of methyl ethyl ketone and labeled Solution C.
EXAMPLE 2
A quantity of 1,000 grams of solution A were added to 256 grams of solution B to form a mixture. The mixture was heated with stirring to 53° C. and components were allowed to react for 10 minutes. The mixture was then quenched with a quenching mixture of 1,500 grams of methyl ethyl ketone, 64 grams Solution C and 570 grams ethyl alcohol. The quenched mixture was cooled down to 10° C. Polycarbonate lenses were dip coated with the cooled mixture, held at 65.6° C. for 20 minutes, and cured for 4 hours in an oven at 121.1° C.
Adhesion was tested by ASTM D3359. Abrasion was tested by 5 strokes of a steel wool mass weighted with a 32-ounce weight. If no scratches are observed, the coating passed. The lenses were tested for adhesion and abrasion. The lenses displayed acceptable adhesion and abrasion. The lenses were dyed for five minutes in BPI black and were found to have a total light transmission of 3%.
EXAMPLE 3
A quantity of 550 grams of solution A were added to 225 grams of solution B to make a mixture. The mixture was heated to 52° C. and components of the mixture were allowed to react for 5 minutes. The mixture was then quenched with a mixture of 650 grams of methyl ethyl ketone, 11 grams of solution C, and 81 grams of ethyl alcohol. The quenched mixture was cooled down to 10° C.
Polycarbonate lenses were dip coated with the mixture, held at 65.6° C. for 20 minutes, and cured for 4 hours in an oven at 121.1° C. The lenses passed the adhesion and abrasion tests and were tinted for various times with BPI black dye. The degree of tinting that occurred with tinting time is described as follows:
______________________________________Tint time, Total lightminutes transmission, %______________________________________5 2.23 11.22 26.11 43.3______________________________________
EXAMPLE 4
The conditions of Example 3 were repeated except that 500 grams of solution A and 500 grams solution B were subjected to different prepolymerization times at 52° C. The different prepolymerization times are listed below. Variations in total light transmission at 3 minute dye immersion is shown below.
______________________________________Prepolymerization time,minutes Total light transmission, %______________________________________ 6 17.0 8 20.510 27.0______________________________________
COMPARATIVE EXAMPLE 1
A coating solution prepared using equimolar amounts of the epoxysilane and the amino silane. Lenses coated with this composition and cured at 121.1° C. for 4 hours exhibited 58% total light transmission. | An improved composition for producing a scratch-resistant coating for a plastic object together with the process of making and applying the coating is herein disclosed. Included in the composition is a mixture of a nonsilane organic epoxy compound and a partially hydrolyzed aminosilane reacted with a carbonyl-containing compound in an organic solvent. The mixture is applied to a plastic surface which is then heated to cure the coating into a hard transparent film which can be tinted quickly and darkly with an organic dye. | 2 |
BACKGROUND OF THE INVENTION
The present invention concerns a method and apparatus to facilitate the repair of warp threads in weaving looms using a system for manipulating fallen drop wires.
Drop wires are conventionally used in warp detector systems. Each warp thread is threaded through a warp detector wire such that, in the event of a break in a warp thread, the corresponding wire drops vertically, whereupon the event is detected in an appropriate manner and the loom is stopped.
Taking into account the large density of the warp threads, i.e. 40 to 60 threads per cm., it is quite obvious that a very tight and compact drop wire system is required. The drop wires are thus always mounted in rows (hereinafter "packs"), wherein the wires of the same row come into contact with a common electrode when the wires drop to provide a signal that a warp thread has broken. As this wire package is very compact, it is obviously quite difficult for the weaver to determine a position of the broken warp thread and to carry out the repair of the broken warp. An improvement aimed at facilitating the repair of a broken weft is described in U.S. patent application Ser. No. 014,778 filed Feb. 13, 1987 and commonly owned with this application. The aforesaid patent application describes a method whereby the fallen drop wire is caught by a gripper and moved above the wire pack in such a way that the weaver can easily carry out a repair. In order to achieve direct accessability with the hands to the wire involved, the adjacent drop wires are pushed laterally apart from each other by means of rotatable arms.
Although such a device provides a noticeable improvement over known warp detector systems, it has, however, the disadvantage that, owing to the position of the presented wire, it is quite difficult to carry out an automatic re-threading.
The present invention concerns a different method whereby the aforesaid disadvantage is overcome and whereby automatic re-threading of the wire is facilitated. This does not preclude, of course, manual repair of the warp thread.
SUMMARY OF THE INVENTION
The method in accordance with the present invention mainly comprises the detection of a fallen drop wire, gripping the fallen wire and rotating the wire about its lengthwise axis to a predetermined angle. The rotation of the drop wire offers the advantages as described below (which may or may not be usable at the same time).
The main advantage of the invention is the fact that the rotation of the wire makes the location of the warp break more clearly evident to the weaver.
Another advantage is that the adjacent drop wires are locally pushed or spread apart from each other whereby accessability to the fallen drop wire is improved and whereby auxiliary spreader elements then can be introduced between the wire pack in order to push the adjacent wires still further apart from each other.
Another advantage is that the rotation of a fallen drop wire places the wire and its thread opening in a plane which is located in cross-direction or nearly cross-direction relative to the direction of the warp threads, whereby re-threading can be carried out more easily by using an automated device. Quite obviously, the removal of the broken warp thread is also facilitated.
BRIEF DESCRIPTION OF THE DRAWINGS
In order that the characteristics of the invention will be better understood, the preferred embodiments are described and illustrated by way of examples which are not to be regarded as limiting in any way. With reference to the Drawings:
FIGS. 1 and 2 are views across a warp stop motion of a loom across drop wire packs and illustrate the gripping and rotating a fallen drop wire in accordance with the invention;
FIG. 3 is a cross-section view along line III--III of FIG. 2;
FIG. 4 is a view similar to FIG. 3, but whereby auxiliary spreader elements have been introduced between warp threads in order to push adjacent drop wires further apart from each other;
FIGS. 5 and 6 illustrate alternative embodiments of apparatus used to spread the drop wires;
FIGS. 7 and 8 illustrate still another alternative embodiment of the invention;
FIG. 9 shows apparatus according to the invention for carrying out the inventive process;
FIG. 10 is a cross-section view taken along line X--X of FIG. 9; and
FIGS. 11 to 14 illustrate the rotation of the drop wire with a part of the broken warp thread present in the drop wire.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
With reference to FIGS. 1 to 3, a warp detector stop motion 1 essentially comprises, as is already known, a large number of drop wires 2 which are mounted in rows (i.e., packs) respectively 3 to 5 of wires suspended on the warp threads 7 extending through thread openings 6.
For each row of drop wires 2, a common guiding element 8 is provided and generally is an electrode for providing a warp break signal upon contact with a fallen drop wire. Under the warp threads 7, support elements, i.e., support shafts 9, can also be mounted. When a break occurs in one of the warp threads 7, the corresponding wire 2 falls downwards, whereby contact is made with the electrode 8. The fallen drop wire will be indicated hereafter by the reference Number 2A. The fallen dropped wire 2A can be located according to a well known method, for instance by means of a moving detection device located under the wires as already described in U.S. patent application Ser. No. 014,778 mentioned above.
In order to facilitate the re-threading of the broken warp through the dropped wire, the method in accordance with the invention is resorted to. Specifically, as illustrated in FIG. 1, the fallen wire 2A is engaged or gripped underneath, for instance, by means of a clamping device 10 (See FIG. 10). Afterwards, the clamping device 10 and thus also at least the bottom end 11 of the wire 2A are rotated to a predetermined angle that is equal for instance to 90°, as illustrated in FIG. 2. In this way, an opening 12 with a width D is obtained along the length of the wire 2A involved (FIG. 3) because the transverse width of each drop wire is greater than the normal space between the wires of each pack in their warp detecting position, whereby the advantage is obtained that this wire 2A is made better accessible to the weaver.
Afterwards, spreader elements 13 and 14 preferably will be introduced into the opening 12 and will be then shifted apart from each other as illustrated respectively in FIGS. 3 and 4, whereby the adajcent drop wires 2 and the warp threads 7 running through these wires are shifted still further away from the dropped wire 2A in order to increase further the size of opening 12. These auxiliary spreader elements 13 and 14 may be of any arbitrary number and of an arbitrary kind. Essentially, the spreaders 13,14 can be supported by a suitable system for movement along and between adjacent packs of drop wires.
In the illustrated embodiment, these elements 13 and 14 comprise forks 15 and 16 that can be disposed over the support elements 9 at the right place; i.e., into the opening 12, by means of cylinders 17 and 18 and a locating device which is not illustrated. The forks 15 and 16 are then moved apart from each other in order to achieve the aforesaid effect.
Also in accordance with the method of the invention, the fallen wire 2A is elevated by means of the clamping device 10 as indicated in dotted lines in FIG. 2. Since the fallen wire 2A is rotated over about 90° at the height of the thread opening 6 relative to its normal position, re-threading can be carried out relatively easily, either manually or automatically, since this threading can occur along a direction 19 (FIG. 5) which is parallel to the direction of the warp thread 7.
During the upwards movement, the wire 2A involved preferably will be rotated back to its normal warp detection position in order to avoid excess friction occurring between the twisted wire 2A and the corresponding electrode 8; and so that the clamping device is not unnecessarily heavily loaded and/or damaged. Before the re-threading is carried out, however, the clamping device 10 is brought back to its rotated position while the fallen drop wire is held at its elevated position (e.g., see FIG. 6).
Since possibly a threading element (i.e., a thread needle) must pass along the support elements 9 as well as through the thread opening 6 during the re-threading, the fallen wire 2A involved must be put in its highest position, i.e., higher than during the normal suspension to the warp thread 7. This is indicated in FIG. 2 by the height H where the fallen wire is shown in hidden lines.
According to an alternative solution of the method described hereabove, the rotation of wire 2A may be carried out only after the fallen wire has been elevated to its highest position, to thereby facilitate the re-threading while the adjacent warp drop wires 2 are not spread further apart. The pushing apart of the wires can indeed be carried out in another way. As illustrated on FIGS. 5 and 6, this can occur, for instance, by the use of a clamping device 10 having wedge-shaped arms 20 and 21.
In the embodiments described hereabove, drop wire 2A is shown as being twisted along its length relative to its rotation angle, but this is not necessarily always the case.
If, as illustrated in FIG. 7, the wires 2, and 2A are mounted with sufficient clearance on the guiding elements or the electrodes 8, the wires can be rotated over a sufficiently large angle without being necessarily twisted along their length. This latter embodiment is illustrated in FIG. 8. Quite obviously, as shown in FIG. 8 wire 2A is simply rotated over its full length.
The resulting advantage is that the wire can be engaged, for instance at its end above the electrode 8, in order to achieve the rotation while, on the other end, a re-threading can be carried out under the electrode.
Quite obviously, the fastening, the rotation and the re-threading can be carried out according to different alternative solutions either at the top end or at the bottom end of the drop wire 2, the chosen method depending upon the kind of wire used.
It is also obvious that the angle selected for rotation of the drop wire 2A at the height of the thread opening 6 need not necessarily be 90° but could be rather a function of the re-threading direction and of the size of the supplied threading element. Generally speaking, it can be stated that the fallen drop wire is rotated or twisted in such a way that the perpendicular projection of the thread opening 6 in a plane perpendicular to the re-threading direction is larger or equal to the width of the particular threading element used. The re-threading direction will normally be the aforesaid direction 19, although such is not necessarily always the case. The width of the aforesaid threading element is for instance, the diameter of the needle chosen for introducing a new thread through the wire 2A.
With reference to FIGS. 3 to 8, it should be remarked that the drop wires 2 are illustrated with a relatively large distance between each other for reason of clarity. Actually, in practice they are located nearly against each other at a distance less than the width of a drop wire.
FIGS. 9 and 10 schematically illustrate apparatus to put the method of the invention into practice. This apparatus mainly comprises a rotatable clamping table 22 whereon the aforesaid clamping device 10 is mounted with the grippers 20 and 21 in such a way that the clamping device 10 can be rotated.
The gripper 20 is actuated by means of a lever 23 and a pneumatic cylinder 24. As illustrated, cylinder 24 actuates lever 23 through a linkage 24a.
The rotatable clamping table 22 can be actuated for instance by means of a drive (i.e., rack and pinion) 25, as illustrated in FIG. 10.
The clamping device 10 can be moved upwardly and downwardly by means of apparatus like a vertically moving carriage 26, while the rotatable clamping table 22 is mounted on a horizontal carriage 27 capable of movement along a cross-direction 22a with respect to carriage 28, which can be driven or shifted under the drop wire packs. This carriage 28 also contains detection elements 29 in order to determine the position of the fallen drop wire 2A. Such a carriage 28 and the corresponding detection elements 29 are sufficiently described in the aforementioned U.S. patent application Ser. No. 014,778.
The operation of the apparatus in accordance with the invention can be clearly understood with reference to the drawings. Quite obviously the whole system can be preferably automated and, upon a fallen drop wire 2A being detected, the clamping device 10 can be automatically brought under this wire.
The gripping of the fallen drop wire 2A need not necessarily be carried out be means of a movable clamping device.
According to an alternative solution, this gripping can also be achieved, for instance, by means of a gripping element with a groove-shaped notch which engages the wire 2A while a rotation movement is applied afterwards to this element.
Quite obviously if another kind of warp detector wire is used, whereby, for instance, the thread is pulled above the electrodes, the method of the present invention remains also applicable if the gripping and rotating device is suitably designed.
The description up to now implies that the broken warp thread 7A is no longer present in the fallen wire 2A. In most of the cases, however, this broken warp thread 7A or at least part of it will still run through the wire 2A, as illustrated in FIG. 11. In such a case, the method in accordance with the present invention is carried out preferably stepwise as illustrated on FIGS. 12 to 14, whereby the rotation direction of the wire 2A is of essential importance.
In a first phase, as shown in FIG. 12, the fallen wire 2A is rotated in such a way that its legs 30 are rotated relative to the warp thread 7A in such a way that this thread is further engaged between the warp detector wire 2A and the adjacent warp threads 7 and warp detector wires 2. Consequently, two areas A and B, where no warp thread is present with a good clearance (including the broken warp thread 7A) and where the spreader elements 13a and 14a may be deposited is obtained in the diagnonal direction relative to the fallen warp detector wire. Spreader elements 13,14 need not necessarily be shaped as forked elements.
As illustrated in FIG. 13, the spreader elements 13a and 14a (shown here as rods corresponding with forked elements 13,14 in FIG. 1) may be placed between warp threads in the openings A,B moved apart from each other whereby, as already described, a larger opening is provided around the fallen warp detector wire 2A.
As far as FIG. 13 is concerned, it should be also noted that the location of the broken warp thread 7A is clearly determined by the side edges 31 and 32 of the rotated warp detector wire 2A, whereby the possibility is created that the broken warp thread 7A can be fastened at these locations by means of catching devices (not shown) in order to carry out further operations.
Finally, as illustrated in FIG. 14, the wire 2A can be rotated back in the other direction, whereby its legs 30 are rotated away from the broken warp thread 7A, in such a way that this thread is made completely free and can be removed without any problem from the wire 2A, whereby this warp detector wire 2A is then in a position suitable for re-threading.
The present invention is by no means limited to the embodiments described by way of examples and illustrated by the Drawings, bu the disclosed method to facilitate the repair of warp threads, the warp detector wires and the apparatus used can be put into practice according to a large number of alternative solutions without departing from the scope of the invention. | A process for manipulating fallen warp thread detector drop wires and revealing their location includes gripping and rotating a fallen wire, while spreading adjacent wires of the pack apart by a spreader and raising the fallen wire above the pack. Apparatus for gripping, rotating, spreading and lifting is disclosed. | 3 |
FIELD OF THE INVENTION
The present invention is directed towards the cleaning of industrial fabrics using cryoblasting techniques. "Industrial Fabrics" as used herein, includes but is not limited to fabrics used in the production of wet laid (paper and paper-related) products and dry laid (melt, blown, spunbond, dry laid cellulosics, non-wovens, etc.) products.
BACKGROUND OF THE INVENTION
While industrial fabrics generally come in a wide variety of styles, many can generally be characterized as formed from a woven pattern of warp and shute yarns, which extend in the machine and cross machine direction. In another variant, fabrics are joined of spirally wound fibers. Some industrial fabrics have a single layer while others are multi-layered, wherein the several layers are bound together by binder fibers woven among the several layers.
The industrial fabrics described above have literally thousands of interstices formed between the yarns. During the life of the fabric, materials used in the paper making process and paper related processes contaminate the fabric by collecting on the surface of the fabric and clogging the interstices. Materials which contaminate industrial fabrics used to make wet laid and dry laid products include cellulosic fibers, synthetic staple fibers, latex adhesives, olefinic polymer deposits, resin, pitch, tar, fillers, extenders, and starch residues, among others.
The adverse effect of these contaminants cannot be underestimated, since the primary function of industrial fabrics is to provide a medium to form, convey, and produce continuous paper, paper-related products, and non-woven products from fibrous raw materials. The fabric must maintain an acceptable degree of openness, which is something that diminishes with the accumulation of contaminants over the life of the fabric. Contamination reduces the performance and useful life of a fabric. Removal of contaminants could therefore have a beneficial effect in improving the useful life of industrial fabrics used to produce wet laid and dry laid products.
Cryoblasting is a process of cleaning surfaces of materials with carbon dioxide in its solid form. While it is analogous to sandblasting, cryoblasting has two distinct advantages over traditional sandblasting. First, the particles of solid carbon dioxide evaporate (or more precisely, sublime) after impacting against the surface. Impacting the surface with particles of solid carbon dioxide physically dislodges and removes contaminants, carrying the contaminants away from the fabric surface for collection at a remote site. These removed contaminants include both solids and liquids. After the solid carbon dioxide sublimes the collected contaminant consists solely of the solids and liquids removed from the fabric surface. The only residue is the liquid or solid removed from the surface of the object. Second, cryoblasting is believed to have chemical cleaning action in addition to mechanical cleaning action. Supercritical carbon dioxide is known to have solvent properties similar to chemical solvents such as hexane, i.e., nonpolar solvents. While not wishing to be bound by any theory, it is believed that at the sight of pellet impact, the local pressure on the solid carbon dioxide pellet causes the formation of supercritical carbon dioxide. This condition is believed to create a local nonpolar environment which has been found to be particularly effective in solubilizing and removing nonpolar residues such as oil and tar residues from surfaces.
Cryoblasting is practiced by two methods. One method uses compressed gas to accelerate particles of solid carbon dioxide. The second method uses a mechanical device to accelerate particles of solid carbon dioxide. The mechanical cryoblasting method was developed at Oak Ridge National Laboratory (ORNL). This method is reportedly more cost effective than the compressed gas method. Cost savings result from lower capital cost for equipment and more efficient use of solid carbon dioxide.
U.S. Pat. Nos. 5,109,636, 4,947,592 and 4,744,181 disclose a particle blast cleaning apparatus and method using solid carbon dioxide.
U.S. Pat. No. 5,108,512 discloses a process for the cleaning of the inner surfaces of a chemical vapor deposition reactor used in the production of semi-conductor grade polycrystalline silicon. The process comprises impacting the surfaces to be cleaned with solid carbon dioxide pellets. The carbon dioxide pellets dislodge silicon deposits from the surface of the reactor without damaging the surface of the reactor and without providing a source for contamination of semi-conductor grade silicon produced in the cleaned reactor.
Generally, the prior art procedures utilizing solid particles of carbon dioxide are directed to the cleaning of hard, durable materials such as steel and concrete. In spite of the durability of such materials, the particle velocities and particle hardness have been found to damage those materials.
SUMMARY OF THE INVENTION
The object of the present invention is to provide a method of removing contaminants from industrial fabrics using solid particles of carbon dioxide.
It is a further object of the invention, given the particle velocities and particle hardness, to develop operating parameters that permit the fabric to be cleaned while minimizing fabric damage.
The applicants have developed operating conditions that clean the fabric without damaging it. The method of cleaning an industrial fabric comprises impacting the fabric with solidified and pelletized carbon dioxide produced by a cryoblaster which projects the carbon dioxide pellets at the fabric. The cryoblaster can be scanned over the entirety of the fabric at a preselected scanning rate and at a preselected rate of projection in order to insure that the fabric is cleaned without damaging it. Alternatively, it could be scanned over selected regions of the fabric in order to spot clean portions of the fabric.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic diagram of the cryoblaster of the preferred embodiment.
FIG. 2 depicts the process employed in example 2.
FIG. 3 depicts the process employed in example 3.
FIG. 4A is a photograph of fabric sample SPNF9 before treatment.
FIG. 4B is a photograph of fabric sample SPNF9 after treatment.
FIG. 5A is a photograph of fabric sample SPF16 before treatment.
FIG. 5B is a photograph of fabric sample SPF16 after treatment.
FIG. 6A is a photograph of fabric sample SPNF11 before treatment.
FIG. 6B is a photograph of fabric sample SPNF11 after treatment.
FIG. 7A is a photograph of fabric sample SPF17 before treatment.
FIG. 7B is a photograph of fabric sample SPF17 after treatment.
FIG. 8A is a photograph of the top of fabric sample SPNF19 before treatment.
FIG. 8B is a photograph of the top of fabric sample SPNF19 after treatment.
FIG. 9A is a photograph of the bottom of fabric sample SPNF19 before treatment.
FIG. 9B is a photograph of the bottom of fabric sample SPNF19 after treatment.
FIG. 10A is a photograph of the top of fabric sample SPF21 before treatment.
FIG. 10B is a photograph of the top of fabric sample SPF21 after treatment.
FIG. 11A is a photograph of the bottom of fabric sample SPF21 before treatment.
FIG. 11B is a photograph of the bottom of fabric sample SPF21 after treatment.
FIG. 12A is a photograph of fabric sample SPF24 before treatment.
FIG. 12B is a photograph of fabric sample SPF24 after treatment.
FIG. 13A is a photograph of fabric sample SPF28 before treatment.
FIG. 13B is a photograph of fabric sample SPF28 after treatment.
FIG. 14A is a photograph of fabric sample SPCTA26 before treatment.
FIG. 14B is a photograph of fabric sample SPCTA26 after treatment.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The cryoblaster used in the preferred embodiment of the present invention consists of two primary elements. One element is the accelerator which consists of a disk twenty-two (22) inches in diameter which rotates at speeds of 4,000 to 12,000 rpm. The rotating disk contains grooves similar in appearance to the vanes on the wheel of a centrifugal pump. Solid CO 2 particles are introduced near the center of the rotating disk. The rotation of the disk causes the particles to move outward towards the edge of the disk. Once the particles reach the edge of the disk, they are thrown at a velocity corresponding to the tangential velocity for the outer diameter of the disk. For a 22-inch diameter disk, the velocity is 1,150 feet per second at 12,000 rpm. At 6,000 rpm, the velocity is proportionally lower and corresponds to 575 feet per second. See Haines, J. R., "Solvent Free Cleaning using a Centrifugal Cryogenic Pellet Accelerator", which is incorporated herein by reference.
The second element of the cryoblaster consists of a pelletizing device which converts liquid carbon dioxide into solid carbon dioxide pellets. This device is fed with liquid carbon dioxide which is stored in a tank at 0° C. under pressure of about 300 psi. As the CO 2 exits the tank and enters the chamber, it expands and forms a pelletized "snow".
The cryoblaster has the capability of delivering solid carbon dioxide pellets at rates ranging between 100 and 600 pounds per hour. The cryoblaster produces a spray of solid carbon dioxide pellets covering an area measuring approximately 2.5 cm by 13 cm. The cryoblaster is connected to a robot which is used to scan the cryoblaster in a controlled manner over the surface of the object. While scanning speeds vary from about 1 mm/sec to several thousand mm/sec, the recommended scanning speed is 120 mm/sec for the cryoblaster. This speed, combined with a delivery rate of at least 200 pounds per hour of solid carbon dioxide, results in nearly 100 percent pellet coverage for most areas being scanned.
As shown in FIG. 1, the equipment required for cryoblasting includes: liquid carbon dioxide storage 5, solid carbon dioxide particle maker 10, mechanical particle accelerator 15, air handling system 20a and 20b, which ensures that the work environment does not contain hazardous levels of carbon dioxide, a vacuum assisted accumulator for collecting contaminants removed from the fabric 25, and a fabric support means 30. Another suitable cryoblaster is the aforementioned one which accelerates the CO 2 particles by a compressed gas system, and cryoblasters which produce CO 2 particles by grinding blocks of solid CO 2 . Particles may also be formed by an extrusion process in which solid CO 2 is forced through a die and pelletized.
In cryogenically cleaning industrial fabrics, pellet velocities and scanning rates are to be maintained within ranges that would not damage fabrics, since higher pellet velocities and/or lower scanning rates can lead to severe fabric damage.
In addition to conducting experiments on stained or soiled fabrics which had run in the field, trials were conducted on new or otherwise clean fabrics. Trials performed on new fabrics are useful in identifying operating conditions which will not damage the fabric. A list of the fabrics and example numbers is provided in Table 1.
TABLE 1______________________________________List of Fabrics Samples and Corresponding Example Numbers______________________________________ID New fabric Samples Example______________________________________P1 polyester (PET) woven fabric 1 and 2P2 polyester (PET) woven fabric 3P3 polyester (PET) woven fabric 3P4 polyester (PET) woven fabric 3PCTA5 polyester (PCTA) woven fabric 3 (copolyester of 1,4-cyclohexane dimethanol terephthalate) fabricPEEK6 (polyetheretherketone) woven 3 fabricP7 polyester (PET) woven fabric 3P8 polyester (PET) woven fabric 3PN9 polyester (PET)/nylon woven 3 fabricPN10 polyester (PET)/nylon woven 3 fabricPN11 polyester (PET)/nylon woven 3 fabricPT12 polyester (PET) woven fabric 5 coated with TeflonP13 polyester (PET) woven fabric 5PPS14 PPS (polyphenylenesulfide) fabric 5PM15 polyester/metal fabric (PET) 6______________________________________ Soiled Fabric Samples Example______________________________________SPNF10 Soiled polyester 3, 4 (PET)/nylon wovenSPNF9 Soiled polyester/nylon 4 fabricSPF16 Soiled PET fabric 4SPNF11 Soiled w/grease 4 PET/nylon fabricSPF17 Soiled PET fabric 4SNF18 Soiled nylon fabric 4SPNF19 Soiled polyester/nylon 5 fabricSPTF20 Soiled polyester fabric 5 with Teflon coatingSPF21 Soiled polyester fabric 5SPNF11 Soiled PET/nylon fabric 5SPNF10 Soiled PET/nylon fabric 5SPNF9 Soiled to PET/nylon 5 fabricSPF23 Soiled polyester fabric 5SPF24 Soiled polyester fabric 6SPF25 Soiled polyester fabric 6SPCTAF5 Soiled polyester 6 (copolyester of 1,4- cyclohexane dimethanol terephthalate) fabricSPCTAF26 Soiled polyester 6 (copolyester of 1,4- cyclohexane dimethanol terephthalate) fabricSPF28 Soiled polyester fabric 6SPF30 Soiled polyester fabric 6______________________________________
EXAMPLE 1
Long strips of fabric measuring approximately 1.25 m by 15 cm were scanned with the fabric length oriented to the scanning direction. Fabric samples used in the following examples were obtained from the Albany International Corp. Dryer Fabrics Division, and the Albany International Corp. Engineered Fabrics Division, Greenville, S.C. and Portland Tenn., respectively. A 1.25 m length of PET woven fabric of design P1 fabric was scanned at a rate of 12 mm per second. The distance between the cryoblaster and the fabric surface was 70 mm. Carbon dioxide pellets were delivered at a rate of 422 pounds per hour. The fabric was scanned in such a way that the pellet velocity was ramped downward from 1150 feet per second to 383 feet per second over the length of the fabric.
After the fabric was subjected to cryoblasting, it was examined for damage. Pellet velocities of 766 feet per second or less appeared to produce no damage, while velocities above 766 feet per second resulted in the fibrillation of monofilaments in the fabric. At the highest velocities (1150 feet per second), the monofilaments were fibrillated that the backside of the fabric resembled that of a felt structure. Pellet velocity of 766 feet per second (8000 rpm) at a scanning rate of 12 mm/sec results in fabric damage to P 1 fabric.
EXAMPLE 2
Scanning rate is another factor to consider. In this example, a sample of woven fabric of design P1 was subjected to cryoblasting at 8,000 rpm (766 feet per second). As in Example 1, long strips of the fabric measuring approximately 1.25 m by 15 cm were scanned with the fabric length oriented to the scanning direction. See FIG. 2. The scanning speed was varied via a step function providing scanning speeds of 120 mm per second, 96 mm per second, 72 mm per second, 48 mm per second, 36 mm per second, 24 mm per second, 18 mm per second, 12 mm per second, and 9 mm per second. For each scanning speed, a fixed length of 120 mm of fabric was cryoblasted. The solid carbon dioxide delivery rate for this experiment was 420 pounds per hour. Examination of the fabric showed that there was no damage to any piece of the fabric, including the portions scanned at the rate of 9 mm per second.
EXAMPLE 3
Several fabric samples were cut into strips approximately 15 cm in width. These strips were laid down adjacent to each other with the length of the strips normal to the scanning direction. See FIG. 3. In this way, the robot and cryoblaster could scan several pieces of each fabric and a sequence of scanning trials could be conducted wherein a new portion of the fabrics could be exposed with each pass. In other words, the cryoblaster could scan a row of fabric samples in a single scan. With each scan, a portion of the fabric is subjected to cryoblasting, while a vast majority of the fabric sample is unaffected.
The cryoblasted area of each fabric measured approximately 13 cm by 15 cm, with the 13 cm dimension corresponding to the length of the stream of pellets produced by the cryoblaster. Fifteen centimeters corresponds to the cut width of the fabric samples. After one scan trial was completed, the fabrics were examined, new experimental conditions were determined, and a second scan was conducted on an unexposed portion of the fabric samples. After the second scan was conducted, fabric samples were examined and new scanning conditions were determined for a third scan. The scanning trials did not exceed four in total and in most cases were limited to two or three scanning trials.
Ten (10) samples of new fabrics were tested. The purpose of scanning new fabrics was to determine the relative levels of damage which might occur to the fabrics, based upon the material comprising the fabric or the structure of the fabric. The fabric samples consisted of PET woven fabrics P2, P3, P4, P7, P8, PET/nylon woven fabrics PN9, PN10, PN11, PCTA woven fabric PCTA5, PEEK woven fabric PEEK6.
The first scanning trial was conducted at a scanning rate of 6 mm per second and a pellet velocity of 766 feet per second (8,000 rpm). The pellet production rate was 256 pounds per hour.
The polyester woven fabric P2 exhibited warp and shute damage. The backside of the fabric exhibited a pattern corresponding to the pattern of the metal grid holding the fabric in place during the trial. PET woven fabric P3 exhibited damage where the metal grid supported the fabric. As with the first fabric, this produced a pattern of damage in the fabric which corresponded to the metal grid supporting the fabric. Polyester woven fabric P4 exhibited extensive damage. The warps were disintegrated leaving behind only the shute filaments. The PCTA woven fabric PCTA5 exhibited slight fracture in the warp strands. The PEEK woven fabric PEEK6 was undamaged. PET woven fabric P7 exhibited slight damage. PET woven fabric P8 exhibited light damage to the warp strands. PET/Nylon woven fabric PN9 exhibited damage to the polyester shutes. PET/nylon woven fabrics PN10 and PN11 exhibited damage to the warps. It has been found that the pattern of damage corresponding to the metal support in fabric designs P3 and P4 can be avoided by removing the metal grid and tensioning the fabric between two or more supports.
Based upon the results of the first scan, a second scan was conducted at a scanning rate of 120 mm per second. The rotational speed of the cryoblaster was maintained at 8,000 rpm (766 feet per second). The pellet production rate was 295 pounds per hour. After the second scan, PET woven fabric P2 and PET woven fabric P4 exhibited warp fibrillation where they were supported by the metal grid. All of the remaining fabrics were undamaged.
A third scan was conducted at a scanning rate of 120 mm per second. The cryoblaster was controlled to a speed of 6,000 rpm (575 feet per second). The pellet production rate was 185 pounds per hour. A new fabric sample was added to the group of ten fabrics bringing the total size of the group to 11 fabrics. This eleventh fabric was a soiled PET/nylon woven fabric SPNF10 which was the first soiled fabric sample to be subjected to cryoblasting in this trial. Cryogenic scanning did not result in damage to any of the fabric samples. The soiled PET/nylon woven fabric SPNF10 appeared to be cleaner in the area that had been scanned by the cryoblaster.
A fourth scan was conducted. This scan was conducted at a scanning speed of 6 mm per second with the cryoblaster operating at 6,000 rpm (575 ft/sec) and the pellet production at 187 pounds per hour. Fabric P2 exhibited light damage, fabric P3 exhibited damage where the fabric was supported by the metal grid, and fabric P4 had extensive damage. The remaining fabric samples appeared to be undamaged, except for the soiled PET/nylon woven fabric SPNF10 which exhibited a slight pattern of damage where the fabric was supported by the metal grid. The soiled PET/nylon woven fabric SPNF10 was considerably cleaner in the area which had been scanned.
From this example it would appear that a scan rate of 6 mm/sec and a pellet velocity of 766 ft/sec is generally unacceptable and damages most fabrics. However, results improve when the scan rate is maintained at 6 mm/sec while lowering pellet velocity, as most fabrics are undamaged.
It is noted that some instances of damage are due not to direct impact between the pellets and fabric, but are due to contact with the fabric and the backside metal support.
PET woven fabric P4 appeared to be particularly susceptible to damage when subjected to cryogenic treatment
EXAMPLE 4
A series of soiled fabrics were mounted for scanning trials in the manner of Example 3. These fabrics included PET/nylon woven fabrics SPNF9, SPNF10, SPNF11, PET woven fabrics SPF16, SPF17 and nylon woven fabric SNF18. These fabrics were obtained after running in the field during the production of paper and nonwoven products. For the first scan, the cryoblaster was operated at a speed of 6,000 rpm, 575 ft/sec! a scanning rate of 120 mm per second, and a pellet production rate of 184 pounds per hour. After the first scan, PET woven fabric SPF16 and PET/nylon woven fabric SPNF10 were observed to be cleaner. The rest of the fabrics were relatively unaffected by the cryoblasting treatment.
A second scan was performed over the same area as the first scan. The scanning rate was now changed to 12 mm per second. The cryoblaster speed was 6,000 rpm and the pellet production rate was 167 pounds per hour. After this scan, all of the fabrics appeared to be much cleaner.
Photographs showing the effect of cryoblasting on fabrics SPNF9, SPF16, SPNF11, SPNF10, and SPF17 are shown in FIGS. 4A, 4B, 5A, 5B, 6A, 6B, 7A, 7B, respectively, with the "A" photographs showing the fabrics before cleaning and the "B" photographs showing the fabrics after cleaning. It is evident from the photos that surface contaminants have been removed by the treatment and the fabrics are much cleaner as a result. SPNF11 is a PET/nylon fabric soiled with grease. The figures evidence that the treatment proved effective at grease removal.
PET woven fabric of design SPF17 was originally contaminated with fibers. See FIG. 7A. The fibers on this fabric have been raised from the surface of the fabric via cryoblasting. This produced a fuzzy surface on the fabric. We found that these fibers could be easily removed by grabbing the fibers and pulling them away from the surface of the fabric. After doing so, this area of the fabric was very clean.
A third scan was performed at a scanning rate of 36 mm/second on a new zone of the fabric samples. The cryoblaster was operated at 6,000 rpm and the pellet production rate was 180 pounds per hour. After this scan, all the fabric samples were cleaner. PET woven fabrics SPF16, SPF17 were very clean.
An image analysis of the surface of PET woven fabric SPF16 (FIGS. 5A and 5B) were made from the photographs of the two scans of the fabric surface before and after cryoblasting. These images were subjected to a Fourier transform to create a Fourier transform image. An inverse Fourier transform image was then created from the fourier transform image. Cross enhancement was then performed on the inverse Fourier transform image. This results in an image in which dirt particles are only visible and appear as white pixels. Counting the white pixels in each image (equal areas) and calculating the ratio of white pixels before and after cleaning yields a cleaning factor which is a quantitative measure of the cleaning effectiveness. The cleaning factor for PET woven fabric SPF16 was 14.5. This cleaning factor indicates that the fabric was contaminated to a level 14.5 times greater before cryoblasting than after cryoblasting.
EXAMPLE 5
The fabric samples subjected to cleaning via cryoblasting were: soiled PET/nylon fabrics SPNF9, SPNF10, SPNF11, new or unsoiled PET fabric coated with Teflon PT12, new or unsoiled PET woven fabric P13, new or unsoiled PPS fabric PPS14, soiled PET woven fabrics SPTF20, SPF21, and SPF23. On the first scan, the cryoblaster was operated at a speed of 6,000 rpm with a scanning rate of 12 mm per second and a pellet production rate of 178 pounds per hour. After the first scan, the contaminated fabric samples were cleaner. New PET woven fabric woven fabric P13 and new PPS woven fabric PPS14 were not damaged by cryoblasting except that new PET woven fabric P13 shows slight fiber damage in these areas where it was supported by the metal grid.
Photographs showing the effect of cryoblasting on selected samples are shown in FIGS. 8A, 8B, 9A, 9B, 10A, 10B, 11A and 11B. FIGS. 8A, 8B, 9A, and 9B show the cleaning effect of cryoblasting for fabric SPNF19. It is evident that the fabric is cleaner on its top and its bottom as a result of the treatment, even though it is treated on only the top side of the fabric.
As with Example 4, image analysis was performed to determine the cleaning factor for soiled PET woven fabric (SPF21, FIGS. 10A, 10B, 11A, and 11B). The cleaning factor for the top side of this fabric was 4.4. The figures show that the fabric is cleaner on both sides although it is treated only on the top side.
EXAMPLE 6
The following group of soiled fabrics of designs SPF24, SPF25, SPF30, SPF28, soiled PCTA woven fabrics SPCTAF5 and SPCTAF26, and new, unsoiled PET/metal fabric PM15 were treated as disclosed herein. The first scan was performed at a scanning rate of 12 mm per second and a cryoblaster speed of 6,000 rpm. The pellet production rate was 175 pounds per hour. After the first scan, all of the fabrics were substantially cleaner. Photographs showing fabric surfaces for samples before and after cryoblasting can be found in FIGS. 12A, 12B, 13A, 13B, 14A and 14B. Some debris on the fabric surface arose from fiber dust being blown onto the fabric from the air turbulence created by the cryoblaster. This dust is an artifact and is debris resulting from damage to fabrics subjected to severe cyroblasting conditions in this and prior examples. The fiber dust is easily removed by vacuum.
PET woven fabric SPF30 was damaged by cryoblasting. This damage is probably related to prior hydrolysis of the PET fabric resulting in reduction of monofilament integrity. There was very slight damage to the unsoiled PET/metal fabric PM15. A second scan was performed at a cryoblaster speed of 6,000 rpm and a scanning rate of 6 mm per second. The pellet production rate was 161 pounds per hour. In this scan, all fabrics were scanned over a zone containing a soil. All of the soiled samples were considerably cleaner. PET woven fabric SPF30 was significantly damaged. PET/metal fabric PM15 exhibited slight damage to the warp.
As with Examples 4 and 5 image analysis was performed to determine the cleaning factor for soiled PET woven fabric SPF28, shown in FIGS. 13A, 13B. The cleaning factor for this fabric was 22.6.
Permeability measurements were made on each dryer fabric sample to compare permeability of dirty and clean areas. The results which are shown in Table 2. The permeability data presented in this table distinguishes between soiled fabrics that are plugged, and soiled fabrics that are not plugged. Where a fabric is not plugged, fabric only has dirt upon its surface, and the holes and interstices of the fabric are not filled with soil. The permeability reduction of fabrics soiled in this way relative to new fabrics is not noticeably large. However, when a fabric is plugged, the filling of the holes causes a substantial drop in permeability.
After cryoblasting, both plugged and unplugged fabrics exhibit an increase in permeability. However, the change in permeability for a plugged fabric is dramatic.
PET woven fabric SPF28 and (see FIGS. 13A, 13B) exhibits a much higher permeability after cleaning. This permeability increase appears to correspond with the photographs, wherein the treated fabric is observed as having a higher degree of openness. That is, FIGS. 13A and 13B show that the material that plugged the untreated fabric has been removed after cryoblasting. Other fabrics exhibit small increases in permeability, which is indicative that the soiling material was located on the surface of the filaments and not plugging spaces between the filaments. That is, these fabrics were not plugged.
It has been found that cryoblasting is very effective either on line at a paper mill (or similar facility) or off line at a facility for refurbishing soiled fabrics. Cryoblasting has potential to clean fabrics for effective recycling of raw materials used to produce the fabrics.
TABLE 2__________________________________________________________________________Permeability Measurement Before and After Cryoblasting Permeability Permeability After Before CryoblastingFabric Sample ID Cryoblasting (CFM) Comments__________________________________________________________________________PET woven fabric (SPF28) 89 139 Plugged holes clearedPCTA woven fabric (SPCTAF5) 391 421 No plugging; surface dirtPET woven fabric (SPF30) 425 336 Material was hydrolyzed or degraded; cleaning fibrillated the monofilaments, plugged the fabric and decreased permeabilityPET woven fabric (SPF25) 84 88 No plugging; surface dirtPET woven fabric (SPF24) 51 57 No plugging; surface dirt__________________________________________________________________________ Fabrics were cleaned with 1 pass (6 mm/s @ 6000 rpm). | The present invention provides a method of removing contaminants from industrial process fabrics relying upon cryogenic techniques, wherein the fabric is impacted with solid particles of carbon dioxide. A cryoblaster projects the carbon dioxide particles at the fabric. The cryoblaster scans over the entirety of the fabric at a scanning rate particle velocity, and particle flow rate in order to insure that the fabric is cleaned without suffering any damage. | 3 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This U.S. Utility Application claims priority pursuant to 35 U.S.C. §119(e) to the following U.S. Provisional Patent Application, the specification of which is incorporated herein by reference for all purposes: U.S. Provisional Application Ser. No. 61/608,915, titled “Method and Processes for Improved Frac Drilling Operations,” filed Mar. 9, 2012, pending.
TECHNICAL FIELD
[0002] A remotely operated system for the purpose of safely and cost-effectively conducting hydraulic fracturing of ground formations and method of using same is disclosed. In particular, a system and method utilizing a remotely operated system of ground valves disposed between fracturing equipment and a well bore, is set forth.
BACKGROUND OF THE INVENTION
[0003] Induced hydraulic fracturing, commonly known as fracking is a technique used to release petroleum, natural gas, or other substances for extraction by utilizing pressurized fluid such as water, brine, foam or the like which fluid breaks or fractures the oil or gas producing strata down the well. Although hydraulic fracturing operations take a relatively short amount of time to complete, the process may be repeated multiple times in “stages” to reach maximum areas of the wellbore. When this is done, the wellbore is temporarily plugged between each stage to maintain the highest pressure possible to get the maximum fracturing result.
[0004] During the fracturing process, pressurized fluid also called a fracturing slurry is often introduced in excess of 7,500 psi in order to cause the rock formations down the well to fracture. Pressures of the magnitude found in hydraulic fracturing processes can usually be tolerated by the well tubing or casing, which extends downwardly from ground level into the wall. However, the valves which are placed at the well head to form a well tree (Charismas Tree) are often not capable of containing such pressures, which may cause a blow-up or rupture of the well head, severe damage to the well itself and the fracturing equipment placed nearby.
[0005] In an effort to contain damage to the fracturing equipment (being a source of pressurized fluid) in a blow-up condition, in addition to a high-pressure valves usually disposed over the Christmas Tree, operators of the hydraulic fracturing equipment utilize manually operated ground valves disposed within the flow lines, which connect the fracturing equipment (e.g. fracturing manifold) with the well head. The valves are manually operated plug and/or block style ground/gate valves also known as fracturing relay valves or fracturing control valves; their primary function is to control the flow of the pressurized fluid pumped by the fracturing pumps to the well casing. Such valves are designed to operate as one-way valves, passing the pressurized fluid from the higher pressure area to the lower pressure-area. Between each stage being completed during the fracturing operation, the valves are manually operated (closed) to prevent further flow of the pressurized fluid while the wellbore is temporarily plugged for future production.
[0006] The manually operated ground valves, however, have proven unsafe and inefficient for the reasons explained below. First, in a blow-up of the well, the manually controlled valves are in a “Danger Zone,” an area of high probability of injury occurring due to the flying debris from the dismantling well. If the field personnel are caught around the valves while attempting to manually stop the flow of the fracturing slurry between the stages of the fracturing operation, that person inevitably is exposed to a grave injury. If the person is outside the Danger Zone at the time of ensuing blow-up, it will not be safe to walk up to the ground valves to manually turn the handweel of the valve in order to prevent further damage to the fracturing equipment. Severe injuries and fatalities are not uncommon when manually operated ground valves are utilized.
[0007] The fluids introduced into the well are not only highly pressurized but are generally corrosive and abrasive because they are frequently laden with corrosive acids and abrasive propellants such as sharp sand, shale, coal or the like. In addition to dangers related to manually controlled ground valves, the presently used in the industry ground valves suffer from a number of significant disadvantages due to the known condition called “bleeding back” during which the pressurized fracturing slurry backs up to the fracturing equipment and causes the ground valves to be exposed to the abrasive fluid.
[0008] Traditionally utilized plug and/or block valves are one-way valves, having Teflon ball and seat design of the seal, which does not completely seal the cavity of the valve's body causing the valve to relatively quickly pack full with sand and debris (wash out), and become extremely difficult, if not impossible to operate due to buckling up during normal fracking. This makes the valve impossible to turn. When in a fully open position, the plug and/or block style valves are not capable of securing a tied seal between the Teflon ball and the seat causing the abrasive and pressurized fluid, sand and other undesirable debris to freely enter the cavity of the valve's body during bleeding back, making the valve eventually inoperable and necessary to replace.
[0009] Further, a flow-T connector of a Zipper Manifold for selectively servicing two or more wells typically disposed between s source of pressurized fluid and the well head, receives the fracturing slurry at 90 degree angle, causing further damage to the ground valves positioned in each outlet of the flow-T connector for selectively isolating the fracturing slurry, and the damage to downstream components.
[0010] Manually controlled plug and/or block type ground valves operating life time is approximately 60 to 70 operational hours, or an average of only 35 to 40 stages of fracturing operation before incurring downtime and loss of productivity. In addition to an unscheduled stoppage of fracturing operation, the replacement becomes cost-prohibitive, if the valves have to be replaced more frequently than their normal operable life time.
[0011] With the use of manually operated ground valves, the breaks between each stage of fracturing operation are further augmented due to the loss of fracturing pumps “prime.” The fracturing pumps utilized in the industry are of pressurized operational design. If the pumps are not pumping fluid with an applied pressure to do so, they lose their prime and will become desynchronized with one another, rendering the pump inoperable and, ultimately, unable to pump. The loss of the pump prime occurs during the fracturing process after each and every stage, while transitioning/shutting down pumps using manually operated ground valves in order to begin the wire line operations.
[0012] Downtime related to the breaks taken between the fracturing stages to open or close the manually controlled ground valves aggregate to an average of approximately 45 minutes every 2-2½ hours of uninterrupted operation of each fracturing stage. Overall, during the 24 hour period of fracturing operation, the down time related to the breaks in stages totals approximately 5 to 6 hours of stoppage where no production activity takes place.
[0013] Accordingly, there is a need for safer and cost-effective fracturing system and method that does not use manually operated plug and/or block type valves. There is also a need for a fracturing method that does not create life threatening conditions and cause injuries to field personnel related to operation of manual ground valves. There is also further need for fracturing method that increases productivity of the well by avoiding the downtime caused by unnecessary repairs and/or replacement of the manually operated valves. It is a further object of the invention to provide such a system which can be disassembled for carrying from place to place, and which can be assembled relatively easily on the site. Thus, there is a need for a remotely operated system and method, which is safer to operate, prolong the average of operational hours for said system and brings the well to a faster and continued production.
SUMMARY OF THE INVENTION
[0014] The embodiments of the present disclosure alleviate to a great extend the disadvantages of using manually operated ground valves disposed within the flow lines, connecting fracturing equipment and the well bore by providing a remotely controlled ground valves which are actuated by an accumulator positioned outside the Danger Zone, thus enhancing the safety and eliminating the down time related to fracturing stages.
[0015] A remotely controlled system operated outside the Danger Zone and method disclosed herein is a field tested system and method that replaces the traditional manually operated, plug and/or block style ground valves currently used throughout the fracturing industry. The remote operation of the ground valves eliminates injury to the field personnel.
[0016] A remotely controlled ground valve system being disposed within the flow lines, connecting the fracturing equipment (being a source of pressurized fluid) and the well head includes at least three (3) ground valves, having preferably metal-to-metal, gate and seat seal design for securing adequate seal in an open position, having dual sided-flow and capability of containing a dual sided pressure from both ports of entry. The at least three (3) ground valves are connected through the inlet and outlet line of each valve, respectively, with one or more high pressure hose(s) and actuated by an accumulator being powered by any means of energy source such as electrical, diesel, pneumatic or hydraulic, wind, or any other available energy source. The accumulator is positioned outside the Danger Zone, which in relation to the remotely controlled valves is approximately up to 150 feet from the closest of the ground valves and up to 200 feet from the furthest of the ground valves.
[0017] The utilization of the system (as tested in the field) increases the operational duration of the remotely controlled ground valves from approximately 60-70 operational hours, which equates to approximately 40-45 stages of fracturing operation to approximately 5,300 hours, which translates to an average of over 3,500 completed stages without a moment of down-time.
[0018] According to one embodiment of the present disclosure, the system includes one or more high pressure hose(s) which deliver pressured substances to actuate the ground valves. In preferred embodiment of the present disclosure, each valve is operated separately. For instance, a first valve in the system may be actuated by the accumulator and opened, while a second and third valve may be actuated to a position of closed. Such independent control provided to the ground valves by the accumulator's controls allows continued fracturing as long as at least one valve is fully operational (capable to be fully opened or fully closed). Yet, in another embodiment, the ground valves can be actuated in-sync and, thus, opened/closed simultaneously.
[0019] Yet, another advantage of the present invention is that the accumulator's controls may be operated manually or may be programmed to operate and function automatically from a control office or anywhere in the field by reversibly remotely actuated a transmitter/receiver set of the type commonly used for opening and closing garage doors from a hand held unit.
[0020] According to one embodiment of the present disclosure, the system comprises a Zipper Manifold for selectively servicing two or more wells, said Zipper Manifold connecting the fracturing equipment with each of the servicing well head, wherein said Zipper Manifold comprises a flow-T connector, wherein the fracturing slurry reaches said flow-T connector at approximately 45 degree angle, thus reducing velocity of the slurry and an erosion of the valves positioned in each outlet of the flow-T connector and the downstream components, said system of valves comprising at least two (2) remotely operated ground valves disposed within the flow lines on both ends of the flow-T connector and at least two (2) manually operated ground valves positioned downstream of the at least two (2) remotely operated ground valves.
[0021] According to one embodiment of the present disclosure, the remotely controlled at least two (2) ground valves of the Zipper Manifold may be operated by a separate accumulator unit or, by the same accumulator unit as the at least three (3) ground valves discussed above. If the at least two (2) remotely controlled valves are operated by the separate accumulator unit, said accumulator is preferably positioned outside the Danger Zone.
[0022] Exemplary embodiments further include a method of fracturing subterranean formations, comprising: disposing at least three (3) ground valves within a flow lines, wherein said flow lines connect s source of pressurized fluid (e.g. fracturing manifold) with the goat head of the well bore; connecting said at least three (3) ground valves through their respective inlet/outlet lines with one or more high pressure hose(s); connecting said high pressure hoses with an accumulator, wherein said accumulator is positioned in relation to said valves at approximately up to 150 feet from the closest and at approximately up to 200 feet from the furthest ground valve; placing the accumulator's controls in an open position to remotely open said valves, wherein a fracturing slurry can pass freely through the flow lines; and after each stage of fracturing is completed, placing each said valve in a closed position.
[0023] Exemplary methods may further comprise placing of Zipper Manifold with a flow lines, said Zipper Manifold comprising: a flow-T connector, wherein a fracturing slurry is received at approximately 45 degree angle; at least two (2) remotely operated ground valves, wherein each valve is disposed on each end of the flow-T connector and wherein each valve is individually controlled by an accumulator's controls, said accumulator placed outside the Danger Zone; and at least two (2) manually controlled ground valves, said valves disposed downstream of the remotely controlled at least two (2) ground valves of the Zipper Manifold.
[0024] According to one embodiment of the present disclosure the system disclosed herein is externally oiled before the system is commissioned to maintain its longevity. It is also the object of the present invention to provide the system, wherein when interior parts have been compromised or damaged, the system is configured to still safely continue operations, allowing the user the flexibility and time required to safely and cost-effectively make alternative decisions and adjustments to the system.
[0025] Although this system has been developed to improve safety and effectiveness of the fracturing operation in an oil and gas wells, it may also find application in a programs for stimulating gas drainage from coal mines and in stimulating water wells for domestic, agricultural or industrial use or for other purposes when it is desirable to inject a particulate material with the fracturing fluid under relatively high pressure.
[0026] The principals of the invention will be further discussed with reference to the drawing(s) wherein a preferred embodiment is shown. The specifics illustrated in the drawings are intended to exemplify, rather than limit aspects of the invention as defined in the claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0027] For a more complete understanding, reference is now made to the following description taken in conjunction with the accompanying drawings in which:
[0028] FIG. 1 is a schematic representation of prior art solution depicting fracturing operation with the use of manually operated ground valves and the showing of an area depicting a Danger Zone during the fracturing operation.
[0029] FIG. 2A is a diagrammatic representation of a typical fracturing layout according to embodiments of the present disclosure.
[0030] FIG. 2B is a simplified diagrammatic representation of the Zipper Manifold according to embodiments of the present disclosure.
[0031] FIG. 3 is a detailed representation of the system of FIG. 2A according to embodiments of the present disclosure.
[0032] FIG. 4 depicts a typical ground valve according to one embodiment of the present disclosure.
[0033] FIG. 5 is a flow chart illustrating an exemplary method of conducting safe and cost-effective fracturing operation according to embodiments of the present disclosure.
DETAILED DESCRIPTION
[0034] Referring now to the drawings, wherein like reference numbers are used herein to designate like elements throughout, the various views and embodiments of a remotely operated system and method of using same for the purpose of safely and cost-effectively conducting fracturing of the subterranean formations are illustrated and described, and other possible embodiments are described. The figures are not necessarily drawn to scale, and in some instances the drawings have been exaggerated and/or simplified in places for illustrative purposes only. One of ordinary skill in the art will appreciate the many possible applications and variations based on the following examples of possible embodiments. As used herein, the “present disclosure” refers to any one of the embodiments described herein, and any equivalents. Furthermore, reference to various aspects of the disclosure throughout this document does not mean that all claimed embodiments or methods must include the referenced aspects.
[0035] FIG. 1 is a schematic representation of a fracturing operation layout often referred to as fracturing field known to a prior art. A typical fracturing field 10 utilizes a variety of equipment and comprises: a wellhead 20 connected through a flow lines 30 with a source of pressurized fluid comprising: a fracturing manifold 40 , said fracturing manifold 40 , connected to a fracturing pumps 50 , said pumps receiving proppant (fracturing slurry consisting of water, sand, gel and other additives utilized in hydraulic operations) through a blender 60 being connected to a hydration unit 70 , a chemical unit 80 and a sand storage tanks 90 and a fluid storage tank 100 . Further in FIG. 1 are depicted at least three (3) ground valves 110 ( 4 shown in the drawings) also known in the fracturing industry as fracking relay valves, gate valves, or a flow control valves disposed within the flow lines 30 , said valves controlling the flow of the fracturing slurry during each stage of the fracturing and being operated manually by the field personnel. As known in prior art, the at least three (3) ground valves 110 are disposed within the flow lines 30 and may be connected with a flow-T connector of the Zipper Manifold (not shown in the drawing), receiving the fracturing slurry through the flow lines 30 at the 90 degree angle.
[0036] FIG. 1 further shows an area 120 depicting a Danger Zone identified in a fracturing field. The Danger Zone 120 covers an area where injuries are likely to occur during the blow-up condition of the well head not being able to contain the pressure. The Danger Zone may be described as an area covering the entire location of the fracturing field and include all on-site associated areas in which fracturing operations are taking place, and having dimensions marked by the outline, and/or outermost boundaries of the equipment footprint designated to be either directly or indirectly involved with and associated with the fracturing process as per FIG. 1 Typically, an area commonly established on the fracturing well-site would be as follows: up to 100 feet radius from the actual well-head/well-bore and approximately 15 feet radius from all outer lying associated equipment. Personnel attempting to close or open the manual ground valves 110 , may be stranded on the field, thus being exposed to injuries and even death by striking debris of a dismantling well bore's components in a blow-up condition.
[0037] Furthermore, the manually controlled ground valves presently used in the industry are plug/block style, one-way valves. An inadequate Teflon ball and seat design of the seal, cause the valves to be frequently packed with sand, debris during the bleeding back of the fracturing slurry, causing substantial damage to the body of the valve's cavity and necessitating frequent replacement.
[0038] By eliminating manual operation of the ground valves by the field personnel and, replacing them with a remotely operated metal-to-metal, gate and seat seal design, the danger of injuries and a loss of life on a fracturing field has been greatly eliminated.
[0039] Furthermore, by utilization of a ground valves having metal-to-metal, gate and seat seal design, a dual sided flow and pressure control is maintained throughout the entire fracturing operation. Since the fracturing operation is conducted in stages, the remotely controlled ground valves are operable to be almost instantly turned to close or open between the stages of each fracturing operation. Typically, with the manually controlled valves it takes approximately 45 minutes for the personnel to close (or open) the valves. This 45 minutes break does not take into an account the situation where the valves are washed out and no longer operable, thus have to be replaced. There is a significant shortage of plug/block style valves, causing the breaks to be even longer before the new valve could arrive.
[0040] Turning now to FIGS. 2A and 2B , according to embodiments of the present disclosure, a system 200 is used in conjunction with fracturing operation 10 to safely and cost effectively conduct a fracturing of subterranean formation. As used herein, the system 200 comprises at least three (3) remotely controlled ground valves 210 ( 4 valves are shown in a drawing) disposed over the flow lines 30 and being actuated by an accumulator 220 , said accumulator connected with said valves 210 through one or more high pressure hose(s) 230 pushing high pressure substance (e.g. liquid or gas) and operable to independently control each ground valve through the accumulator's controllers (as shown in FIG. 3 ) designated for each ground valve.
[0041] FIG. 2B shows a simplified diagrammatic view of the general fracturing field 10 according to embodiments of the present disclosure depicting Zipper Manifold 260 for selectively servicing two or more wells, having a flow-T connector 240 designed to receive the fracturing slurry at approximately 45 degree angle, thus reducing velocity in the outlets, which reduces erosion to the system of valves and the downstream components, said system of valves comprising at least two (2) remotely operated ground valves 280 disposed on both ends of the flow-T connector 240 and at least two (2) manually operated ground valves 300 following downstream the at least two (2) remotely operated ground valves 280 .
[0042] According to one embodiment of the present disclosure, the remotely operated at least two (2) ground valves 280 of the Zipper Manifold may be controlled by a separate accumulator unit 220 , or by the same accumulator unit 220 as the at least three (3) ground valves 210 ( FIG. 2A ) discussed above (not shown in FIG. 2B ). If the at least two (2) remotely controlled valves 280 are operated by the separate (from the accumulator operating valves 210 , FIG. 2A ) accumulator unit 220 , said accumulator is preferably positioned outside the Danger Zone 120 ( FIG. 1 ). This variation in embodiments of the present disclosure will become apparent to those skilled in the art upon further examination of the drawings, or may be learned by practice of the invention.
[0043] FIG. 3 is a detailed representation of system 200 in FIG. 2A according to one embodiment of the present disclosure. In FIG. 3 , at least three (3) (4 valves shown 12′-18′) ground/gate valves, ranging from 5,000 to 20,000 psi working pressure capabilities may be utilized. The exemplary ground valve 12 ′ is shown in FIG. 4 and may be of any commercially available brand or make. The recommended ground valves to practice the invention are a hydraulic gate valves of Cameron FC, FETE, EE trim as depicted in FIG. 4 . The ground valves 12 ′ through 18 ′ are disposed within the flow lines 30 ( FIG. 3 ), said flow lines 30 connecting fracturing manifold 40 with a goat head 22 directly seating on the Christmas Tree of the well head 20 ( FIG. 1 ). Exemplary flow lines may be 3″ or 4″ 1502 flow iron line. Exemplary ground valves 12 ′ through 18 ′ shown in FIG. 3 are independently actuated (controlled) through an accumulator's controls 12 through 18 . The independent control of every ground valve through an accumulator's controls, allows for continued fracturing operation as long as at least one ground valve of the system is fully operational (capable of being fully closed and fully opened).
[0044] According to one embodiment of the present disclosure, the ground valves may have their usual manual actuator (such as handweel or lever on its stem) supplemented by the hydraulic accumulator capable of actuating the ground valves, said hydraulic accumulator powered by any available energy source.
[0045] Suitable accumulator 220 ( FIG. 3 ) utilized to operate remotely the ground valves 12 ′- 18 ′ may be 4-station with 4 pressure bottles, diesel, pneumatic, hydraulic or electric. As an example, a 4 station hydraulic accumulator withstanding at least 3500 psi of Meyer brand may be used. In accordance with one embodiment of the present disclosure, said accumulator 220 , having 4 accumulator's controls (stations), 12 - 18 ( FIG. 3 ), each station operable independently to actuate at least three (3) ground valves (4 valves shown in FIG. 3 ) 12 ′ through 18 ′, respectively. The accumulator 220 is configured to remotely control said ground valves, 12 ′ through 18 ′ and is positioned outside the Danger Zone 120 as illustrated in FIG. 1 .
[0046] In different embodiments, the components of system 200 of FIG. 2A and the Zipper Manifold 260 in FIG. 2B may be combined together (not shown in the drawings) such that the at least three (3) remotely controlled ground valves 210 may be disposed within the flow lines 30 between a source of pressurized fracturing fluid (e.g. fracturing manifold) and the Zipper Manifold 260 ( FIG. 2B ), said at least three (3) ground valves 210 and at least two (2) ground valves 280 of the Zipper Manifold 260 controlled by different accumulator units, said units positioned outside the Danger Zone. In other variations, if combined with the Zipper Manifold 260 , the ground valves 210 of system 200 ( FIG. 2A ), may be disposed within the flow lines 30 and controlled by the same accumulator unit as the at least two (2) remotely operated valves 280 of the Zipper Manifold 260 ( FIG. 2B ), said accumulator unit positioned outside the Danger Zone.
[0047] FIG. 4 illustrates an exemplary valve 12 ′ according to one embodiment of the present disclosure. An inlet 410 and outlet 420 lines allow the high pressured substance (e.g. fluid or gas) to control closing or opening of the vales, the exemplary valve 12 ′ having: a hydraulic cylinder 430 , a hydraulic piston 440 , a 70 dura o′rings 450 , a hydraulic stem 460 , a body bushing and seat 470 , a seat/gate guide 480 , a bonnet seal ring 500 , a type ‘U’ packing 510 , a metal to metal seal gate 520 , a packing retainer nut 530 , a tail/balance stem 540 , and a tail stem housing 550 .
[0048] According to embodiments of the present disclosure, the accumulator is removed from the Danger Zone and placed in relation to the ground valves of system 200 ( FIG. 2A ) at the distance of approximately up to 150 feet from the closest ground valve 16 ′ disposed within the flow line 30 ( FIG. 3 ) and as far as approximately up to 200 feet from the farthest ground valve 14 ′ disposed within the flow line 30 ( FIG. 3 ). A remotely positioned accumulator 220 eliminates the need of a field personnel directly operating ground valves 12 ′ through 18 ′ ( FIG. 3 ) and at the same time eliminates any proximity of the personnel to the Danger Zone. The accumulator may be operated through a manually controlled system of the accumulator's controls 12 through 18 , or the accumulator's controls may be actuated by a transmitter/receiver set of the type commonly used for opening and closing garage doors from a small unit such as may be hand held (not shown on the drawings).
[0049] According to one embodiment of the present disclosure, the system utilizes one or more high pressure hose(s) 230 ( FIG. 3 ) of the length up to 200 ft and ½″ to 2″ in diameter and of at least 6,000 psi pressure capabilities. Said high pressure hoses 230 may be hydraulic or pneumatic and connect the ground valves 12 ′ through 18 ′ with the accumulator 220 , said ground valves 12 - 18 ′ being remotely opened or closed through the move of a high pressure substance (e.g. fluid or gas), said move of the high pressure substance controlled by said accumulator 220 .
[0050] Referring now to FIG. 5 , there is illustrated a simplified diagrammatic view of the process flow 500 using system 200 as detailed in FIG. 3 , hereinabove, comprising: disposing at least three (3) ground valves within a flow line, said flow line connecting a source of pressurized fluid with a well head Block 502 ; connecting said the at least 3 ground valves through said valves' inlet and outlet line with one or more high pressure hose(s) Block 504 ; connecting said one or more high pressure hose(s) with an accumulator, said accumulator having at least three (3) accumulator's controls, wherein said accumulator is positioned in relation to the at least three (3) ground valves at approximately up to 150 feet from the closest of said valves and at approximately up to 200 feet from the furthest of said ground valves Block 506 ; before directing a fracturing slurry from a source of pressurized fluid (e.g. fracturing manifold) through a flow line, placing said accumulator's controls in an open position to remotely open each of the at least three (3) ground valves to allow said fracturing slurry to pass through each of the opened ground valve Block 508 ; after each fracturing stage is completed, placing said accumulator's controls for each said ground valve in a close position to stop the flow of the fracturing slurry Block 510 .
[0051] It should be understood that the drawings and detailed description herein are to be regarded in an illustrative rather than a restrictive manner, and are not intended to be limiting to the particular forms and examples disclosed. On the contrary, included are any further modifications, changes, rearrangements, substitutions, alternatives, design choices, and embodiments apparent to those of ordinary skill in the art, without departing from the spirit and scope hereof, as defined by the following claims. Thus, it is intended that the following claims be interpreted to embrace all such further modifications, changes, rearrangements, substitutions, alternatives, design choices, and embodiments. | The purpose of this invention is to improve on the safety and to allow more efficient production of subterranean formation during fracturing operations with a reduced down-time, minimal supervision and maintenance expense by utilizing remotely operated ground valves having metal-to-metal, gate and seat seal design operable to maintain a dual sided flow and pressure control. Use of a new 45-degree flow-T connector of a Zipper Manifold in combination with the system described is particularly useful for reducing erosion with proppant-laden fracturing fluid. | 4 |
BACKGROUND OF THE INVENTION
(1) Field of the Invention
Innovations disclosed by the present invention relate to the protection of a computer software product from unfair use on more than one customer system. This invention is based on the use of a protection file that contains internalized attributes that characterize a specific customer system environment. The protection file is encrypted and contains a digest, so that attempts to convert a protection file for use on another system are futile. Programs within the product distributor's software product interrogate the protection file to determine if the internalized attributes correspond with the attributes of the prevailing system environment. The protection file is either prepared on the product distributor's system, or is prepared by special programs that operate on the customer's system. These special programs are contained within an encrypted composite file. At any moment, no more than one of the special programs that participate in protection file preparation is decrypted. Thus, attempts to reverse engineer the process that prepares the protection file are futile.
(2) Description of the Related Art
Various-strategies are used to prevent unfair use of software products today.
The most common technique uses a key, which is a series of characters, that is typed during product installation. Often this key does not contain information regarding the customer's system environment, and the product can be installed on other systems by typing the key during installation there as well.
Another method prepares a special key file (license) that is stored on customer systems, so that the product is only operable if the license is present. However, this method fails if the software is copied to another system, and the license is copied to that system as well; i.e. the license file does not contain information regarding the attributes of a specific system.
Another method uses an electronic device, called a ‘dongle’, that is attached to a customer's printer port to enforce use of the product on systems that have this device. This requires product distributors to acquire and ship an electronic device with every product shipment. This approach is particularly inappropriate for software that is distributed by communication media downloads.
U.S. Pat. No. 5,917,908 describes a method which encodes a key that is unique to a customer's system environment, along with positional information regarding where the key is stored within the customer's storage media, but this solution always requires an interaction between the customer and the product distributor after the product is received. Furthermore, this patent lacks a method for backing up the protection file, in case the original protection file is lost or damaged.
Problems associated with software protection strategies are described on page 179 of the book “A Gift of Fire”, by Sara Baase (1997 by Prentice-Hall, Inc. Upper Saddle River, N.J. 07458; ISBN 0-13-458779-0).
SUMMARY OF THE INVENTION
The present invention is a fail-safe technique for ensuring a software product operates on secured customer systems, without opportunities for reverse engineering the technology that secures these products. A protection file is created that is stored in the storage media associated with a customer's software utilization-system. The protection file contains internalized attributes that characterize a specific customer system environment. The system identifier of IBM mainframe computers, is an example of an attribute that characterizes that system. The protection file is encrypted and contains a digest, so that attempts to convert a protection file for use on another system are futile. Programs within the product distributor's software product interrogate the protection file to determine if the internalized attributes correspond with the attributes of the prevailing system environment.
When the computer software product is distributed on copyable media, the protection file must be created on the product distributor's system environment. The unique attributes of the customer's system environment are encoded within a binary file, that is sent to the product distributor by electronic mail. The binary file that is encoded during this process is not the same as the protection file that.is required for software product usage. Upon receiving the binary file, the product distributor decodes the attributes and prepares the required protection file. The product distributor sends the protection file to the customer by electronic mail, along with instructions describing where the protection file should be placed within the customer's storage medium.
When the computer software product is distributed via a communications media download, the protection file can be created directly on the customer's system environment. However, this requires encryption of the programs that prepare the protection file. These programs create the protection file by a cascade of successive steps. A parameter that is passed to the product distributor's installation program contains the required keys for decoding the programs in all steps. Each program that participates in this process:
eliminates the previous program
extracts the key that is required for decrypting the next program
decrypts the next program
invokes the next program with the remaining parameters after key extraction
At the conclusion of the last program, only the last program remains. If a system outage occurs during the protection file preparation process, no more than two programs associated with this process will remain on the customer's system. Every other program, including the first and last program, do not participate in protection file preparation. The logic that is encoded within a single program that participates in protection file preparation should be minimal, to thwart reverse engineering attempts. The parameter that contains the keys for decoding remaining programs, is lost as a consequence of the system outage. The customer must use the technique associated with acquiring a protection file for ‘copyable media’ that was described above.
Subsequently, the customer can use the technique associated with acquiring a protection file for ‘copyable media’, in case the protection file is lost or damaged. The customer can also store copies of the protection file on various storage media, and use these as subsequent replacements for a protection file that is lost or damaged.
The invention associated with this patent is characterized by the following significant innovations.
Innovation #1:
attributes that uniquely characterize a customer system can be encoded in a key file.
Innovation #2:
the key file, prepared by Innovation #1 can be sent to the product distributor, who responds with a protection file.
Innovation #3:
a protection file can be directly created when software is downloaded using a communication media.
Innovation #4:
the programs that create the protection file are encrypted. The keys to decrypt these programs are passed as a parameter to a program that is invoked on the customer's system during the conclusion of the download process. The parameter is passed in a volatile memory area, and is lost if a system outage occurs during the download process. The parameter is sufficiently intricate, so that a protection file cannot be prepared with prevailing files after the system outage has occurred.
Innovation #5:
accidental loss or damage of a protection file, can be overcome by using backup copies, or using Innovation #1 and #2 again.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagram illustrating a software product distribution overview.
FIG. 2 is a diagram illustrating how a computer system attributes are encoded in a ‘key’ file.
FIG. 3 is a diagram illustrating how the key is encoded as a protection file.
FIG. 4 is a diagram illustrating how the key file is sent to the product distributor.
FIG. 5 is a diagram illustrating how the product distributor prepares the corresponding protection file.
FIG. 6 is a flowchart illustrating a procedure that encrypts key information to produce the protection file.
FIG. 7 is a diagram illustrating how the protection file is sent to the client.
FIG. 8 is a flowchart illustrating how other programs validate the protection file for the current system.
FIG. 9 is a diagram illustrating how the system attributes could be encoded directly as a protection file, during a network download, without distributor involvement.
FIG. 10 is a diagram illustrating how the program that creates the protection file is activated with a special parameter string, which provides the keys to successively decrypt the programs in the encrypted program bundle.
FIG. 11 is a diagram illustrating the organization of the protection file prior to encryption, or after decryption.
FIG. 12 is a diagram illustration the organization of the composite file of encrypted protection file preparation programs.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
A description will be given of an embodiment of the present invention.
A customer system (a computer system) to which the protection system of the present inventions is applied is formed as shown in FIG. 1 . Referring to FIG. 1, the customer system has a computer processing unit (CPU), display device (video display tube (VDT)), keyboard, persistent storage file system (hard disk), and either a device that can read copyable media (floppy drive, CD-ROM drive, magneto-optical (MO) disk) or a device that can participate in communication media interactions (modem, network interface card).
Two software product distribution techniques are displayed in FIG. 1 . FIG. 1A illustrates a technique that distributes the software on copyable media, and acquires a protection file from the product distributor's site. FIG. 1B illustrates a technique that prepares the protection file directly on the customer system, without requiring further distributor involvement.
Protection of Products that are Distributed on Copyable Media
The product distributor prepares the contents of one or more units of copyable media. This media contains the installation program, product programs (applications) and associated files. This media also contains the key discovery program. The customer acquires the media from the product distributor by completing a terms of sale agreement. The product distributor delivers the copyable media to the customer using conventional package shipping agents. The copyable media is accompanied with a product serial number.
Software products that are distributed on copyable media are loaded into the customer's copyable-media device. An installation program that was provided by the product distributor is activated on the CPU. The installation program converts product programs and other files to a directory (folder) in the customer's storage system. The installation program then displays a fill-in-the blank registration form on the customer's display device. This form has a field where the product serial number is entered. The form has various other fields; i.e., name, mailing address, phone numbers, etc. When the customer has completed the registration form, the installation program activates the key discovery program, which prepares a binary ‘key’ file containing attributes that are unique to the current system environment. The binary ‘key’ file includes a digest that ensures the integrity of the file's contents. FIG. 2 shows the key discovery process. After the binary ‘key’ file has been prepared, the installation program transmits information entered in the form's fields as an electronic mail message to the product distributor. The binary ‘key’ file is sent as an attachment of the message. FIG. 4 shows how the message and ‘key’ are sent. After the message has been sent, the binary ‘key’ file is erased from the customer's storage system.
FIG. 5 shows how the distributor converts the key file to a protection file. When a product distributor's sales support representative receives the registration electronic mail message from the customer, the digest within the binary ‘key’ file is authenticated. If the digest does not match the contents of the binary ‘key’ file, then the file is invalid, and the sales support representative must communicate with the customer regarding the situation. The customer must initiate the product registration activity again.
If the digest matched the contents of the binary ‘key’ file, the information in the message and the binary ‘key’ file is added as an entry in the customer information database, using the product serial number as a database key (there is no relationship between a database key, and the ‘key’ file). If an entry with the same product serial number is discovered in the customer information database, a comparison is made between the information in the binary ‘key’ file that was sent with the electronic mail message, and the binary ‘key’ file that was previously stored in the customer information database. If these do not match, the sales support representative must communicate with the customer regarding the previous product registration. The sales support representative may establish a new sales agreement with the customer that sent the electronic mail message, in which case a new product serial number is established. The information in the message and the binary ‘key’ file is added as an entry in the customer information database, using the new product serial number as a database key. If the customer declines to establish a new sales agreement, then preparation of a protection file is avoided, and the product registration request is no longer processed.
If a previous entry was not present in the customer information database, or the previous entry's binary ‘key’ matched the message's binary ‘key’, or a new product serial number was established, preparation of the protection file can ensue. FIG. 3 is an overview of the conversion of the ‘key’ to a protection file. FIG. 6 is a flowchart of the conversion process. The generated protection file contains:
1. Key information—attributes that are unique to the customer's system
2. Gibberish—to conceal the location of the key information
3. Digest—a 16 byte binary value that ensures the integrity of the protection file
The sales support representative uses a support application to activate the first protection file preparation program with the name of the binary ‘key’ file as a parameter. The support application passes an additional string parameter to the first protection file preparation program. Other protection file preparation programs are encrypted within a composite file, as shown in FIG. 10 .
The product distributor must ensure that the sales support application, the first protection file preparation program, and other protection file preparation programs that are encrypted within a composite file are stored where only authorized employees can access them. If these are accessed by unauthorized parties, opportunities exist for illegal preparation of protection files, or reverse engineering the protection file preparation process.
The first protection file preparation program extracts information from the additional string parameter to determine how to decrypt the second protection file preparation program from the encrypted composite file. FIG. 10 illustrates the protection file preparation process. The second program is invoked with the name of the binary ‘key’ file as a parameter, and the remainder of the additional string parameter as a second parameter. There are four stages of protection file preparation. Each stage is performed by a different program within the encrypted composite file. Each stage except the first erases the program before it. When the last stage completes, the first protection file preparation program erases the last stage's program. FIG. 11 shows the organization of the protection file prior to encryption, or after decryption.
Stage 1: random gibberish is added to the body of the protection file.
The following is a sketch of the algorithm that is used to add gibberish to the file. Here it is assumed that the extent of the body of the protection file is 4096. Other extents could be used instead.
setRandomRoot(currentTime)
extent=4096
loop(i:1 . . . extent)
body[i]=random( )
Stage 2: system attribute information is added to the body of the protection file.
The following is a sketch of the algorithm that is used to add system attribute information to the file. Assume the system attribute information has 16 bytes. These bytes are stored at arbitrary locations within the body of the protection file. Here the factors of 4851 are used to identify where individual bytes are stored. Note: 4851 is the sum of the first 98 integers; i.e. 1+2+. . . +98. It is recommended that the offsets are dynamically computed, instead of providing these as constants in the program.
systemAttributeInformation [ ]=AcquiresystemAttributeInformation( )
offset [ ]={3, 7, 9, 11, 21, 33, 49, 63, 77, 99, 147, 231, 441, 539, 693, 1617}
attributeLength=length(systemAttributeInformation)
loop(i:1 . . . attributeLength)
body[offset[i]=systemAttributeInformation[i]
Stage 3: a digital digest is appended to the end of the protection file.
The digest is computed by analyzing the body of the protection file using the MD5 algorithm. The resulting digest is 16 bytes in length. It is stored immediately after the last byte of the body of the protection file. The MD5algorithm is distributed by RSA Security, Inc. A description of this algorithm and its source code are available in Internet RFC 1321.
Stage 4: the protection file is encrypted.
Finally, the entire protection file is encrypted using a key-less algorithm. An example of a suitable encryption algorithm follows. More sophisticated algorithms can also be used. In this algorithm contents are processed a word at a time. The size of a word is dependent on the system environment. In the algorithm below the word size is assumed to be 4 bytes. Proceeding from the left toward the middle, words are swapped with those from the right toward the middle. Before swapping, words are exclusive ORed with a mask, and then rotated leftward 20 bits. Then the mask is rotated rightward 2 bits. The value word[n] is a reference to the Nth word within the entire range of the protection file's contents. The mask value shown below is examplary. Other similar mask values could be used instead.
bodysize=4096
digestsize=16
wordsize=4
left=1
right=(bodysize+digestsize)/wordsize
middle=right/2
mask=2146426330[hexadecimal 7FEFDDDA]
loop(i:1 . . . middle)
leftword=word[i]
rightword=word[(right+1)−i]
xor(leftword, mask)
xor(rightword, mask)
rotateLeft(leftword, 20)
rotateLeft(rightword, 20)
word[(right+1)−i]=leftword
word[i]=rightword
rotateRight(mask, 2)
After the above encryption has completed, it is difficult to determine where various bytes of the original protection file reside. In addition, the bytes of the digest have become scrambled as well. Attempts to alter the byte values of the system attribute information is considerably problematic. Altering the digest so that it matches the altered system attribute information is virtually impossible. The digest contains 128 bits (8*16). Thus, 2 to the 128th trial and error attempts are necessary to compute the correct digest that matches the body of the protection file.
Further integrity can be attained by using multiple digests. The computation of each digest augments the body of the protection file with a computable gibberish segment of arbitrary length. A gibberish segment can be computed by setting the seed of the random number generator to a known value. A sequence of random numbers is then computed. The remainder of the first random number-with respect to a known value (e.g. 250), is added to a minimal size (e.g. 250) to compute the segment's length. Byte values within the segment are determined by subsequent random numbers. If 32 digests are computed, then there are 4096 bits (8*32*16) in all. Under these circumstances, 2 to the 4096th trial and error attempts would be necessary to compute the correct digest that matches the body of the protection file.
At this point, the protection file is ready to be sent to the customer, for insertion into the appropriate directory (folder) of the customer's storage system. FIG. 7 is an overview that shows how the protection file is sent to the customer. This is done by sending an electronic mail reply to the customer's electronic mail registration request. The text of the message acknowledges that the customer has registered the product serial number. The protection file is provided as a binary file attachment. Instructions within the electronic mail message identify how and where the protection file should be stored. For example, the file should be named PROTFILE.DAT, and stored in the same directory (folder) as the product program (application) executable files. The file could be stored in other well known directories as well.
Protection of Products that are Distributed on Communication Media Downloads
FIG. 9 shows the steps that proceed when products are delivered by communication media downloads.
The product distributor prepares a communications site (internet web page). The customer uses the communication media device (modem, network interface card) to acquire software products from this communications site. The customer completes a terms of sale agreement, and a financial transaction is performed to purchase a product. Afterwards downloading of the product ensues.
The product download operation is managed by the ‘Download Supervision Program’, which is activated on the CPU. This program receives files from the distributor's site, and converts these to the first protection file preparation program, product programs (applications) and associated files. One of the files is the composite file that contains encrypted protection file preparation programs. Another file contains the customer's product serial number. The key discovery program is one of the programs that is prepared, in case an outage occurs which would require preparing the protection file by using the copyable media technique. All downloaded files are stored in one or more directories (folders) within the customer's storage system.
At this point the protection file preparation process is performed. The file has a name that is known by product programs (applications); such as, PROTFILE.DAT. The file is prepared in the same directory (folder) as product programs (applications). The file could be stored in other well known directories as well.
The Download Supervision Program activates the first protection file preparation program, with a string parameter. The first protection file preparation program extracts information from the additional string parameter to determine how to decrypt the second protection file preparation program from the encrypted composite file. FIG. 10 illustrates the protection file preparation process. The second program is invoked with a parameter which is the remainder of the original string parameter that followed the information that was used to extract the second program. There are four stages of protection file preparation. Each stage is performed by a different program within the encrypted composite file. Each stage erases the program before it.
More than four programs are contained within the encrypted composite file. Every other program erases the prior program, and invokes the next program, without participating in the preparation of the protection file. When the last program completes, it is the only program remaining on the customer's system. The first and last programs also do not participate in protection file preparation. If a system outage occurs during the preparation of the protection file, no more than two preparation programs will be present on the customer's system in decrypted form. Only one of these programs participates in protection file preparation. This reduces exposure of the logic contained in these programs to reverse engineering attempts.
The information required to extract and decrypt the protection file preparation programs is passed as a volatile parameter. The value of this parameter is lost when a system outage occurs. Thus, the customer does not have sufficient information to continue the protection file preparation process after the system outage has occurred. In this case, the protection file must be prepared by using the copyable media technique described earlier.
An implementation of the algorithms described here should periodically try to detect if the customer is executing the program in a debugging environment and cease to operate if so.
FIG. 11 shows the organization of the protection file prior to encryption, or after decryption.
Stage 1: Random Gibberish is Added to the Body of the Protection File.
See the algorithm that added gibberish to the protection file in the copyable media technique above.
Stage 2: System Attribute Information is Added to the Body of the Protection File.
See the algorithm that added system attribute information to the protection file in the copyable media technique above.
Stage 3: a Digital Digest is Appended to the End of the Protection File.
The MD5 algorithm is used, as described in the copyable media technique above.
Stage 4: the Protection File is Encrypted.
See the encryption algorithm that was described in the copyable media technique above.
At this point, the protection file is ready for use by product programs (applications) on the customer's system. The customer should be advised to prepare one or more backup copies of the protection file.
How Product Programs (Applications) Determine they are Executing on a Secured System
FIG. 8 shows how product programs (applications) ensure that the protection file is appropriate for the current customer system.
Each product program (application) contains embedded logic that compares attributes within the protection file versus prevailing attributes of the customer's system. The protection file (e.g. PROTFILE.DAT) is located in the same directory (folder) as the product program (application), or another well known directory. Information within the protection file is processed in three stages. An implementation of these algorithms should periodically try to detect if the customer is executing the program in a debugging environment and cease to operate if so.
Stage 1: the Protection File is Decrypted.
The entire protection file is decrypted using a key-less algorithm. An example of a suitable encryption algorithm follows. If a more sophisticated algorithm was used when the file was encrypted, the counterpart decryption algorithm must be used instead.
In this algorithm file contents are processed a word at a time. The size of a word is dependent on the system environment. In the algorithm below the word size is assumed to be 4 bytes. Proceeding from the left toward the middle, words are swapped with those from the right toward the middle. Before swapping, words are rotated rightward 20 bits, add then exclusive ORed with a mask. Then the mask is rotated rightward 2 bits. The value word[n] is a reference to the Nth word within the entire range of the protection file's contents.
bodysize=4096
digestsize=16
wordsize=4
left=1
right=(bodysize+digestsize)/wordsize
middle=right/2
mask=2146426330[hexadecimal 7FEFDDDA]
loop(i:1 . . . middle)
leftword=word[i]
rightword=word[(right+1)−i]
rotateRight(leftword, 20)
rotateRight(rightword, 20)
xor(leftword, mask)
xor(rightword, mask)
word[(right+1)−i]=leftword
word[i]=rightword
rotateRight(mask, 2)
Stage 2: a Digital Digest is Computed for the Protection File's Body.
The MD5 algorithm is used, as described in the copyable media technique above. A digest is computed for the body of the protection file and compared with the digest that resides at the end of the decrypted protection file. If these digests do not match the protection file is invalid for the current system environment, because the protection file has become corrupted intentionally or accidentally.
Stage 3: System Attribute Information is Compared Versus the Value in the Body of the Protection File.
Attributes that uniquely identify the customer's system are acquired by calling various programs available within the current system environment. The following is a sketch of the algorithm that is used to compare the acquired system attribute information to the file. Assume the system attribute information has 16 bytes. The factors of 4851 could be used to identify where the individual bytes are stored in the body of the protection file. Note: 4851 is the sum of the first 98 integers; i.e. 1+2+. . .+98.
systemAttributeInformation[ ]=AcquiresystemAttributeInformation( )
offset[ ]={3, 7, 9, 11, 21, 33, 49, 63, 77, 99, 147, 231, 441, 539, 693, 1617}
extent=length(systemAttributeInformation)
loop(i:1 . . . extent)
if mismatch(body[offset[i]],
systemAttributeInformation[i])
error( )
If the system attribute information does not match the values in the protection file, then the product program (application) is not permitted to execute on the current customer system. Either the file was copied from another system, or the protection file has become corrupted intentionally or accidentally. The customer can replace a corrupted protection file with a backup copy if one is available. Otherwise, a new protection file must be obtained by using the copyable media technique.
How a Protection File Preparation Program is Encrypted
Protection file preparation programs are encrypted with a variation of the encryption routine that was described earlier. The following is an example of a suitable key-less- encryption algorithm. More sophisticated algorithms can also be used. In this algorithm program contents are processed a word at a time. The size of a word is dependent on the system environment. In the algorithm below the word size is assumed to be 4 bytes Proceeding from the left toward the middle, words are swapped with those from the right toward the middle. Before swapping, words are exclusive ORed with a mask, and then rotated leftward 20 bits. Then the mask is rotated rightward 2 bits. The value word[n] is a reference to the Nth word within the entire range of the program contents. The mask and the program's origin and size are parameters to the encryption routine.
word[ ]=GetProgramorigin( )
programsize=GetProgramsize( )
wordsize=4
left=1
right=programsize/wordsize
middle=right/2
mask=GetMask( )
loop(i:1 . . . middle)
leftword=word[i]
rightword=word[(right+1)−i]
xor(leftword, mask)
xor(rightword, mask)
rotateLeft(leftword, 20)
rotateLeft(rightword, 20)
word[(right+1)−i]=leftword
word[i]=rightword
rotateRight(mask, 2)
How the Composite File of Encrypted Protection File Preparation Programs is Prepared
The composite file of encrypted protection file preparation program is prepared as a collection of segments. Gibberish segments of various sizes are added at the beginning, end, and between all of the encrypted program segments. FIG. 12 shows the organization of the composite file.
How a Protection File Preparation Program is Decrypted
Protection file preparation programs are decrypted with a variation of the decryption routine that was described earlier. The following is an example of a suitable key-less decryption algorithm. More sophisticated algorithms can also be used. In this algorithm file contents are processed a word at a time. The size of a word is dependent on the system environment. In the algorithm below the word size is assumed to be 4 bytes. Proceeding from the left toward the middle, words are swapped with those from the right toward the middle. Before swapping, words are rotated rightward 20 bits, and then exclusive ORed with a mask. Then the mask is rotated rightward 2 bits. The value word[n] is a reference to the Nth word within the entire range of the program contents. The mask and the program's origin and size are parameters to the decryption routine. These are the parameters that are passed to the various stages shown in FIG. 10; i.e. param_ 1 , param_ 2 , and param_ 3 . The GetMask( ), GetProgramOrigin( ), and GetProgramSize( ) functions below obtain the values from the decryption routine's parameter string.
word[ ]=GetProgramorigin(parameterstring)
programsize=GetProgramsize(parameterString)
wordsize=4
left=1
right=programsize/wordsize
middle=right/2
mask=GetMask(parameterString)
loop(i:1 . . . middle)
leftword=word[i]
rightword=word[(right+1)−i]
rotateRight(leftword, 20)
rotateRight(rightword, 20)
xor(leftword, mask)
xor(rightword, mask)
word[(right+1)−i]=leftword
word[i]=rightword
rotateRight(mask, 2)
Although the present invention has been described and illustrated with specific reference to certain detailed arrangements, it will be apparent to those skilled in this field that alternative embodiments will achieve the same results without deviating from the basic concept of the invention. All such embodiments and their equivalents are deemed to be within the scope of the invention as set out in the description. | Computer software can be secured so that it only operates on a customer system that has a protection file that is unique to the system. The software is inoperable when copied to other systems, even though the protection file is copied as well. The protection file is sufficiently encoded so that attempts to alter the file for use on another system will be futile. The process of encoding the protection file is sufficiently complex, so that attempts to reverse engineer the construction of the file will also be futile. The logic that encodes the protection file is never available for direct use on the customer system. For software that is distributed on copyable media, the protection file is created by a program on the product distributor's system. When the protection file is prepared during a software download request, multiple programs are used. These programs are encrypted within a composite file. The keys for decrypting these programs are passed as a parameter to a product installation program at the conclusion of the download process. All significant programs associated with the preparation of a protection file on the customer's system are eliminated after the file is created. | 6 |
This application is a U.S. national stage application under 35 U.S.C. §371 of International Application No. PCT/EP2011/059677, filed Jun. 10, 2011, claiming priority to United Kingdom Patent Application No. 1010766.2, filed Jun. 25, 2010, and to U.S. Provisional Application No. 61/358,856, filed Jun. 25, 2010, each of which is incorporated by reference in its entirety into this application.
The present invention relates to a delivery system for a self-expanding implant to line a bodily lumen, which includes a sheath to hold the implant in a radially compressed configuration prior to and until deployment in the lumen, when the sheath is withdrawn along the axis of the lumen.
Self-expanding implants such as stents and stent grafts are often delivered to a stenting site within a bodily lumen with the use of a catheter delivery system that is advanced percutaneously and transluminally. Although most stents and stent grafts are for the cardiovascular system, self-expanding implants can also be delivered transluminally to body lumens that carry bodily fluids other than blood. A stent without a coating is often called a “bare” stent. Stent grafts that carry a covering of a material such as expanded polytetrafluoroethane (ePTFE) are often called “covered” stents or “stent grafts”. A self-expanding stent need not be made of metal but usually is, and that metal is usually a nickel titanium shape memory alloy commonly known as “NITINOL”.
Given that a self-expanding stent will expand when freed of the constraint of the catheter delivery system, it follows that the catheter delivery system confining the stent will be subject to radially outward pressure from the confined stent, at least at body temperature 37° C. With NITINOL, the outward radial pressure dwindles to zero as the temperature of the stent is reduced to temperatures around 0° C. and below, with the austenitic crystal lattice changing, as the temperature reduces, to a martensitic crystal lattice.
Thus, at low temperatures, with the self-expanding stent in the martensitic state, the hoop stress on the sheath surrounding the stent in the delivery system will be relatively low, even to the extent of being close to zero. However, as the temperature rises towards body temperature, the radially outward pressure on the confining sheath will increase. Given that the confining sheath has to be flexible if the distal end of the catheter delivery system is to advance along a tortuous bodily lumen, it is invariably made of a synthetic polymeric material rather than metal. Such materials are subject to deformation and the deformation of polymers is a time-dependent phenomenon. Suppose that the self-expanding stent confined within its sheath is stored for a period of weeks or months, at room temperature or above. There is the possibility, perhaps likelihood, that the sheath will stretch and the stent will expand radially to some extent, during the extended period of storage.
Even more significant, in coated stents such as those made of Nitinol with an ePTFE covering, relaxation of the compacted ePTFE layer on the stent also contributes to radial distortion of the sheath.
As the quest continues for ways to deliver implants to ever-smaller diameter locations within the body, through ever-more tortuous delivery paths, the pressure on designers of implants and delivery systems to reduce to ever-smaller values the passing diameter of the distal end of the catheter system where the implant is located, continues to increase. This pressure pushes designers to think of sheath designs of ever-smaller wall thickness. The smaller the wall thickness of the sheath, the greater the difficulty of resisting the radially outward pressure imposed on the sheath by the stored implant.
One promising route to reduce yet further the wall thickness of the confining sheath is, perhaps paradoxically, to provide that the sheath has a double layer, namely, as a cylindrical sheath that doubles back on itself. It starts proximally of the implant, extends distally over the full length of the implant and then is turned back radially outwardly on itself, to continue back along the length of the implant, extending proximally, to a position proximal of the proximal end of the implant. That turned back end of the sheath, proximal of the implant, can be pulled proximally, when the time comes to release the stent. That proximal pull will draw proximally, progressively, the point along the length of the sheath where the sheath material doubles back on itself. That location where the sheath material doubles back on itself progresses proximally along the length of the implant, releasing as it goes the stent portion radially inside it, so that, when it finally reaches the proximal end of the implant, the implant is fully released into the bodily lumen.
The present invention represents a way to minimise the wall thickness of sheath material surrounding a self-expanding implant, so that the passing diameter of the distal end of a catheter-type implant delivery system can be reduced yet further.
According to the present invention there is provided in such a delivery system a confining element, preferably in the form of a sleeve, to surround the sheath during a storage period between placement of the implant within the sheath and said withdrawal of the sheath, the confining element serving to reduce the hoop stress in the sheath during said storage period and being removable from the sheath prior to advancement of the sheath into the said bodily lumen.
It will appreciated by skilled readers that, when the confining element acts to reduce the hoop stress in the sheath during the storage period this, in turn, can reduce the amount of time-dependent creep deformation of the sheath in contact with the stent during the storage period, that would otherwise tend to increase the diameter of the sheath, under pressure from the implant within it. In some cases such an increase could result in increasing the passing diameter of the distal end of the delivery system to a value higher than is needed for delivery of the implant, and higher than the minimum that can be achieved with the specific delivery system prior to any period of extended storage. In others, the increase could lead to fouling of the sheath during movement relative to other components of the delivery system.
It may be convenient to make the confining element as a sleeve of a heat-shrinkable material and shrink it around the sheath during manufacture of the delivery system. Such a shrinking step will bring the confining structure into embracing contact with the distal end of the delivery system. Thus, the microstructure of the heat shrunk material can be more resistant to creep stretching under hoop stress from the confined implant than the same material prior to being subjected to the heat shrinking step.
The proposal to put the sheath inside a sleeve is of no value unless the sleeve can easily be removed when the time comes to use the delivery system for delivering the implant. At that point, the sleeve must be removed prior to advancing the distal end of the delivery system into the body of the patient. One convenient way to strip off the sleeve is to include with the sleeve an elongate pull element that will, when it pulled in the proper direction, part the sleeve progressively, from one end of the sleeve towards the other, to release the hoop stress in the sleeve and release the sheath from the surrounding sleeve. One need only think of the way in which the clear plastic film around a packet of cigarettes is released from the cigarette packet to understand how any such elongate pull element might work. To assist the operation of the pull element in the environment of an operating theatre, the inventor contemplates providing the free end of any such pull element with a finger ring to receive a finger and serve as a pull ring to pull the pull element to part the sleeve. The inventor envisages making the sleeve of a PET material (polyethylene terephthalate) (polyethylenephthalate). The above mentioned self-expanding implant release system that relies on a sheath that doubles back on itself will work optimally only when the sheath material can slide on itself, so that the outer of the two coaxial layers of the sheath can easily slide proximally over the abluminal surface of the inner layer of the sheath. Suppose that such a doubled back sheath is confined inside a surrounding sleeve that imposes uniform pressure on all parts of the surface of the outer layer of the doubled back sheath. It is not inconceivable that there will be some tendency for the two facing layers of the sheath somehow to “stick” to each other, at least locally. Self-evidently, it is important that the confining sleeve shall not induce such adherence between the two facing layers of the sheath confined within it. Preferred embodiments of the present invention offer improved prospects to defeat any such tendency for adherence between the two layers of a roll back sheath.
Specifically, a preferred system according to the present invention will include means to establish spaced pressure relief zones interposed between the sheath and the sleeve for preferentially carrying the forces acting between the sheath and the sleeve, whereby zones of the sheath that lie between adjacent pressure relief zones are relieved of the full magnitude of said forces.
In other words, by confining to particular pressure zones the radially inward squeezing action of the sleeve on the sheath, the intervening parts of the surface area of the sheath will be spared the radially inward pressure and so the outer of the two facing layers of the sheath will not be pressed with full force against the abluminal surface of the inner of the two sheath layers. Indeed, with careful design of the sleeve system, it ought to be possible to arrange for there to be a physical gap between the abluminal surface of the inner sheath layer and the luminal surface of the outer sheath layer, in locations between two adjacent pressure zones. Skilled readers will appreciate that confinement of the full squeezing force of the sleeve on the sheath to specific spaced zones interspersed with pressure relief zones offers the possibility to neutralise any tendency for the two sheath layers to stick to each other in the pressure zones.
This is particularly the case if the pressure zones are confined to lines of contact on the abluminal surface of the outer layer of the sheath that run parallel to the axis of the sheath and implant. This is because any such line of contact, where sticking is likely to occur preferentially, runs along the length of the implant and therefore should present a minimal sticking problem when the sheath is progressively peeled backwards along the length of the implant from its distal end to its proximal end.
Specifically, suppose there are six lines of contact between the sleeve and the sheath, evenly distributed at 60° intervals around the circumference of the sheath. After the sleeve has been removed, and the sheath is pulled proximally to release the implant, we can take it that any sticking is likely to be found at one or more of those six points of contact distributed evenly around the circumference. However, when most of the circumference of the sleeve is peeling back from any sticking, such adherence as is to be found at the six points of contact is broken by shearing and so ought to provide hardly any impediment to the smooth and progressive rolling back of the sheath membrane to release the implant.
One way to provide a plurality of such lines of contact parallel with the axis of the sheath and implant is to provide between the sheath and the sleeve a plurality of elongate members, evenly distributed around the circumference of the sheath and sleeve and all parallel to the axis of the sheath and implant. It may be useful to provide such elongate members as tubes. It may be optimal to select the tube diameter and the number of tubes such that they are in close proximity, or even in contact with each other, in the annular gap between the sheath and the sleeve. In one preferred embodiment, for example, there are six such tubular elongate members, thus with their long axis at spaced intervals of 60° around the circumference of the axis of the implant. Another possibility is four tubes at 90° intervals parallel but spaced apart from each other.
Skilled readers will appreciate that there is no absolute need to have adjacent elongate members in continuous contact with each other, side-by-side, over the full length of the implant. When there are enough points of contact distributed along the length of the elongate members, at spaced intervals, there is no need for any such side-by-side contact between the spaced contact points. If spacers are used, there need be no contact at all between the adjacent elongate members. In the illustrated embodiment described below, it is shown how wall portions of elongate tubular members can be selectively removed to provide spaced points of side-by-side contact but a continuous line of contact of each elongate tubular member with the sheath confined radially within it.
It will likely be convenient and effective to provide the above-mentioned elongate members as components made of metal. It is envisaged that the extra cost to a delivery system for an implant caused by the provision of the elongate members and sleeve will be minimal in relation to the performance advantages obtainable, particularly in relation to the storage periods and temperatures that are liable to be encountered in practical day-to-day use of such implant delivery systems.
BRIEF DESCRIPTION OF THE DRAWINGS
For a better understanding of the present invention, and to show more clearly how the same may be carried into effect, reference will now be made, by way of example, to the accompanying Drawings, in which:
FIG. 1 is a section taken transverse to the long axis of the distal end of a delivery system for a self-expanding implant;
FIG. 2 is a section taken in a plane normal to the long axis of the distal end of a delivery system for a self-expanding implant; and
FIG. 3 is an isometric view through an assembly of elongate members applicable to the embodiment shown in section in FIG. 1 together with an example of an isolated elongate member for use in such an assembly.
DETAILED DESCRIPTION
Best Mode
There now follows a description of one exemplary embodiment for putting the present invention into effect.
FIG. 1 shows a first embodiment of the present invention, being a delivery system for a self-expanding implant to line a bodily lumen. The inner components of the delivery system are essentially conventional, but will be described here to aid the reader in understanding the interaction between the various components of the system.
Defining an axis of the delivery system is inner catheter 11 , which runs from a distal end of the delivery system (on the left hand side of the Figure) to a proximal end of the delivery system (not shown in the Figure but some distance beyond the right hand of the Figure).
Inner catheter 11 defines a lumen through which guide wire 21 runs. Guide wire 21 is provided to be inserted percutaneously and guided through the body passages which the stent delivery system is to navigate before the delivery system itself is introduced, in order to more easily guide the proximal end of the stent delivery system to its intended location in the body.
Coaxial with the inner catheter, and located around it in a compressed configuration is implant 31 , in the present instance being a self-expanding NITINOL stent. The stent is held in a radially compressed configuration onto the inner catheter by means of inner sheath layer 41 , which radially surrounds the stent and applies inwardly radial pressure thereto to maintain the stent in its compressed configuration. In the system depicted, inner sheath 41 extends distally and then folds back on itself at a distal turning point to return proximally as outer sheath 42 . This configuration is conventionally known as a roll-back design, as will be explained later in terms of stent deployment.
Outer sheath 42 extends proximally until a region A, where its radius reduces to that of pull portion 51 , where it attaches. Pull portion 51 extends proximally to the proximal end of the delivery system to convey an actuating tensile force from the operator to outer sheath 42 . In contrast, push element 61 is provided to restrain the stent 31 from proximal axial movement relative to inner catheter 11 . Accordingly, push element 61 is provided fixed in relation to inner catheter 11 , in some embodiments by means of the inward pressure of inner sheath 41 . Atraumatic tip 91 is provided distal of stent 31 to shield the distal end of inner sheath 41 and outer sheath 42 from the body passages through which the stent delivery system travels, and vice versa.
What has been described so far is for the most part conventional. However, the embodiment shown in FIG. 1 also provides a confining structure 80 , including rod members 81 a , 81 b , 81 c , 81 d , 81 e and 81 f , of which only 81 a and 81 d are shown. The rod members lie essentially parallel to inner catheter 11 at substantially equal circumferential spacings therearound and are confined themselves by sleeve 82 . The radial configuration is shown in FIG. 2 , in which the structures inward of outer sheath 42 have been simplified for clarity.
Confining element 82 , here being a confining sleeve, provides inward radial pressure on the rods, which themselves provide inward radial pressure on outer sheath 42 at each of the six points of contact of the rods to the outer sheath around the circumference thereof. On the other hand, between the points of contact no pressure is applied. This can be seen more easily in FIG. 2 , including the phenomenon of close compression of the layers 41 , 42 at the contact points of the rods 81 , while voids 71 exist between layers 41 , 42 at regions between the points of rod circumferential contact.
By applying this radial compression to outer sheath 42 , the tendency of stent 31 to distort, by virtue of its natural tendency to expand and thus apply radial pressure, inner and outer sheaths 41 and 42 is inhibited.
Prior to use in surgery, the stent delivery system is provided in the form shown in FIG. 1 in which it may be stored for an extended period.
The user, just prior to surgery, removes the confining structure 80 , by, for example, splitting sleeve 82 and discarding the rods 81 . The stent will then be available for use in its design-intended configuration, having dimensions and geometry undistorted over time by the aging process.
Next, the guide wire is inserted into the body percutaneously and navigated beyond the stent site. The delivery system is then directed along the guide wire to reach a particular body lumen, for example a cardiac artery. In the configuration of stent shown in the present embodiment, the pull element 51 is then retracted by application of tensile force from the proximal end of the system. The outer sheath 42 thus slides proximally over inner sheath 41 such that the folded portion distal of inner sheath 41 and outer sheath 42 progressively rolls back to expose the stent. Meanwhile, push element 61 , being coupled to inner catheter 11 , which is held static at the stenting site by compression forces from the proximal end of the system, restrains the stent from proximal movement to ensure accurate deployment at the intended stenting site. As the pull element is retracted, radial pressure is released on the stent and stent 31 assumes its expanded configuration, such that the inner radial void of the stent becomes larger than atraumatic tip 91 , and the stent engages with the walls of the bodily lumen.
The stent delivery system may then be swiftly and easily retracted the way it arrived, leaving the stent secured in place.
Of course, many other configurations of stent delivery system than roll-back systems may be used in conjunction with confining structure 80 . Indeed, confining structure 80 provides an effective means of containing any self-expanding implant delivery structure which is otherwise liable to expand over time and therefore potentially exceed its design tolerances. For example, confinement structure 80 can be used with stent delivery systems having pull-back, rather than roll-back, sheaths.
The construction of elements within confining structure 80 may be, as has been mentioned, conventional. On the other hand, the innovative confining structure 80 may itself be realised in a number of different forms. Considering the arrangement of FIGS. 1 and 2 , confining structure 80 is provided as longitudinal rods spaced equidistantly about the circumference of the outer sheath 42 , but other configurations to those shown in FIG. 1 are entirely possible.
For example, the rods may instead be formed as hollow cylinders and/or their arrangement and spacing around the circumference of the outer sheath may be varied. For example, four rods or eight rods may be contemplated, and their diameter varied in comparison to the diameter of the outer sheath.
In some embodiments, a split-wire 83 , shown schematically in FIG. 2 , may be provided, running the length of the sleeve, to enable the user to easily and swiftly split the sleeve before use, without the use of a separate tool. Such a split-wire may run distally (portion 83 a ) within the sleeve between two of the rods and may then loop at the distal end before returning (portion 83 b ) to the proximal end on the outside of the sleeve, terminating in a pull-ring 84 . Pulling on the pull-ring will then cause the wire to split the outer sleeve longitudinally, distal to proximal. Thin steel wire is suitable as a split-wire, in some embodiments.
In one embodiment, the rods do not touch but approach each other closely. This permits a high degree of contact with the outer sheath and confinement thereof while preventing variations in confining force or inability to sufficiently compress due to the rods touching one to another. In another embodiment, the rods are configured to touch one another at a desired level of confining pressure or confining diameter, to prevent the inner components of the stent delivery system becoming crushed by overpressure.
In the above embodiment, the conventional stent structure lying within the confining structure, namely that lying within the radius of the outer sheath, typically has a diameter of around 2.4 mm. In such a configuration, stent diameters themselves of around 2.1 mm are conceivable, in their compressed state. Of course, in their expanded state such stents typically achieve outer diameters of around 7 mm, depending on application. For such applications, rods of the confining structure having a diameter around 2 mm may be appropriate.
As to the other components, the atraumatic tip 91 is typically formed from polyurethane, the inner catheter is typically a polyimide tube, while the inner and outer sheaths are typically formed from 80 μm-thick PET which are respectively cold drawn (for the inner sheath) and heat shrunk (for the outer sheath) to a reduced thickness during manufacture. The thickness may be reduced from an original thickness of 80 μm down to a reduced thickness of 40 μm, in one exemplary embodiment. Further details of the construction of typical roll-back stent delivery systems to which the present invention may be applied may be found in published patent applications, such as WO 2006/020028 A1.
The rods are envisaged to be made from steel or polyamide, but other materials, including both metals and polymers, are well within the choice of the skilled designer to select. However, both steel and polyamide are considered to be especially able to give the required resistance to distortion preferred in embodiments of the present invention.
Indeed, if the rods are sufficiently resistant to deformation, it may not be required to provide a sleeve running the entire length of the confining structure, but to merely provide a number of compressing ligatures spaced along the length of the rods, in the manner of the hoops used to compress a traditional barrel of beer, wine or ale. Therefore, another embodiment is possible wherein the outer sleeve is replaced by a series of rings which may be slid along the rods to release them. Alternatively, a clamshell clamping arrangement may be provided around the rods, which arrangement may be released by a catch prior to use of the delivery system.
Another embodiment is contemplated having a configuration of confining structure as shown in FIG. 3 . FIG. 3 does not show the inner stent delivery components or the outer sleeve, but shows how a bundle of six tubes may be arranged to perform the same function as the rods 81 , even though portions of the tubes have been cut out circumferentially, except for certain circumferentially intact portions spaced along the length. These uncut portions, having a complete circumference, transfer the compressive force of the sleeve through the tubes to the confined inner components of the stent delivery system. On the other hand, where the circumference is not complete, sufficient of the circumference remains to provide a line of pressure along the stent delivery components to achieve the effects of the invention. In this embodiment, the characteristics of the material from which the tubes are formed will determine how closely the full-circumference portions need to be spaced and how much of the circumference may be removed in the intervening cut-out portions. However, it is envisaged that the advantages of the present invention may be obtained even when the cut-out portions retain only around 130° of circumference each.
As to the construction of an embodiment of the complete confined delivery system, starting from a complete conventional stent delivery system, the rods are located in their predetermined positions around the conventional delivery system and heat-shrink tubing applied to the outside. This heat-shrink tubing is typically PET tubing, which will shrink radially within around five seconds when a temperature of 200° C. is applied. During manufacture of stent delivery systems, it is generally considered highly undesirable to apply heat to a region proximate to a compressed-shape memory stent, in case the memory of the expanded configuration is distorted or destroyed, leading to potential catastrophic deployment failure. However, in the described embodiment, heat-shrinking of the outer sleeve is entirely possible, since the intervening rods and air gaps provide sufficient insulation to prevent effective heat transfer to the stent during the period when the heat-shrink tube is heated to cause it to shrink and radially confine the rods.
The present invention is not limited to the presently-disclosed embodiments, but rather solely by the scope of the appended claims. The skilled reader will easily contemplate how embodiments of the confining structure may be incorporated into other constructions of implant delivery systems where dimensional creep due to aging is undesirable. Such embodiments may not be herein explicitly described, but with nevertheless be clearly within the ambit of the skilled reader without undue experimentation and without the exercise of inventive skill. | The present disclosure provides a delivery system for a self-expanding implant ( 31 ) which includes a sheath ( 41, 42 ) which surrounds and constrains the implant prior to delivery and a confining element ( 80 ) which surrounds the sheath during storage. The confining element preferably includes elongate members ( 81 ) running axially along the sheath, which compress the sheath and the stent to reduce hoop stress in the system without promoting undesired adhesion between layers of the sheath. | 0 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] Not Applicable
STATEMENTS REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] Not Applicable
REFERENCE TO A MICROFICHE APPENDIX
[0003] Not Applicable
BACKGROUND OF THE INVENTION
[0004] This invention relates to the arts of disassociation of water to produce the associated resultant gaseous mixture and energy; more specifically, this invention relates to the arts of the ultra-high temperature cyclic thermal disassociation of water.
[0005] This invention relates to a new apparatus and method for the production of hydrogen, oxygen, and energy from the cyclic disassociation and combustion of water. The necessity for a commercially viable, clean source of renewable energy is only becoming more apparent. Because of hydrogen's available clean uses, apparent abundance, and appropriate combustive properties, hydrogen is looked upon as the source of energy to replace our current reliance on fossil fuels. Unfortunately, large-scale, efficient methods of hydrogen production have remained hidden from the World's brightest researchers. Many have attempted but all devised methods have inherent shortcomings.
[0006] In U.S. Pat. No. 6,977,120 B2, Chou discloses a mixed hydrogen-oxygen fuel generator system using an electrolytic solution to generate gaseous hydrogen-oxygen fuel through the electrolysis of water molecules. Electrolysis has been known for many years and has yet to become commercially viable except in the production of small quantities of high-purity hydrogen and oxygen. Generally, such electrolysis methods have weaknesses such as excessive consumption of electricity, the perilous creation of highly explosive gases, and overheating that requires the shutting down of the process. Chou attempts to overcome such shortcomings by using an electrode plate design that decreases electrical consumption, a method to create a mixed hydrogen-oxygen fuel that bums at a controlled temperature, and a cooling system that re-circulates the electrolytic solution. The claimed improvements purportedly increase the efficiency of the overall electrolysis method. However, Chou does not realize the nature of the produced gaseous hydrogen-oxygen fuel and only uses the electrolyticly-derived mixture for producing a flame with a controlled ignition temperature. The current invention does not utilize classical electrolysis of water for the disassociation of water because of its inherent inefficiencies. Electrolysis just requires too much electricity to viably produce enough hydrogen to meet demand.
[0007] Another attempt at overcoming the inherent limitations of classical electrolysis is Streckert, U.S. Pat. No. 6,939,449 B2. While Chou disclosed a low-temperature, about 30° C., apparatus and method, Streckert utilizes temperatures about 200° C. above room temperature. Streckert emphasizes the need for commercially viable, small scale electrolytic devices. Streckert still suffers from the failures of electrolysis by creating hydrogen for fuel purposes inefficiently, which leads to excessive power consumption.
[0008] Other attempts at creating an efficient device and method for the disassociation of water have been attempted using the Sun as the main source of energy. The Vialaron patent, U.S. Pat. No. 4,696,809, discloses an apparatus and method for the continuous photolytic disassociation of water. Vialaron describes the disclosed invention as a thermolytic but is more accurately described as photolytic because of the preferred use of electromagnetic radiation to achieve disassociation temperatures. Vialoron describes submerging a refractory body in water and focusing energy thereupon such that disassociation temperatures are reached. This heating creates a thin film of dissociated water about the surface of the refractory body. Submersing the refractory body in water replaces other methods of quench cooling the produced gases because the generated hydrogen and oxygen dissolve and diffuse into the water. The resultant bubbles of dissociated gasses are swept away from the refractory body by flowing water, which in turn maintains the desired temperature of the refractory body. The dissolved, produced gases are then extracted by conventional hydrogen, oxygen methods well-known in the art. The preferred embodiment describes the use of mirrors to focus electromagnetic radiation on the refractory body.
[0009] Another attempt at photolytically dissociating water is described by Pyle in U.S. Pat. No. 4,405,594 specifically as a photo separatory nozzle. Pyle describes the preferred apparatus as comprising a reflective dish that focuses solar energy, or electromagnetic radiation, upon a focal point with a concentration ratio of about or greater than 2000:1. Such is necessary to achieve the requisite temperatures to dissociate water into its constituent elements. Pyle discloses the use of a ceramic orifice, through which super-heated steam is forced, to pass over the refractory material that is the focal point of the solar energy. The sudden expansion and concomitant drop in pressure serves to retard recombination so that the lighter constituent gases, namely hydrogen, may be separated from the heavier, such as oxygen and gaseous water.
[0010] These electromagnetic dependent inventions suffer from the inherent limitations of all inventions dependent upon the use of the Sun as the electromagnetic radiation generator. This dependence results in decreased capabilities because most parts of the Earth have access to the Sun's radiation for no more than half of the day. If the device were moved to polar regions, efficiency would be decreased because of the Sun's radiation having to travel through more of the Earth's atmosphere. Also, efficiency or reflection would decrease throughout time of operation as the mirrors' surfaces become soiled.
[0011] Another method of dissociating water into hydrogen and oxygen has been disclosed by Lee in U.S. Pat. No. 6,726,893 B2. Lee discloses the well-known thermolytic disassociation of water, but provides semi-permeable membranes to drive the equilibrium of the reaction to the products, namely hydrogen and oxygen. Lee teaches that at about 1600° C., the concentrations of hydrogen and oxygen are 0.1 and 0.042%, respectively. By removing both the produced hydrogen and oxygen, the equilibrium of the disassociation reaction is driven to reactants and the disassociation can take place at lower temperatures. Lee prefers temperatures at least as high as 700° C., but preferably around 1500-1600° C., as determined by economics and engineering. Unfortunately for Lee, the economics of providing such high temperatures as required by the disassociation needs of water have traditionally limited the commercial viability thermolytic disassociation processes.
[0012] Others have addressed such limitations of thermolytic disassociation such as Vialaron as discussed above. Heller, U.S. Pat. No. 4,419,329, attempts to utilize a different approach: supplying energy to the water to be dissociated through use of ionization and magnetic fields. Heller discloses a device and method to dissociate water into hydrogen and oxygen that provides a P—N semiconductor system to ionize a stream of flowing steam. The device then heats the steam, through traditional methods, and accelerates the steam using a sweeping magnetic field, which results in molecular speeds of about 16,000 feet/second. The steam is subjected to increasing kinetic energy until it obtains an equivalent energy of about 13.5 electron-volts, at which point the steam dissociates. The dissociated gas is then passed through a porous platinum plug, which serves as a catalyst, to impart the accumulated kinetic energy to the resultant stable forms of hydrogen and oxygen. This invention suffers from the same problem of supplying heat to the water despite compensating by accelerating the steam flow through the use of the magnetic field. Heat generation is generally inefficient and dependent upon nonrenewable sources like fossil fuels.
[0013] Others have attempted to circumvent such heating inefficiencies by supplementing the addition of heat with chemical reactions, such as Baldwin, U.S. Pat. No. 6,899,862 B2. Baldwin describes a method of thermochemically dissociating water. Baldwin prefers the use of an aqueous solution of sodium hydroxide and a disassociation-initiating material such as metallic aluminum. It is thought that the sodium hydroxide solution contacts the metallic aluminum and releases hydrogen from water through a reduction-oxidation reaction. The free hydrogen is then extracted by processes well-known in the art. This invention suffers from a deficiency not present in the currently disclosed invention in that the process reaction will result in the using up of the sodium hydroxide solution and the metallic aluminum. This will result in increasing reaction inefficiencies throughout time and require the replenishment of these materials, which will increase overall hydrogen production costs. Also, a deterrent to use of thermochemical processes is the creation of toxic or dangerous materials upon degradation of the catalyst, which raises both health and economic concerns. Such is the failure of thermochemical disassociation of water.
[0014] Another innovative attempt at dissociating water is disclosed in Leach, U.S. Pat. No. 4,272,345. Leach teaches the use of heat exchangers, taking advantage of heat that would otherwise be wasted, to dissociate the water into hydrogen and oxygen. However, waste heat from normal chemical and industrial processes is insufficient to dissociate water by itself. Leach overcomes this limitation by the addition of a chemical process much as described above in Baldwin. Leach uses a different metallic catalyst, manganese oxide, but results in the same sequestration of oxygen. This technique suffers from the same deficiencies as Baldwin in that the manganese oxide will be used up and will require replenishment. In addition to the metallic catalyst, Leach teaches the use of a host and sensitizer material, such as a compound of calcium, tungsten, and neodymium, which emits coherent, monochromatic radiation at an absorption band of water, thus imparting energy to the molecule. Leach teaches a different technique for fully dissociating water. The Leach apparatus and method applies very high intensity infrared radiation to steam produced from a series of heat exchangers to excite the polar, covalent bonds of the already energetic water molecules. This further excitation results in the disassociation of the steam water to hydrogen and oxygen. A resonant cavity and high pass filtering film arrangement may be employed to shift the very high intensity infrared radiation into the ultraviolet frequency range to further excite the water molecules. The Leach patent fails in general commercial viability in that it requires a source of heat sufficient to transform water into steam outside of the disclosed techniques. The conservation of heat aspect of the Leach patent is impressive but is inappropriate for the uses of the currently-disclosed invention.
[0015] A non-hydrogen producing invention, but one that is still within the art, is disclosed by Kim, U.S. Pat. No. 6,443,725 B1. Kim discloses a heat generating apparatus, for use in commercial heating, that utilizes the cyclic combustion of Brown gas. Kim discloses that Brown gas is a gas generated in the electrolytic structures of oxyhdrogen gas generators as in Korea Utility Model Registration No. 117445, Korean Industrial Design Registration Nos. 193034, 193035, 19384266, and 191184, and Japan Utility Model Registration No. 3037633. This invention, through its dependency upon an electrolytically produced fuel, suffers from the inefficiencies associate with such fuel production as discussed above. Brown gas is disclosed as a mixture of gas that includes atomic hydrogen and oxygen dissociated from water. The Kim patent supplies ignited Brown gas to a semi-sealed combustion chamber, which has only an exhaust port. The ignited Brown gas heats the chamber to over 1000° C. through the disassociation process and teaches that the dissociated gas then recombines to water. The gaseous water is then dissociated again by the infrared rays radiated from the heated chamber walls. This patent utilizes the cyclic nature of dissociated water but fails to disclose recognize the importance of such a reaction. This patent also fails to produce mechanical work from the heat that is generated.
[0016] The current invention is superior to and distinct from the above-disclosed inventions in several ways. The current invention can use a conventional counter-current flow heat exchanger to transfer the heat associated with the disassociation and recombination of water in order to produce steam, which has many well-known, workable uses. The current invention also produces a gaseous mixture that can be used to drive a standard hydrogen fuel cell. The invention herein disclosed also produces a stable, circular, surface reaction from an abundantly available source, namely water, which can produce both usable hydrogen and oxygen and usable energy for work.
BRIEF SUMMARY OF THE INVENTION
[0017] The current invention relates to an apparatus and method for dissociating water producing a resultant gaseous mixture composed of monatomic hydrogen (H + ), monatomic oxygen (O 2− ), diatomic hydrogen (H 2 ), diatomic oxygen (O 2 ), hydroxyl (OH − ), and water (H 2 O) and energy using ultra-high temperature cyclic thermal disassociation. Use of the apparatus may begin by igniting an initial mixture of dissociated water and aiming the stream produced at a target material within a reactor tube. The flow of the gaseous mixture entering the reactor tube is controlled by a valve, which also serves to control the temperature of the reaction. The initial mixture of dissociated water will have a greater concentration of monatomic hydrogen and monatomic oxygen and is produced by any of the well-known methods in the art. An arc or laser can be used to ignite the stream of gaseous mixture into a plasma-like state. The arc or laser may be maintained throughout the process, which increases the overall efficiency of production of the resultant gaseous mixture and energy, or the arc or laser may be ceased while still producing the resultant gaseous mixture and energy.
[0018] The stream of the gaseous mixture is directed through a reactor tube at a target material creating a reaction area at the surface of the target material. The target material preferably has a high refractory index, a demonstrated ability to resist the containment of heat, a molecular structure susceptible to the absorption of monatomic hydrogen, and a porous structure. Target materials with the desired and demonstrated qualities include aluminum silicate, platinum group metals, and graphite foam. The target material can be placed as a block within the reactor tube or can line the reactor tube.
[0019] The efficiency of the system is dependent upon the surface area of the target material because the observed phenomenon occurs about the surface of the target material. The tube configuration is the least efficient, while the U-shaped and W-shaped configurations are intermediately efficient, and while the six-pointed star configuration is yet more efficient. More efficiency can be obtained by decreasingly tapering the area through which the ignited plasma-like gaseous mixture flows from the entrance to the exit of the reactor tube as the ignited gaseous mixture travels down the length of the reactor tube.
[0020] It is thought that the monatomic hydrogen reacts with the target material, or gets trapped by the target material, and creates a region of increased positive charge. This, in turn, causes the congregation of the negatively-charged monatomic oxygen atoms. The congregation of negatively-charged monatomic oxygen results in the increased strength of the negatively-charged area, which overpowers the monatomic hydrogen's affinity for the target material such that the monatomic hydrogen and monatomic oxygen recombine to form water. Upon recombination, there is a concomitant production of energy. It is believed that the energy produced from the recombination excites the water created from a neighboring reaction and dissociates that molecule to result in monatomic hydrogen and monatomic oxygen. The resultant monatomic hydrogen and monatomic oxygen are then free to repeat the process of separation, charge congregation, and recombination to water; or, they are free to flow out of the reactor tube.
[0021] Once out of the reactor tube, the resultant mixture of dissociated gas can be used again in several configurations. It is preferred that the resultant dissociated gaseous mixture be passed through a flashback arrestor so as to both quench cool and dehydrate the product stream as well as prevent flashback and cessation of the reaction cycle. The dissociated gas mixture retains a sufficiently high concentration of hydrogen ions so that it may be used in a standard hydrogen fuel cell. The resultant gaseous mixture can also be used exclusively or in conjunction with hydrocarbon fuels as a fuel additive to run a standard internal combustion engine. Most importantly, the resultant gaseous mixture of dissociated water can be recycled such that it reenters the reactor tube and proceeds through the cyclic disassociation reaction again until being swept away. Because the resultant gaseous mixture can be recycled to combine with the initial mixture of dissociated water to supply the reactor with reactants, flow of such initial gaseous mixture may be decreased. This recirculation of the resultant gaseous mixture also indicates, and as has been shown, that the mixture can supply a second and third reactor with each reactor's need of an initial gaseous mixture of dissociated water. These second and third reactors can be arranged, either simultaneously or independently, in series or parallel configurations.
[0022] In order to take advantage of the excess heat generated by the reaction, an industry-standard heat exchanger is placed about the reactor tube. The heat generated by the reactor tube is more than sufficient to produce workable steam from the water supplied to the heat exchanger. One skilled in any art associated with the supplication of heat necessary for a reaction or phase change will recognize the utility of the disclosed invention. Also, the steam provided can be used in any number of devices that require the use of steam to provide work. The steam generated can be used in subsequent heat exchangers to provide heat for any purpose that requires the achievement of temperature change. The above-disclosed series and parallel arrangements of reactors can be designed such that the reactors can be placed in a single heat exchanger body so that the inlet flow of heat exchanger fluid can be increased to provide for increased output of steam. Also, this arrangement allows for more heat to be supplied to chemical reactions to increase the reactivity and drive the reaction to produce more products. The use of the heat exchanger also protects the integrity of the materials used to form the reactor tube from thermal decomposition and degradation.
[0023] Another embodiment of the current invention provides steam to the reactor tube so that the production of hydrogen, oxygen, and the resultant gaseous mixture can be increased. The steam that enters the reactor tube is excited by the heat generated by the reaction such that upon entry it dissociates. The entering, dissociating steam provides more reactants to participate in the cyclic reaction of disassociation, charge congregation, recombination, and subsequent disassociation. However, the available steam must be maintained at a sufficiently low pressure so as to not lower the reaction temperature so much so that the reaction cycle is ceased. The reaction provides enough heat to the heat exchanger to provide both the steam input into the reactor tube to provide more reactants and a product stream of steam to provide work for other independent processes. The input of steam to the reactor tube also increases the output of hydrogen, oxygen, and the resultant gaseous mixture such that the output stream of the reactor tube can provide enough gaseous mixture to be recycled as well as enough to create a product stream of hydrogen and oxygen, which can then be separated into usable hydrogen and oxygen gases using known methods or can be used in hydrogen fuel cells or combustion engines as disclosed above. The introduction of steam to the reactor tube can also provide the lone reactants for the reactor, if maintained at a sufficiently low pressure so as to not cease the reaction, so that the requirement of a recycle stream of resultant dissociated water is no longer necessary; all resultant dissociated water mixture can be diverted as products or serve as initial dissociated gaseous mixture for other reactor tubes.
[0024] The advantages of the current invention overcome the above-described art by providing an efficient, commercially viable, and clean source of energy, hydrogen, and oxygen.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0025] FIG. 1 is an isometric left perspective view of the apparatus.
[0026] FIG. 2 is a right cross-sectional view of the apparatus demonstrating tube target material configuration.
[0027] FIG. 3 is a right cross-sectional view of the apparatus illustrating a flow configuration with a recycle stream.
[0028] FIG. 4 is an isometric left perspective view of the apparatus demonstrating steam inlet tubes.
[0029] FIG. 5 a is a right cross-sectional view of the apparatus highlighting reactor flow.
[0030] FIG. 5 b is a right cross sectional view of the apparatus highlighting the heat reactor fluid flow.
[0031] FIG. 6 is an isometric left perspective view of another embodiment of the invention.
[0032] FIG. 7 a is a right cross-sectional view of the invention highlighting reactor flow streams.
[0033] FIG. 7 b is a right cross-sectional view of the invention highlighting heat exchanger fluid flow.
[0034] FIG. 8 is an isometric right perspective view of a target material in a U-shaped configuration.
[0035] FIG. 9 is an isometric right perspective view of a target material in a W-shaped configuration.
[0036] FIG. 9 a is an isometric view of the back of a target material in a W-shaped configuration.
[0037] FIG. 10 is an isometric right perspective view of target material in 6-point star configuration.
DETAILED DESCRIPTION OF THE INVENTION
[0038] FIGS. 1 through 10 depict and illustrate some particular embodiments of a device to produce hydrogen, oxygen, and workable heat from a gaseous mixture of dissociated water. It is contemplated that one skilled in the art will see that the claimed invention can take on additional embodiments not herein described. For example, the current invention is discussed as having only two baffles within the heat exchanger body, but other configurations are heat exchangers are well known and intended to fall within the scope of this claimed invention.
[0039] FIG. 1 specifically illustrates the most basic configuration of the disclosed hydrogen, oxygen, and heat generating apparatus 10 . A generally cylindrical, elongated reactor tube 11 , with inner surface 12 , outer surface 13 , generally flat annular front edge 14 , and generally flat annular back edge surface 15 , is shown encased in generally cylindrical, elongated heat exchanger body 19 . Heat exchanger body 19 is of greater radius than and is arranged concentrically with reactor tube 11 and comprises inner surface 20 , outer surface 21 , generally circular front hole 166 , generally circular back hole 170 , front heat exchanger cap 22 , back heat exchanger cap 23 , and heat exchanger flow connectors 24 and 25 . Heat exchanger caps 22 and 23 are generally flat circular discs containing holes therethrough for the acceptance of reactor tube 11 . Front heat exchanger cap connects to heat exchanger body 19 at front corner 159 . Front heat exchanger cap 22 contacts and connects to outer surface 13 of reactor tube 11 at front corner 157 . Back heat exchanger cap 23 connects to heat exchanger body 19 at back corner 160 . Back heat exchanger cap 23 contacts and connects to outer surface 13 of reactor tube 11 at back corner 158 . Front hole 166 extends through heat exchanger body 19 near front heat exchanger cap 22 while back hole 170 extends through heat exchanger body 19 near back heat exchanger cap 23 .
[0040] A gaseous mixture of dissociated water is directed through the entry of reactor tube 11 as defined by inner surface 12 and bound by front edge surface 14 . Generally cylindrical left ignition tube 16 and generally cylindrical right ignition tube 17 are attached to reactor tube 11 and allow for an ignition source to be provided across reactor tube 11 so as to ignite the gaseous mixture of dissociated water. Left ignition tube 16 is attached to reactor tube 11 about generally circular hole 31 at corner 161 . Right ignition tube 17 is attached to reactor tube 11 about generally circular hole 32 at corner 162 . Holes 31 and 32 in reactor tube 11 provide access to the gaseous mixture of dissociated water. Once ignited, the stream is directed at a target material 18 , shown here in a U-shaped configuration as a generally elongated rectangular prism. Target material 18 can take on other configurations as shown in FIG. 2 as target material 33 in generally cylindrical, elongated tube configuration. Target material is constructed of a material with a high refractory index, high heat capacity, a porous structure, and the ability to absorb monatomic hydrogen. Functional materials have been found to include aluminum silicate, platinum group metals, and graphite foam. Target material 18 of FIG. 1 is simply placed within reactor tube 11 so that the ignited stream of dissociated water may pass over it.
[0041] Target material 18 absorbs monatomic hydrogen from the ignited gaseous mixture of dissociated water stream in such a quantity to build localized regions of positive charge. This polarization of target material 18 attracts monatomic oxygen to congregate about the surface of target material 18 . The monatomic oxygen builds an area of negative charge about target material 18 until the charge is strong enough to pull the monatomic hydrogen from target material 18 , and the monatomic hydrogen and monatomic oxygen condense to form water molecules. The condensation to water molecules releases energy which can be absorbed by neighboring molecules or be transferred to reactor tube 11 , through inner surface 12 and outer surface 13 , to heat fluid contained in heat exchanger body 19 . The dissociated water molecules are thought to generally participate in the following cyclic reaction:
[0000] 2H − +O 2− →H 2 O+heat
[0000] H 2 O+heat→2H − +O 2−
[0042] Target material 18 provides the opportunity for the charged elements to separate and congregate charge. In words, the dissociated water contacts target material 18 , then the monatomic hydrogen congregates on or in target material 18 and creates a region of positive charge. Monatomic oxygen congregates about the surface of target material 18 to create a region of negative charge. The strengths of the separated regions of charge increase such that they overcome the monatomic hydrogen's affinity for target material 18 to result in recombination of the monatomic hydrogen and monatomic oxygen to condense into water molecules, thereby releasing energy. The energy then contributes to the disassociation of the resultant water molecules, which can then repeat the cycle of charge congregation, recombination, energy release, and disassociation. The gaseous mixture can continue to travel the length of reactor tube 11 to the exit of reactor tube 11 as defined by inner surface 12 and bounded by back edge surface 15 .
[0043] Continuing in FIG. 1 , heat exchanger body 19 is configured about reactor tube 11 so as to pass fluid over outer surface 13 of reactor tube 11 while being bound by inner surface 20 of heat exchanger body 19 , generally circular front hole 166 , generally circular back hole 170 , front heat exchanger cap 22 , and back heat exchanger cap 23 . The heat generated by the reaction within reactor tube 11 passes through inner surface 12 and outer surface 13 to be transferred to the fluid passing through heat exchanger body 19 . Heat exchanger body 19 is constructed with inner surface 20 , outer surface 21 , front heat exchanger cap 22 , and back heat exchanger cap 23 . Heat exchanger fluid flows through both front heat exchanger flow connector 24 and back heat exchanger flow connector 25 . Both flow connector 24 and flow connector 25 are generally cylindrical elongated tubes. Flow connector 24 comprises outer edge 163 , which connects to a flow inlet stream (not shown), and inner edge 164 , which connects to heat exchanger body 19 about hole 166 at corner 165 . Flow connector 25 comprises outer edge 167 , which connects to a fluid outlet (not shown), and inner edge 168 , which connects to heat exchanger body 19 about hole 170 at corner 169 . Within heat exchanger body 19 and about reactor tube 11 are baffles 26 and 27 . Baffles 26 and 27 are generally flat and semi-circular and extend perpendicular to the longitudinal axes of generally elongated cylindrical concentric heat exchanger tube 19 and reactor tube 11 . More specifically, front baffle 26 extends from and contacts inner surface 20 of heat exchanger body 19 at connection 171 . Front baffle 26 extends to contact outer surface 13 of reactor tube 11 at connection 172 . Front baffle extends beyond reactor tube 11 so as to drive the fluid within completely about reactor tube 11 . Back baffle 27 extends from and contacts inner surface 20 of heat exchanger body 19 at connection 173 . Back baffle 27 extends to contact outer surface 13 of reactor tube 11 at connection 174 . Back baffle extends beyond reactor tube 11 so as to drive the fluid within completely about reactor tube 11 . The heat exchanger's fluid's path is directed by inner surface 20 and heat exchanger baffles 26 and 27 , and bounded by heat exchanger caps 22 and 23 .
[0044] The heat exchanger's fluid's flow may be concurrent, such that the fluid enters at a lower temperature through front heat exchanger fluid connector 24 , travels the length of reactor tube 11 about baffles 26 and 27 , respectively, and exits through back heat exchanger fluid connector 25 at a higher temperature; or, the heat exchanger's fluid's flow may be counter-current such that the fluid enters at a lower temperature through back heat exchanger fluid connector 25 , travels the length of reactor tube 11 about baffles 27 and 26 , respectively, and exits through front heat exchanger fluid connector 24 at a higher temperature. Preferably and as described, the heat exchanger's fluid flows in a counter-current design so as to increase the efficiency of heat transfer from reactor tube 11 to the heat exchanger fluid. The heat exchanger fluid can be chemical reactants that require heat to increase the efficiency of the reaction or can be water to accomplish the phase transition to steam. Also, hydrogen, oxygen, and heat generating apparatus 10 can be utilized for any of the traditional uses of previously-known heat exchangers.
[0045] FIG. 2 most effectively demonstrates target material 33 's tube configuration as well as provides a two-dimensional cross-sectional view of hydrogen, oxygen, and heat generating apparatus 10 . The embodiment in FIG. 2 is the generally the same as described above, but that target material 33 is used. More specifically, generally cylindrical elongated reactor tube 11 extends concentrically through generally cylindrical elongated tube heat exchanger body 19 with front heat exchanger cap 22 , back heat exchanger cap 23 , front baffle 26 , back baffle 27 , front fluid connector 24 and back fluid connector 25 . Reactor tube 11 extends through and connects to front heat exchanger cap 22 and back heat exchanger cap 23 . Heat exchanger fluid flows counter-currently through heat exchanger body 19 , bound by inner surface 20 and directed about outer surface 13 of reactor tube 11 by baffles 27 and 26 , entering through fluid connector 25 and exiting from fluid connector 24 .
[0046] Target material 33 comprises a generally cylindrical elongated tube with inner surface 175 , outer surface 176 , front edge 177 , and back lip 178 . Back lip 178 of target material 33 comprises outer edge 179 , front surface 180 , and back surface 181 . Target material 33 extends through and contacts inner surface 12 of reactor tube 11 with outer surface 176 . Target material 33 extends from a location in reactor tube 11 posterior to the location of holes 31 and 32 (not shown) out the exit of reactor tube 11 as defined by inner surface 12 and bound by generally flat, annular back edge 15 . Back lip 178 extends radially outward such that front surface 180 of back lip 178 , extending generally perpendicularly from outer surface 176 to outer edge 179 , contacts back edge 15 of reactor tube 11 . A gaseous mixture of dissociated water enters generally cylindrical elongated reactor tube 11 , which is lined by target material 33 , through the entrance to reactor tube 11 as defined by inner surface 12 and bound by front edge 14 of reactor tube 11 . Generally circular hole 31 extends through reactor tube 11 to allow for an ignition device to ignite the stream of gaseous mixture of dissociated water. In this figure, hole 31 is associated with left ignition tube 16 , which cannot be seen. An arc, laser, or other ignition device is allowed access to ignite the stream of gaseous mixture of dissociated water through holes 31 and 32 (not shown). The ignited mixture is directed down the center of target material 33 and reactor tube 11 . The cyclic reactions of charge congregation, recombination and condensation, energy release, and re-disassociation take place throughout the length of target material 33 , at target material surface 175 , and reactor tube 11 , but have been found to be more prominent at node points along the length of inner surface 175 of target material 33 . For example, through thermal imaging, it has been shown that for a ½ inch diameter reactor tube 11 and a flow rate of 2 liters per minute, the reaction is strongest at 1.5 inch increments down the length of reactor tube 11 . FIG. 2 also clearly shows a two-dimensional representation of the path of the heat exchanger fluid through heat exchanger fluid connector 25 , about outer surface 13 of reactor tube 11 , about baffles 27 and 26 , respectively, and exiting out of heat exchanger fluid connector 24 . More specifically, fluid enters connecter 25 at outer edge 167 and flows through to inner edge 168 , entering heat exchanger body 19 . Once inside, the fluid travels past reactor tube 11 , bounded by back heat exchanger cap 23 and baffle 27 . The fluid then takes a u-turn towards front heat exchanger cap 22 about baffle 27 , due to the boundary of inner surface 20 of heat exchanger body 19 , so as to pass over outer surface 13 of reactor tube 11 for a second time. The fluid completely passes over outer surface 13 of reator tube 11 to take another forward u-turn toward front heat exchanger cap 22 about baffle 26 , due again to the boundary of inner surface 20 of heat exchanger body 19 . The fluid then completely passes over outer surface 13 of reactor tube 11 for a third time to exit heat exchanger body 19 through hole 166 . The fluid finally flows out through connector 24 from inner edge 164 to outer edge 163 . Throughout the three passes of the heat exchanger fluid about the outer surface 13 of reactor tube 11 , heat is transferred from reactor tube 11 to the heat exchanger fluid throughout the length of reactor tube 11 . Again, inner surface 20 of heat exchanger body 19 and front and back heat exchanger caps 22 and 23 , respectively, bound the heat exchanger fluid flow.
[0047] FIG. 3 discloses and defines useful streams associated with hydrogen, oxygen, and heat generating apparatus 10 with resultant gaseous mixture of dissociated water recycle stream 38 . For purposes of example, reactor tube 11 contains target material 33 in generally cylindrical elongated tube configuration. Reactor input stream I 34 combines with reactor recycle stream 38 , before entering reactor tube 11 through the entrance defined by inner surface 12 and bound by front edge 14 , to form reactor input stream II 35 . Reactor recycle stream 38 's flow rate can be equal to zero such that the only source of reactants is reactor input stream I 34 . Reactor input streams I and II, 34 and 35 , respectively, and reactor recycle stream 38 are composed of a gaseous mixture of dissociated water containing mostly monatomic hydrogen and monatomic oxygen. Reactor input stream II 35 is ignited by an arc or laser through holes 31 and 32 (not shown) in reactor tube 11 and directed down the center of reactor tube 11 and target material 33 . Reactor output stream 36 can be split, after exiting reactor tube 11 and back lip 178 of target material 33 and preferably flowing through a flashback arrestor (not shown), into reactor product stream 37 and reactor recycle stream 38 , all of which generally have the same composition of monatomic hydrogen, monatomic oxygen, and associated gasses. Reactor output stream 36 will generally have a higher water content than the other streams such that it is preferable to flow reactor output stream 36 through a flashback arrestor to remove such water molecules. Reactor product stream 37 's flow rate can be decreased so that at least a portion of reactor output stream 36 is recycled through reactor recycle stream 38 .
[0048] FIG. 4 discloses and illustrates the addition of generally cylindrical elongated steam inlet tubes to reactor tube 11 . Steam inlet tubes 41 and 42 introduce steam to reactor tube 11 at locations determined as the specific nodes of maximum reaction, dependent upon inlet flow rate of the dissociated gaseous mixture. The specific locations of the nodes can be easily observed using infrared heat detection technology of common knowledge. Specifically, First steam inlet tube 41 introduces steam to reactor tube 11 at a distance between the entrance to reactor tube 11 as defined by inner surface 12 and bound by front edge 14 and the front baffle 26 . Second steam inlet tube 42 introduces steam to reactor tube 11 at a distance between front baffle 26 and back baffle 27 . First steam inlet tube 41 extends from outer edge 182 to inner edge 183 . First steam inlet tube 41 extends through and contacts the edge of hole 43 in heat exchanger body 19 at connection 184 . First steam inlet tube 41 continues through the heat exchanger fluid to hole 45 in reactor tube 11 and inner edge 183 contacts reactor tube 11 about hole 45 at connection 185 . Second steam inlet tube 42 extends from outer edge 186 to inner edge 187 . Second steam inlet tube 42 extends through and contacts hole 44 in heat exchanger body 19 at connection 188 . Second steam inlet tube 42 continues through the heat exchanger fluid to hole 46 in reactor tube 11 , and inner edge 187 contacts reactor tube 11 about hole 46 at connection 189 . Target materials 58 and 59 are placed, in U-shaped configuration, to accept steam flowing through steam inlet tubes 41 and 42 , respectively. Such placement of target materials 58 and 59 in reactor tube 11 , such that target materials 58 and 59 are placed directly over holes 45 and 46 , respectively, require that holes must be bored through each target material so as to provide a path through target materials 58 and 59 for the provided steam. The same can be accomplished by moving the placements of target materials 58 and 59 forward or backward so that the incoming steam has direct access to the ignited flow of the incoming gaseous mixture dissociated water. Or, the same may be accomplished by placing the U-shaped target materials opposite the incoming steam so as to accept the incoming steam in the channel defined within the U-shaped configuration, i.e. where the reaction is taking place on the inside surface of the U-shape.
[0049] FIG. 4 discloses and demonstrates two substantial elements of the claimed invention. First, the combustion and recombination of water into a dissociated gaseous mixture back into water is a cyclic reaction that can take place at several locations within one reactor tube 11 . Here, target material 58 and target material 59 are illustrated and provide more surface area for the cyclic reactions to take place, resulting in increased heat generation. The addition of multiple target materials in a U-shaped configuration lead to the design of target material 33 in tube configuration to line reactor tube 11 of FIG. 2 and results in increased heat generation. The increased heat generation will cause more heat to be transferred to the fluid flowing through heat exchanger body 19 , about baffles 26 and 27 . Thus, if hydrogen, oxygen, and heat generating apparatus 10 is set up to impart heat to water to change the water to steam, the input flow rate through either front heat exchanger flow tube 24 or back heat exchanger flow tube 25 can be increased so as to turn more water into steam and thereby produce more energy to accomplish more work. FIG. 4 only discloses two locations for steam inlet and target material placement, but fewer locations are possible as disclosed above and more locations can be added to increase heat production and possible work.
[0050] Second, FIG. 4 discloses and illustrates the addition of steam to reactor tube 11 . Two locations are shown, but again, fewer or more locations are possible. The import of the introduction of steam can be more easily understood in examining FIGS. 4 , 5 a , and 5 b in conjunction. Referring to FIG. 5 a , reactor input stream I 34 combines with reactor recycle stream 38 , before entrance into reactor tube 11 , to form reactor input stream II 35 . The composition of each of streams 34 , 38 , and 35 is generally the same and is a gaseous mixture of dissociated water containing almost exclusively monatomic hydrogen and monatonic oxygen. Reactor input stream II 35 enters reactor tube 11 through an entry as defined by inner surface 12 and bound by front edge surface 14 . An arc or laser is activated between holes 31 and 32 in reactor tube 11 , through left ignition tube 16 and right ignition tube 17 (not shown), respectively, so as to ignite the flowing gaseous mixture of dissociate water from reactor input stream II 35 . Ignited reactant flow stream 52 is directed at target material 58 (shown in FIG. 4 ), which begins the cyclic reaction disclosed above. However, during the condensation step of the cyclic reaction, there is a concomitant pressure drop that allows steam flow stream 53 to be drawn through steam inlet tube 41 to increase the reaction production by providing more water molecules to participate in the cyclic reaction process. Ignited reactant flow stream 52 combines with steam flow stream I 53 at target material 58 . Upon entry of steam flow stream I 53 to reactor tube 11 , the steam molecules are immediately dissociated because of the available energy from the cyclic reaction process. Reactant flow stream II 54 is composed of a gaseous mixture of dissociated water, just as streams 34 , 35 , 38 , and 52 , but has an increased flow rate because of the addition of steam from steam input stream I 53 through first steam inlet tube 41 results in an increase of moles of the gaseous mixture of dissociated water. The above-described process is repeated at the location of target material 59 (shown in FIG. 4 ) and second steam inlet tube 42 . Second steam inlet tube 42 extends through hole 44 in heat exchanger body 19 to hole 46 in reactor tube 11 . Steam flow stream II 55 enters reactor tube 11 at target material 59 to combine with reactant flow stream II 54 . Reactant flow stream II 54 's cyclic reaction with target material 59 decreases the pressure within the area about target material 59 within reactor tube 11 , thereby pulling into reactor tube 11 steam flow stream II 55 . Steam flow stream II 55 provides more water molecules to dissociate, congregate charges, recombine and condense, release energy, and redissociate. Reactor product flow stream 56 has an increased flow rate, just as reactant flow stream II 54 , due to the increase of water for disassociation. Reactor product flow stream 56 then exits reactor tube 11 as reactor output stream 36 , both having the same composition of dissociated water containing mostly monatomic hydrogen and monatomic oxygen. It is preferred that reactor output stream 36 be sent to a flash back arrestor (not shown) before any secondary uses. The flash back arrestor decreases the amount of liquid water and water vapor dissolved in the gaseous mixture, quench cools the products, and prevents flashback, which would end the reaction cycle.
[0051] Just as described above with FIG. 3 , reactor output stream 36 of FIG. 5 a can be split into reactor product stream 37 and reactor recycle stream 38 , both having the same composition of dissociated water containing mostly monatomic hydrogen and monatomic oxygen. However, as shown in FIG. 5 a , the setup can be changed slightly because of the addition of steam through first and second steam inlet tubes 41 and 42 , respectively. The temperatures achieved in reactor tube 11 are sufficient to maintain the cyclic reaction and drawing of steam flow stream I 53 and steam flow stream II 55 , thereby providing new reactants in the form of steam. This addition of steam to reactor tube 11 through steam inlet tubes 41 and 42 theoretically allows for the flow rates of reactor recycle stream 38 and reactor input stream I 34 to both be set to zero while maintaining the cyclic reaction within reactor tube 11 . Thus, the only input to reactor tube 11 may be that steam as introduced through steam inlet tubes 41 and 42 . However, it has been demonstrated that steam may be produced and used in the reaction cycle and that the reactor products can obtain secondary uses. The maintenance of the cyclic reaction results in the continued generation of a gaseous mixture of dissociated water through reactor product stream 37 and generation of heat to be transferred to the heat exchanger fluid flowing through heat exchanger body 19 about baffles 26 and 27 .
[0052] FIG. 5 b discloses and highlights another novel feature of the present invention. Heat exchanger flow 57 is set up in classic counter-current design through heat exchanger body 19 about baffles 27 and 26 , respectively. Heat exchanger input stream 39 enters heat exchanger body 19 through back heat exchanger flow tube 25 . When arranged as in FIG. 5 b , heat exchanger input stream 39 is liquid water. Upon entrance to heat exchanger body 19 , input stream 39 becomes heat exchanger flow 57 . Heat exchanger flow 57 , initially liquid water, flows through heat exchanger body 19 about outer surface 13 of reactor tube 11 around baffles 27 and 26 , respectively. Heat exchanger flow 57 absorbs heat generated by the cyclic reaction within reactor tube 11 and effects a phase transition to become water vapor and is such upon exiting front heat exchanger flow tube 24 . Upon exit, heat exchanger flow 57 becomes heat exchanger output stream 40 and is now water vapor. Heat exchanger output stream 40 contains sufficient steam to supply both heat exchanger product stream 47 and heat exchanger recycle stream I 48 . Heat exchanger product stream 47 can be used for any of the well-known uses for steam, such as operating a turbine. Heat exchanger recycle stream I 48 provides the steam used as input to reactor tube 11 , through first and second steam inlet tubes 41 and 42 , respectively, to result in the increased production of hydrogen, oxygen, and heat as discussed above. Steam input stream I 51 is drawn from heat exchanger recycle stream I 48 by the decrease in pressure associated with the cyclic reaction about target material 58 . Heat exchanger recycle stream II 50 will have a decreased volume equal to that drawn by steam input stream I 51 . Steam input stream II 49 , which supplies steam to the cyclic reaction about target material 59 , draws its necessary steam from heat exchanger recycle stream II 50 . Currently, steam pressure must be low such that too much steam is not forced into reactor tube 11 so as to drive down the reactor temperature thereby ceasing the reaction.
[0053] The above disclosure results in the possibility to run hydrogen, oxygen, and heat generating device 10 , after supplying and igniting an initial quantity of gaseous mixture of dissociated water, with reactor input stream I 34 and reactor recycle stream 38 's flow rates both being set equal to zero, and only operate on input of steam to reactor tube 11 . In this configuration, dissociated water will be produced and drawn off in reactor product stream 37 through only the supplying of liquid water in heat exchanger input stream 39 . Also, enough steam is produced in heat exchanger body 19 to draw off product steam through heat exchanger product stream 47 while supplying the necessary steam through heat exchanger recycle stream I 48 .
[0054] Efficiency of the reaction is determined by the amount of available surface area on which the reaction may take place. The most simple and least efficient configuration of target material is an elongated rectangular prism. Another configuration, and more efficient, is the elongated cylindrical target material of FIG. 2 . However, more efficient and more preferable target material designs will now be described. Referring to FIG. 8 , a more efficient U-shaped configuration is illustrated. The target material is an elongated ‘U’ with square corners. Front surface 201 of U-shaped target material 200 is a generally vertical, flat ‘U’ shape such that the vertical thickness varies throughout the width of U-shaped target material 200 and that outer heights 202 and 203 are of greater vertical span than center height 204 of U-shaped target material 200 . Horizontal wall edges 205 , 206 , 207 , and 208 are all generally parallel and horizontal. Outer horizontal wall edges 206 and 207 are generally horizontal and parallel with bottom horizontal wall edge 205 and are vertically separated from bottom wall edge 205 by a distance defined by outer heights of 202 and 203 , respectively; central horizontal wall edge 208 is also horizontal and parallel with edge 205 and vertically separated from bottom wall edge 205 by a distance defined by center height 204 , which is less than outer heights 202 and 203 . Also, center height 204 is bound on the left by outer height 202 and bound on the right by outer height 203 so as to be located centrally between both outer heights 202 and 203 . Front surface 201 is also bound by outer vertical edges 209 and 210 and inner vertical edges 211 and 212 . Outer left vertical edge 209 extends vertically from bottom horizontal wall edge 205 to horizontal wall edge 206 along the distance of outer height 202 . Outer right vertical edge 210 extends vertically from bottom horizontal wall edge 205 to horizontal wall edge 207 along the distance of outer height 203 . Inner vertical edge 211 extends vertically between central horizontal wall edge 208 and horizontal wall edge 206 , and extends vertically the distance equal to the difference between the outer vertical height 202 and center height 204 . Inner vertical edge 212 extends vertically between central horizontal wall edge 208 and horizontal wall edge 207 , and extends vertically the distance equal to the difference between the outer height 203 and center height 204 . In summation and starting from the upper most right corner, outer vertical edge 210 extends vertically down for a distance equal to outer height 203 to bottom horizontal edge 205 . Bottom horizontal edge 205 extends horizontally a distance equal to the combined lengths to horizontal edges 207 , 208 , and 206 , respectively, to outer vertical edge 209 . Outer vertical edge 209 then extends vertically upward the distance equal to outer height 202 to horizontal edge 206 . Horizontal edge 206 extends inwardly to inner vertical edge 211 . Inner vertical edge 211 extends vertically downward a distance equal to the difference between outer height 202 and center height 204 to horizontal edge 208 . Horizontal edge 208 extends to inner vertical edge 212 , which extends vertically and upwardly a distance equal to the difference in outer height 203 and center height 204 to horizontal edge 207 . Horizontal edge extends horizontally outwardly to return to the uppermost right corner of front surface 201 .
[0055] Continuing in FIG. 8 , the general ‘U’ shape of front surface 201 is extended as if extruded through, along length 213 , into three dimensions, creating outer vertical surfaces 214 and 215 , horizontal bottom surface 216 , horizontal top surfaces 217 , 218 , and 219 , inner vertical surfaces 220 and 221 , and back surface 222 . All horizontal surfaces 216 , 217 , 218 , and 219 are generally parallel, while horizontal top surfaces 217 and 218 are coplanar; and all vertical surfaces 214 , 215 , 220 , and 221 are also generally parallel. Horizontal, flat surface 218 connects to and contacts vertical, flat surface 215 along corner 223 , from which vertical surface 215 extends vertically downward to corner 224 and horizontal bottom surface 216 . Horizontal bottom surface 216 extends horizontally to corner 225 , at which horizontal bottom surface 216 contacts and connects to vertical, flat surface 214 . Vertical surface 214 extends vertically and upwardly from corner 225 to corner 226 , where it contacts and connects to horizontal flat surface 217 . Horizontal flat surface 217 extends inwardly and horizontally to corner 227 , where it contacts and connects to vertical, flat surface 220 . Vertical flat surface 220 extends vertically and downwardly to corner 228 , where it contacts and connects to horizontal, flat top surface 219 . Horizontal top surface 219 extends generally horizontally from corner 228 to corner 229 , where horizontal top surface 219 connects to and contacts vertical wall 221 . Generally vertical surface 221 extends vertically and upwardly from corner 229 to corner 230 where it connects to and contacts generally flat horizontal top surface 218 , which then extends horizontally to corner 223 . Generally vertical back surface 222 has the same general shape as vertical front surface 201 as all corners, 223 , 224 , 225 , 226 , 227 , 228 , 229 , and 230 extend in a parallel manner so as to allow the flat surface walls 214 , 215 , 216 , 217 , 218 , 219 , 220 , and 221 to bound generally flat, vertical back surface 222 in the same shape as front surface 201 .
[0056] W-shaped target material configuration is illustrated in FIGS. 9 and 9 a . Generally flat, vertical front surface 271 and generally flat, vertical back surface 272 are both of a general ‘W’ shape and connected by and through generally flat surfaces 273 through 283 . The shape of W-shaped target material 270 is intended to increase the surface area with which the plasma-like ignited gaseous mixture may react. Specifically, the shape of front surface 271 is bound many edges 284 through 294 . Outer vertical edges 284 and 286 are coplanar with and parallel to inner vertical edges 288 and 293 . Bottom horizontal edge 285 is coplanar with and parallel to inner horizontal edges 289 and 292 and upper horizontal edges 287 and 294 . Inner edges 290 and 291 are neither horizontal nor vertical and define the inner peak of the general ‘W’ shape of front surface 271 . The general shape of front surface 271 is such that the vertical extensions of horizontal edges 287 and 294 above bottom horizontal edge 285 , which are equal, are greater than the vertical extensions of inner horizontal edges 289 and 292 above bottom horizontal edge 285 , which are also equal. The extensions of edges 290 and 291 above bottom horizontal edge 285 increase from initial vertical extensions equal to those of inner horizontal edges 289 and 292 to reach a greatest vertical extension above horizontal edge 285 where edges 290 and 291 meet at point 295 , the top, center of front surface 271 . However, the vertical extension of point 295 above bottom edge 285 is less than the vertical extensions of edges 287 and 294 above bottom horizontal edge 285 .
[0057] Remaining in FIG. 9 , edge 291 bounds front surface 271 and extends from point 295 outwardly and downwardly to inner horizontal edge 292 , which then continues to extend outwardly but horizontally to inner vertical edge 293 . Inner vertical edge 293 extends upwardly and vertically from inner horizontal edge 292 to upper horizontal edge 294 . Upper horizontal edge 294 extends horizontally and outwardly to outer vertical edge 284 , which extends vertically and downwardly to bottom horizontal edge 285 . Bottom horizontal edge 285 then extends inwardly and horizontally, past the center point of front surface 271 , to outer vertical edge 286 . Outer vertical edge 286 then extends vertically and upwardly from bottom horizontal edge 285 to upper horizontal edge 287 , which then extends horizontally and inwardly to inner vertical edge 288 . Inner vertical edge 288 extends vertically and downwardly from upper horizontal edge 287 to inner horizontal edge 289 , which then extends horizontally and inwardly to edge 290 . Edge 290 extends from inner horizontal edge 289 upwardly and inwardly to contact inner edge 291 at point 295 . Thus, the “W” shape of front surface 271 and W-shaped target material configuration 270 is defined.
[0058] The general shape of W-shaped target material configuration 270 is the shape of front surface 271 as if it were extruded through from two to three dimensions a distance defined by the separation between front surface 271 and back surface 272 . Such extension creates surfaces to connect front surface 271 and back surface 272 , which has a generally similar shape as front surface 271 . Generally vertical outer surface 273 extends vertically and downwardly from corner 296 to corner 297 , where it contacts and connects with generally flat and horizontal bottom surface 274 . Bottom surface 274 extends horizontally and inwardly from corner 297 to corner 298 where it contacts and connects to generally vertical outer surface 275 . Outer Surface 275 extends vertically and upwardly from bottom surface 274 and corner 298 to corner 299 , where it contacts and connects to upper horizontal surface 276 . Upper horizontal surface 276 extends inwardly and horizontally to corner 300 , where it meets generally vertical and flat inner surface 277 . Inner surface 277 extends vertically and downwardly from corner 300 to corner 301 , where it contacts and connects to inner horizontal surface 278 . Inner horizontal surface 278 extends inwardly and horizontally to corner 302 where it contacts and connects to inner point surface 279 . Inner point surface 279 extends both inwardly and upwardly from horizontal inner surface 278 to corner 303 , where it meets inner point surface 280 . Inner point surface 280 extends outwardly and downwardly from corner 303 to corner 304 where it contacts and connects to inner horizontal surface 281 . Inner horizontal surface 281 then extends outwardly and horizontally from corner 304 to corner 305 , where it contacts and connects to generally vertical and flat inner surface 282 . Inner surface 282 extends vertically and upwardly from corner 305 to corner 306 , where it contacts and connects to upper horizontal surface 283 . Upper horizontal surface 283 extends outward from corner 306 to corner 296 , where it contacts and connects to vertical outer surface 273 .
[0059] As shown specifically in FIG. 9 a , the shape of back surface 272 is bound by many edges 307 through 317 and has the same generally shape as that of front surface 271 . Outer vertical edges 272 and 309 are coplanar with and parallel to inner vertical edges 311 and 316 . Bottom horizontal edge 308 is coplanar with and parallel to inner horizontal edges 312 and 315 and upper horizontal edges 310 and 317 . Inner edges 313 and 314 are neither horizontal nor vertical and define the inner peak of the general ‘W’ shape of back surface 272 . The general shape of back surface 272 is such that the vertical extensions of horizontal edges 310 and 317 above bottom horizontal edge 308 , which are equal, are greater than the vertical extensions of inner horizontal edges 312 and 315 above bottom horizontal edge 308 , which are also equal. The extensions of edges 313 and 314 above bottom horizontal edge 308 increase from initial vertical extensions equal to those of inner horizontal edges 312 and 315 to reach a greatest vertical extension above horizontal edge 308 where edges 313 and 314 meet at point 318 , the top, center of back surface 272 . However, the vertical extension of point 318 above bottom edge 308 is less than the vertical extensions of edges 310 and 317 above bottom horizontal edge 308 .
[0060] Remaining in FIG. 9 a , edge 314 bounds back surface 272 and extends from point 318 outwardly and downwardly to inner horizontal edge 315 , which then continues to extend outwardly but horizontally to inner vertical edge 316 . Inner vertical edge 316 extends upwardly and vertically from inner horizontally edge 315 to upper horizontal edge 317 . Upper horizontal edge 317 extends horizontally and outwardly to outer vertical edge 307 , which extends vertically and downwardly to bottom horizontal edge 308 . Bottom horizontal edge 308 then extends inwardly and horizontally, past the center point of back surface 272 , to outer vertical edge 309 . Outer vertical edge 309 then extends vertically and upwardly from bottom horizontal edge 308 to upper horizontal edge 310 , which then extends horizontally and inwardly to inner vertical edge 311 . Inner vertical edge 311 extends vertically and downwardly from upper horizontal edge 310 to inner horizontal edge 312 , which then extends horizontally and inwardly to edge 313 . Edge 313 extends from inner horizontal edge 312 upwardly and inwardly to contact inner edge 314 at point 318 .
[0061] The most preferred and the expectedly most efficient embodiment of the target material is the star configuration, as shown in FIG. 10 . Star-configuration target material 231 is generally an elongated cylinder with a star-shaped hole extending centrally through and down the length of the cylinder. The configuration as shown exhibits a star containing six points. The elongated star-shaped passageway and the elongated cylindrical material are concentric. Also, star-configuration target material 231 has both generally flat and vertical front and back surfaces, 232 and 233 , respectively. Both front surface 232 and back surface 233 are generally circular and bounded by and connected to outer cylinder surface 234 at corners 235 and 236 , respectively. Moreover, both front surface 232 and back surface 233 are perpendicular to the central axis of the elongated cylinder such that star-configuration target material 231 is generally an elongated, right cylinder. Outer cylinder surface 234 connects front surface 232 to back surface 233 so as to make one continuous outer surface 234 with corners 235 and 236 . The elongated cylinder is solid but for the star-shape passageway, through which the excited plasma-like gaseous mixture is directed, as defined by inner surfaces 237 , 238 , 239 , 240 , 241 , 242 , 243 , 244 , 245 , 246 , 247 , and 248 . Each inner surface 237 through 248 is in itself an elongated rectangle connected to each neighboring rectangle along the long edges so as to form an elongated star shape. Each of the short edges contacts either front surface 232 or back surface 233 so as to produce a star-shaped hole in each. More specifically, the star-shaped hole in front surface 232 is bounded by front short edge 237 a of inner surface 237 extending from inner point 260 to outer point 249 ; and front short edge 238 a of inner surface 238 extending from outer point 249 inwardly to inner point 250 . From inner point 250 , front short edge 239 a of inner surface 239 extends outwardly to outer point 251 ; and front edge 240 a of inner surface 240 extends inwardly from outer point 251 to inner point 252 . From inner point 252 , front short edge 241 a of inner surface 241 extends outwardly to outer point 253 ; and front edge 242 a of inner surface 242 extends inwardly from outer point 253 to inner point 254 . From inner point 254 , front short edge 243 a of inner surface 243 extends outwardly to outer point 255 ; and front edge 244 a of inner surface 244 extends inwardly from outer point 255 to inner point 256 . From inner point 256 , front short edge 245 a of inner surface 245 extends outwardly to outer point 257 ; and front edge 246 a of inner surface 246 extends inwardly from outer point 257 to inner point 258 . From inner point 258 , front short edge 247 a of inner surface 247 extends outwardly to outer point 259 ; and front edge 248 a of inner surface 248 extends inwardly from outer point 259 to inner point 260 . All outer points, 249 , 251 , 253 , 255 , 257 , and 259 , are closer to corner 235 than they are to the center of surface 232 , and each angle at each point is equal to each other angle at each other outer point. Also, all inner points, 250 , 252 , 254 , 256 , 258 , and 260 , are closer to the center of surface 232 than they are to corner 235 and each angle at each inner corner is equal to each other angel at each other inner corner. Throughout the length of the cylinder, inner surface 237 extends outwardly toward outer surface 234 to contact inner surface 238 at outer point 249 . Inner surface 238 then extends inwardly toward the center of the elongated cylinder to contact inner surface 239 at inner point 250 . Inner surface 239 then extends outwardly to contact inner surface 240 at outer point 251 . Inner surface 240 extends inwardly to contact inner surface 241 at inner point 252 . Inner surface 241 then extends outwardly to contact inner surface 242 at outer point 253 . Inner surface 242 then extends inwardly to contact inner surface 243 at inner point 254 . Inner surface 243 then extends outwardly to contact inner surface 244 at outer point 255 . Inner surface 244 then extends inwardly to contact inner surface 245 at inner point 256 . Inner surface 245 then extends outwardly to contact inner surface 246 at outer point 257 . Inner surface 246 then extends inwardly to contact inner surface 247 at inner point 258 . Inner surface 247 then extends outwardly to contact inner surface 248 at outer point 259 . Inner surface 248 then extends inwardly to contact inner surface 237 at inner point 260 . At all inner points and outer points, 249 through 260 , inner surfaces 237 through 248 contact both of their two neighbors, one neighbor along each long side of the elongated inner surfaces 237 through 248 , so as to form the star-shaped passageway through which the excited gaseous mixture is directed.
[0062] Continuing in FIG. 10 , the star-shaped hole in back surface 233 is bounded by all the back short edges, 237 b through 249 b , of inner surfaces 237 through 249 , and more specifically, back short edge 237 b of inner surface 237 extending from inner point 260 to outer point 249 ; and back short edge 238 b of inner surface 238 extending from outer point 249 inwardly to inner point 250 . From inner point 250 , back short edge 239 b of inner surface 239 extends outwardly to outer point 251 ; and back edge 240 b of inner surface 240 extends inwardly from outer point 251 to inner point 252 . From inner point 252 , back short edge 241 b of inner surface 241 extends outwardly to outer point 253 ; and back edge 242 b of inner surface 242 extends inwardly from outer point 253 to inner point 254 . From inner point 254 , back short edge 243 b of inner surface 243 extends outwardly to outer point 255 ; and back edge 244 b of inner surface 244 extends inwardly from outer point 255 to inner point 256 . From inner point 256 , back short edge 245 b of inner surface 245 extends outwardly to outer point 257 ; and back edge 246 b of inner surface 246 extends inwardly from outer point 257 to inner point 258 . From inner point 258 , back short edge 247 b of inner surface 247 extends outwardly to outer point 259 ; and back edge 248 b of inner surface 248 extends inwardly from outer point 259 to inner point 260 .
[0063] Remaining in FIG. 10 , the star-configuration target material 231 is illustrated in tube configuration, the length of which may be short or extend the entire length of a reactor tube. However, if any tube configuration target material passes over a steam inlet tube to a reactor, there must be a hole in the target material through which the steam may access the interior of the tube and the ignited stream of gaseous dissociated water, where the reaction is taking place. In FIG. 10 , such hole is defined by outer edge 261 , inner surface 262 , and inner edge 263 . Outer edge 261 defines an orifice or aperture in outer surface 234 so as to allow steam to pass from a steam inlet tube through target material 231 , past outer edge 261 in outer surface 234 , bound by inner surface 262 , past inner edge 263 , and into the center of star configuration target material 231 , where the reaction is taking place. In this configuration and as shown, outer edge 261 is a generally circular edge in outer surface 234 . Inner surface 262 forms generally an elongated, right cylinder through target material 231 and contacts and connects to outer surface 234 at and about outer edge 261 . Inner surface 262 extends through star configuration target material 231 and contacts and connects to inner surfaces 248 , 237 , 238 , and 239 at inner edge 263 so as to complete the aperture through target material 231 and allow for the incoming steam to have access to the ignited gaseous stream of dissociated water.
[0064] Now referring to FIG. 6 , hydrogen, oxygen, and heat generating device 100 is another embodiment of the presently disclosed invention containing three reactor tubes, which can be arranged in series or parallel configuration, enclosed in a single heat exchanger body. The reactor tubes are arranged in this manner so as to increase the production of hydrogen, oxygen, and heat. Reactor tube I 101 with inner surface 102 , outer surface 103 , front surface edge 104 , and back surface edge 105 is centrally located in heat exchanger body 123 . Reactor tube I 101 extends through heat exchanger body 123 , and more specifically, outer surface 103 of reactor tube I 101 connects to and extends through front heat exchanger cap 126 at edge 320 . Reactor tube I 101 also extends through baffles 130 and 131 and outer surface 103 of reactor tube I 101 connects and extends through baffles 130 and 131 through edges 322 and 323 respectively. Reactor tube I 101 extends through back heat exchanger cap 127 and outer edge 103 of reactor tube I 101 connects to and extends through edge 321 . Reactor tube I 101 also contains left and right ignition tubes 106 and 107 , respectively, to provide access for an ignition device to the flowing mixture of dissociated water, connected to reactor tube I 101 about edges 324 and 325 , respectively. Again, the stream is directed at target material 108 , which provides the surface for the cyclic reaction and draws steam through first steam inlet tube 132 , through the entrance to reactor tube I 101 as defined by inner surface 102 and bound by front edge 104 of reactor tube I 101 . It should be noted that, with respect to all reactor tubes, the target material can be presented in a U-shape, W-shape, tube, or six-pointed star configurations, or any other that provides a sufficient surface to maintain the cyclic reaction of disassociation of steam, charge congregation, recombination, energy release, and redisassociation. First steam inlet stream 132 extends through and connects to hole 134 in heat exchanger body 123 , through the heat exchanger fluid into reactor tube I 101 through hole 136 in reactor tube 101 . The reaction takes places as described above with regard to hydrogen, oxygen, and heat generating device 10 . FIG. 6 depicts a block configuration of target material in which two generic blocks are provided, target materials 108 and 157 . Target material 157 is located so as to accept steam from second steam inlet tube 133 , which extends through and connects to hole 135 in heat exchanger body 123 , through the heat exchanger fluid, into reactor 101 about hole 137 . Again, the above-disclosed reaction takes place about target material 157 , producing more gaseous mixture of dissociated water to exit reactor tube 101 through an exit defined by inner surface 102 and bound by back surface edge 105 of reactor tube 101 .
[0065] Reactor tube II 109 is defined by inner surface 110 , outer surface 111 , front edge surface 112 , and back edge surface 113 . A gaseous mixture of dissociated water enters reactor tube II 109 through an entry defined by inner surface 110 and bound by front edge surface 112 . Reactor tube II 109 extends through heat exchanger body 123 located generally above the position of reactor tube I 101 , and more specifically, outer surface 111 of reactor tube II 109 connects to and extends through front heat exchanger cap 126 at edge 326 . Reactor tube II 109 also extends through baffles 130 and 131 and outer surface 111 of reactor tube II 109 connects and extends through baffles 130 and 131 through edges 328 and 329 , respectively. Reactor tube II 109 extends through back heat exchanger cap 127 and outer edge 1111 of reactor tube II 109 connects to and extends through edge 327 . Reactor tube II 109 also contains left and right ignition tubes 114 and 115 , respectively, to provide access for an ignition device to the flowing mixture of dissociated water, connected to reactor tube II 109 about edges 330 and 331 , respectively. FIG. 6 does not show steam inlet tubes provided to reactor 11 , but one skilled in the art would readily see that steam could be provided to increase hydrogen, oxygen, and heat production. A gaseous mixture of dissociated water exits reactor tube II 109 through an exit defined by inner surface 111 and bound by back edge surface 113 .
[0066] Hydrogen, oxygen, and heat generating apparatus 100 also contains reactor tube III 116 , located directly below reactor tube I 101 , which is defined by inner surface 117 , outer surface 118 , front edge surface 119 , and back edge surface 120 . A gaseous mixture of dissociated water enters reactor tube III 116 through an entry defined by inner surface 117 and bound by front edge surface 119 . Reactor tube III 116 extends through heat exchanger body 123 , and more specifically, outer surface 118 of reactor tube III 116 connects to and extends through front heat exchanger cap 126 at edge 332 . Reactor tube III 116 also extends through baffles 130 and 131 and outer surface 118 of reactor tube III 116 connects and extends through baffles 130 and 131 through edges 334 and 335 , respectively. Reactor tube III 116 extends through back heat exchanger cap 127 and outer edge 118 of reactor tube III 109 connects to and extends through edge 333 . Reactor tube III 116 also contains left and right ignition tubes 121 and 122 , respectively, to provide access for an ignition device to the flowing mixture of dissociated water, connected to reactor tube III 116 about edges 336 and 337 , respectively. The gaseous mixture of dissociated water is ignited by an arc or laser, which extends across the stream through left and right ignition tubes 121 and 122 , respectively. The ignited stream of dissociated water is directed at target material 159 , at which the cyclic reaction takes place as disclosed above. FIG. 6 does not show steam inlet tubes provided to reactor III, but one skilled in the art would readily see that steam could also be provided to reactor tube 116 in order to increase hydrogen, oxygen, and heat production. A gaseous mixture of dissociated water exits reactor tube III 116 through an exit defined by inner surface 118 and bound by back edge surface 120 .
[0067] Reactor tube I 101 , reactor tube II 109 , and reactor tube 116 are contained within generally elongated rectangular prism heat exchanger body 123 , with inner surface 124 , outer surface 125 , front heat exchanger cap 126 , and back heat exchanger cap 127 . Heat exchanger body 123 also contains elongated cylindrical front heat exchanger flow tube 128 , located on top of heat exchanger body 123 and nearest the entrances to the reactor tubes, connected to outer surface 125 at edge 338 and about hole 339 , and elongated cylindrical back heat exchanger flow tube 129 , located on bottom of heat exchanger body 123 and nearest the exits of the reactor tubes, connected to outer surface 125 at edge 340 and about hole 341 . Heat exchanger body 123 also contains baffles 130 and 131 , connected to inner surface 124 of heat exchanger body 123 at connections 342 and 343 , respectively. Connection 342 extends about the about the top portions of inner surface 124 so that fluid flow may be directed down over reactor tube II 109 , reactor tube I 101 , and reactor tube 116 , respectively in that order, and flow back up on the other side of baffle 130 . Connection 343 extends about the bottom portions of inner surface 124 so as to direct fluid flow up over reactor tube III 116 , reactor tube I 101 , and reactor tube II 109 , and back down again on the other side of baffle 131 . The fluid flowing through heat exchanger body 123 can be run concurrently or counter-currently with respect to the flow within the reactor tubes. In a counter-current arrangement, heat exchanger fluid would enter heat exchanger body 123 through back heat exchanger flow tube 129 , flow about outer surfaces 103 , 111 , and 118 of reactor tubes I 101 , II 109 , and III 116 . The heat exchanger fluid would flow about the reactor tubes around baffles 131 and 130 , respectively, all the while absorbing heat from the reactor tubes, until the heat exchanger fluid exits heat exchanger body 123 through front heat exchanger flow tube 128 . Again, the heat exchanger fluid can be any chemical reactants or water transforming from liquid to vapor.
[0068] FIGS. 7 a and 7 b disclose and illustrate one stream configuration of hydrogen, oxygen, and heat generating device 100 , in which reactor tube I 101 is arranged in series with both reactor tubes II 109 and III 116 , which are arranged in parallel configuration. One skilled in the art would readily realize multiple similar configurations such as a complete series arrangement in which reactor tube I 101 produces reactants for reactor tube II 109 that then produces reactants for reactor tube III 116 . Reactor tube I input stream 138 enters reactor tube I and is ignited to produce reactant flow stream I 139 . Reactant flow stream I 139 is combined with steam from steam input stream I 155 to react as disclosed above about a target material not shown for ease of flow understanding. The steam from steam input stream I 155 immediately dissociates in reactor tube I 101 and participates in the cyclic reaction, in conjunction with reactant flow stream I 139 , about a target material to produce reactant stream II 140 . Reactant stream II 140 then combines with steam, which immediately dissociates, from steam input stream 154 and reacts about the surface of target material, not shown, to produce reactor tube I product flow stream 141 . Reactor tube I product flow stream 141 then exits reactor tube 101 to become reactor tube I product stream 142 , which, after having been passed through a flashback arrestor (not shown), has the same composition and flow rate as reactor tube I product flow stream 141 . In the presented configuration, reactor tube I product stream 142 is split between reactor tube II recycle input stream 143 and reactor tube III input stream 146 , all having the same composition of dissociated water, which contains mostly monatomic hydrogen and monatomic oxygen.
[0069] Reactor tube II recycle input stream 143 then enters reactor tube II 109 and is ignited by an arc or laser to become reactor tube II flow stream 144 . Reactor tube II flow stream 144 then reacts in the manner disclosed above about the surface of a target material not shown for ease of flow understanding. Reactor tube II flow stream 144 then exits reactor tube 109 as reactor tube II product stream 145 , having the same composition of dissociated water as reactor tube II flow stream 144 . In the illustrated configuration, reactor tube II product stream is drawn off as product for use in well-known hydrogen-oxygen separation processes.
[0070] Reactor tube III recycle input stream 146 then enters reactor tube III 116 and is ignited by an arc or laser to become reactor tube I flow stream 147 . Reactor tube III flow stream 147 then reacts in the manner disclosed above about the surface of a target material not shown for ease of flow understanding. Reactor tube III flow stream 147 then exits reactor tube 116 as reactor tube III product stream 148 , having the same composition of dissociated water as reactor tube III flow stream 148 . In the illustrated configuration, reactor tube III product stream is also drawn off as product for use in well-known hydrogen-oxygen separation processes.
[0071] Referring specifically to FIG. 7 b , which shows the heat exchange production of steam for use in reactor tube I 101 , Heat exchanger input stream 149 enters heat exchanger body 123 through back heat exchanger flow tube 129 . In this configuration, heat exchanger input stream 149 is composed of liquid water. Heat exchanger flow 156 travels about the outer surfaces 103 , 111 , and 118 of reactor tubes I 101 , II 109 , and III 116 . Heat is transferred from the reactor tubes to heat exchanger flow 156 to accomplish, as here, the phase transition of water to steam; but in other configurations, the heat transfer could drive the thermodynamics of a chemical reaction to increase production of products. Heat exchanger flow 156 continues in counter-current flow around baffles 131 and 131 , respectively, and exits heat exchanger body 123 through front heat exchanger flow tube 128 to become heat exchanger output stream 150 . Here, heat exchanger output stream 150 is composed of water vapor. Heat exchanger output stream 150 can be drawn off as product in heat exchanger product stream 151 or can supply any of the reactor tubes with steam to drive the cyclic reaction about target material. In this configuration, steam is drawn off as product in heat exchanger product stream 151 as well as used to supply reactor tube I 101 . Heat exchanger recycle stream I 152 supplies to reactor tube I 101 , through first steam inlet tube 132 , the flow of which is indicated in FIG. 7 b as steam input stream I 155 . Heat exchanger recycle stream II 153 , which is the same as heat exchanger recycle stream I 152 but for decreases associated with steam input stream I 155 , provides reactor tube I 101 with steam through second steam inlet tube 133 , the flow of which is indicated in FIG. 7 b by steam input stream II 154 . Because of the steam input to reactor tube I 101 , reactor tube I input stream 138 's flow rate may be decreased as the amount of steam provided is increased
[0072] Given the above disclosure for hydrogen, oxygen, and heat production, it is expected that those skilled in the art would readily recognize various configurations and uses for the disclosed invention without exceeding the scope of the following claims. | An apparatus and method is provided for the ultra-high temperature cyclic thermal disassociation of water to produce usable hydrogen, oxygen, associated gases, and heat by igniting a previously-dissociated quantity of water and directing the resultant flame at a target material within a reactor whereupon the monatomic elements of the dissociated water recombine to water vapor, release energy, absorb the released energy, and re-dissociate, thereby producing a mostly monatomic mixture of dissociated water. Preferably, steam is produced in a heat exchanger arranged about the reactor and additionally provided to the reactor to undergo thermolytic disassociation. | 2 |
FEDERALLY SPONSORED RESEARCH
Not Applicable
SEQUENCE LISTING OR PROGRAM
Not Applicable
BACKGROUND
1. Field of the Invention
Apparatus and method for preparing and injecting an air stream with dry ice particles or other sublimable particles to be blasted against a surface to be cleaned.
2. Description of Prior Art
Blasting or cleaning a surface with a stream of high-pressure air mixed with sublimable particles is a well-known art. The most used blast media for this purpose is dry ice particles of various sizes. Dry ice is the solid form of carbon dioxide. One of the advantages of using dry ice over other media such as silica sand, glass beads or steel grit is that upon impact the dry ice instantly returns to a gas state leaving no residue to collect or dispose of Dry ice is also much more forgiving on the surfaces it impacts compared to many other media.
In the case of traditional media, both the media and contaminate being removed must be collected and disposed of properly. If the contaminate is a hazardous substance the used media will also have to be treated as a hazardous substance thereby creating more hazardous waste to contended with. Only the contaminant being cleaned off a surface must be disposed of when dry ice blasting is used thus creating less waste then traditional media blast cleaning systems.
Dry ice blasting can and does replace dangerous and environmentally unfriendly cleaning chemicals thereby reducing the exposure of humans and the environment to these chemicals.
Reducing the use of these chemicals also reduces the chance of improper disposal of chemicals into the environment and improves air quality by eliminating the volatile organic chemicals emitted into the air by many cleaning chemicals.
The art includes two generally available types of dry ice blasting systems that use high-pressure air to facilitate the blasting. The two hose system uses two hoses to transport the air and dry ice separately to a ventri suction type blast nozzle where they are mixed. The second type carries the air and dry ice together in one hose to the blast nozzle. The single hose systems, as they are known, use some type of mechanical means to inject or feed dry ice into the air stream at a source of dry ice to be carried to a blast nozzle by one hose.
One advantage of the single hose system is that they generally produce more blasting power then two hose systems of similar size. The single hose systems also have an ergonomical advantage in that the user must manipulate only one hose to facilitate blasting thus significantly reducing the weight he or she must support.
Dry ice is readily available commercially in various forms including block, nugget, and rice. All forms of dry ice can be used for blasting, but block and sometimes nugget types require additional processing to produce dry ice particles of appropriate size for use in blasting. The rice form is the smallest commercially available form of dry ice particles and requires no additional processing as most dry ice blasting machines are designed to use it.
The problem of how to inject dry ice particles into a stream of air is made difficult by the very problematic nature of dry ice. Dry ice chills or freezes most things it comes in contact with or in close proximity to including the vary mechanisms used to act upon it because of its very low temperature (−78° C./−109° F.). This low temperature can lead to condensation or frozen condensation on or inside the equipment and can, through thermal contraction, substantially change the dimensions of critical components. Therefore it is important to avoid mechanically complex designs in this art in order to maintain good reliability.
Dry ice also attracts moisture from the air to its surface were it freezes and degrades its quality. Dry ice particles tend to aggregate into clumps, especially when moisture is present. Once aggregated into clumps it is difficult or impossible to feed through conventional mechanisms of the art.
Manufactures and users of dry ice blasters are all aware of the difficulties of injecting dry ice into a stream of air. The art has many examples of attempts to overcome these difficulties and to improve the art. The art of injecting dry ice particles into a stream of air would appear to be a simple problem to over come. However the fact that there continues to be efforts to overcome the inherent problems of this art indicates there is still room for improvement in the art of dry ice blasting.
The most important problems in the art that need to be overcome are the problems with the inability to consistently feed a metered amount of dry ice particles into a stream of air to create a consistent ratio of dry ice to air in the blast hose at all times. Often the feed of dry ice is intermittent and inconstant in the present art. A second problem that needs to be addressed is the fact that most of the art relies on complicated and therefore relatively expensive mechanisms to overcome the aforementioned problem. The price of equipment keeps this environmentally friendly method of cleaning out of the hands of the individuals and small and medium sized companies who often continue to depend on cleaning methods that are less friendly to the environment then dry ice blasting.
A device that both consistently feeds and accurately meters dry ice into the air stream via an air lock must solve the problem. Several devices are known that try to perform both functions by using moving elements with cavities that are filled with dry ice particles and then attempt to supply the dry ice into the air stream. For example, star wheels, reciprocating plates and rotary disks with cavities move at a given frequency past a dry ice feed station and then move to alien the dry ice filled cavity with the flow of the air stream to discharge it and mix dry ice into the air stream.
U.S. Pat. No. 4,947,592 (1990) and U.S. Pat. No. 5,109,636 (1992) both to Lloyd disclose a star wheel design and U.S. Pat. No. 5,415,584 (1995) and U.S. Pat. No. 5,492,497 (1996) both to Brooke and U.S. Pat. No. 4,744,181 (1988) to Moore disclose reciprocating plate(s) designs. Both design types feed dry ice and meter dry ice into the air stream with similar mechanisms. In these cases the cavities of the wheel and reciprocating plates are fixed in size. The only way to adjust the ratio of dry ice to air is to adjust the frequency at which the cavities are brought into alignment with the air stream. This works only in restricted limits. Problems arise as the ratio of dry ice to air is reduced. To accomplish this, the rotating wheel or the reciprocating plate(s) must be slowed to decrease the discharge frequency. This slowing tends to create an undesirable pulsing of dry ice in the blast hose and at the nozzle when the cavities are not aligned with the airflow stream.
Another problem with the above designs is the fact that as the cavities turn or move slower the greater the chance that the dry ice in them will aggregate into clumps that can not be discharged into the air stream. These clumps often freeze in the cavities thereby increasing the undesirable pulsing of dry ice. If all the cavities become clogged in this way the mechanism will fail to operate. If the mechanism is stopped for a period of time the dry ice that remains in the cavities, that has not yet been discharged into the air stream, may freeze in the cavities and cause pulsing or may freeze the mechanism so that it cannot be restarted.
U.S. Pat. No. 6,346,035 (2002) to Anderson discloses a device that claims to have overcome the above problems, but in reality the devise still faces several of the above problems with an added one that effects the safety of the operator and those in proximity to the operating blaster. This design uses an auger to feed and meter dry ice into a rotating air lock that feeds the dry ice into the air stream. The rotating air lock rotates at a set speed thereby reducing the pulsing effect caused by changing the frequency at which the cavities are discharged in the above-mentioned art. On shut down the auger stops feeding dry ice to the air lock, but the air lock continues to rotate and the stream of high pressure air continues for a set time. This eliminates the possibility of dry ice freezing in the rotor's feed cavities, but more importantly it creates an unsafe condition. Most regulatory agencies require a “dead man” device on abrading blast cleaning equipment that is to promptly stop the flow of air and abrading media when the operator removes his or her bodily input that keeps the machine operating. The continued airflow and diminishing dry ice flow after shut down of this design negates the function of any “dead man” safety device. The auger feed mechanism of this design is also susceptible to being jammed or clogged by aggregated clumps of dry ice as the above-mentioned art.
U.S. Pat. No. 6,346,035 (2002) to Anderson and U.S. Pat. No. 4,947,592 (1990) and U.S. Pat. No. 5,109,636 (1992) both to Lloyd all require the use of two motors to inject dry ice into the air stream going to the cleaning nozzle. By using two motors the designs uses excessive energy that could have been used directly for the cleaning action. Using two motors also makes the machines more complex and thereby reduces reliability.
Known prior art suffers from a number of the following disadvantages:
(a) The ratio of dry ice to pressurized air is a set ratio or is sometimes limited to a narrow adjustment of the ratio. Limited ratios restrict the flexibility to use the art in cleaning applications. (b) Pulsing of dry ice from the blast nozzle is a negative possibility in several of these designs. (c) The designs are complex with many intricate moving parts that are specific to each design. (d) Two of the designs include multiple motors that reduce the energy that can be used for cleaning. (e) The designs have a relatively high number of parts that are complex in nature. These complex designs increase manufacturing costs by increasing the need for more manufacturing/warehouse space, manufacturing plant equipment, and highly trained employees. (f) The designs have tendencies to become clogged with aggregated clumps of dry ice. (g) The designs must keep parts dimensionally within tolerance to avoid the negative effects of the extreme low temperature. The low temperature can change the dimensions of some parts so drastically that thy can no longer function properly. (h) The designs must continue to purge pressurized air from the nozzle after the actuation trigger is released to remove dry ice from the system thus causing a safety hazard.
OBJECTS AND ADVANTAGES
Accordingly several objects and advantages of my invention are:
(a) A design that will inject dry ice into an air stream at a wide range of air to dry ice ratios with no pulsation of dry ice in the hose and nozzle. (b) A design that is significantly simpler with fewer elements then previous art. (c) A design that uses only one drive motor. (d) A design that is significantly less expensive to manufacture then previous art. (e) A design that is resistant to being jammed or clogged by aggregated clumps of dry ice. (f) A design that is resistant to the effect of low temperatures. (g) A design that is self-clearing of dry ice particles so that upon stoppage no dry ice will remain to clog or bind the system. (h) A design that can safely stop the flow of air and dry ice promptly on shut down.
Further objects and advantages of my invention will become apparent from a consideration of the following drawings and descriptions.
SUMMARY
A system according to this invention includes a source of dry ice particles or other suitable particles, a regulated source of pressurize air, and an air lock mixing element receiving and combining both dry ice particles and air. An adjustable speed drive motor with a drive sprocket and an idler sprocket move an endless loop conveyor cable assembly through the dry ice source and carry it into the air lock where it is mixed with a air stream. A hose and a nozzle to receive the air laden with dry ice particles from the air lock mixing element to discharge the air laden with dry ice particles toward the object to be cleaned.
DRAWINGS
Drawings Figures
FIG. 1 shows a side view, partly in cross-section, of a preferred embodiment of the invention in a horizontal configuration.
FIG. 2 shows a detailed cross-section of an air lock assembly used in this invention.
FIG. 3 shows a side view, partly in cross-section, of an additional embodiment of the invention in a vertical configuration.
FIG. 4 shows a side view, partly in cross-section, of an alternative embodiment of the invention in an enlarged vertical configuration.
FIG. 5 shows a side view, partly in cross-section, of an alternative embodiment of the invention in an angled configuration.
REFERENCE NUMERALS IN DRAWINGS
10 Adjustable speed motor
12 Drive sprocket
13 Conveyor passage
14 Conveyor cable outlet
16 Seal adjustment stop
18 V-seal packing
20 Air lock assembly
21 Air passage
22 Inlet port
24 Outlet port
26 Mixing chamber
28 Conveyor cable inlet
30 Horizontal dry ice hopper
31 Hopper port
32 Idler sprocket
34 Wire rope
36 Conveyor airlock piston
38 Conveyor cable assembly
40 Frame
42 Vertical dry ice hopper
43 Enlarged vertical dry ice hopper
44 Angled dry ice hopper
DETAILED DESCRIPTION
FIG. 1 Preferred Embodiment
A horizontal dry ice hopper 30 is mounted on a frame 40 . The frame supports an adjustable speed motor 10 and an idler sprocket 32 . An air lock assembly 20 is supported by horizontal dry ice hopper 30 , but also can be alternately supported by frame 40 or plumbing that rigidly supports air lock assembly 20 between adjustable speed motor 10 , horizontal dry ice hopper 30 , and idler sprocket 32 .
A conveyor cable assembly 38 is routed horizontally in a path along the bottom of horizontal dry ice hopper 30 through air lock assembly 20 around a drive sprocket 12 around idler sprocket 32 through a hopper port 31 and back into horizontal dry ice hopper 30 .
Horizontal dry ice hopper 30 is a wedge shape with the “V” shape of the wedge facing downward. The “V” shape forms a horizontal valley along the inside bottom of hopper 30 . Conveyor cable assembly 38 travels along the valley from hopper port 31 to air lock assembly 20 .
Conveyor cable assembly 38 is constructed by attaching a plurality conveyor airlock pistons 36 equally spaced apart to a section of wire rope 34 to form a continuous loop. Conveyor airlock pistons 36 are a cylindrical shape with a hole centered through the length of the piston to facilitate the passage of wire rope 34 . A portion of the cylindrical shape of conveyor airlock pistons 36 has a reduced diameter to facilitate the crimping of pistons 36 to wire rope 34 . The crimps should firmly attach pistons 36 to wire rope 34 forming a seal between wire rope 34 and the hole through each piston. 36 to restrict the flow of air between the two. The ends of wire rope 34 are spliced together utilizing one or more of the crimps that attach the pistons 36 to wire rope 34 after being fed through hopper 30 and air lock assembly 20 to create the endless loop feature of conveyor cable assembly 38 .
The diameter of conveyor airlock pistons 36 and the space between them must be considered along with the speed range of adjustable speed motor 10 in establishing the maximum and minimum feed rate of dry ice that will be possible with this invention. Larger diameter pistons 36 generally will increase the feed rate of dry ice and increase the size of dry ice particles that can be fed through the invention. Spacing pistons 36 to close together will both decrease the feed rate of dry ice and the efficiency of feeding dry ice into air lock assembly 20 at higher motor speeds.
Hopper port 31 is a section of tubing with an inside diameter larger then the diameter of conveyor airlock pistons 36 . Hopper port 31 is longer then the distance between any two adjacent conveyor airlock pistons 36 .
FIG. 2 Air Lock Assembly
FIG. 2 shows air lock assembly 20 is constructed with two tubular passages intersecting each other at a 90° angle. The center axes of both passages are on the same plane. A mixing chamber 26 is formed were the passages intersect each other. An air passage 21 has an inlet port 22 at one end and an outlet port 24 at the opposite end. A conveyor passage 13 has a conveyor cable inlet 28 at one end and a conveyor cable outlet 14 at the opposite end.
Conveyor cable inlet 28 is constructed to accept a v-seal packing 18 . The mixing chamber 26 end of conveyor cable inlet 28 the inside diameter is reduced to secure v-seal packing 18 from moving into mixing chamber 26 . The outward-facing end of conveyor cable inlet 28 is threaded on the inside diameter to accept a seal adjustment stop 16 .
Conveyor cable outlet 14 is constructed to accept v-seal packing 18 . The mixing chamber 26 end of conveyor cable outlet 14 the inside diameter is reduced to secure v-seal packing 18 from moving into mixing chamber 26 . The outward-facing end of conveyor cable outlet 14 is threaded on the inside diameter to accept seal adjustment stop 16 .
Seal adjustment stops 16 are rings threaded on the outside diameter to fit the threaded inside area of conveyor cable inlet 28 and conveyor cable outlet 14 . The inside diameter is larger then the diameter of conveyor airlock pistons 36 .
V-seal packing 18 should be longer then the distance between two adjacent conveyor airlock pistons 36 and are installed behind seal adjustment stops 16 in conveyor cable inlet 28 and conveyor outlet 14 . Cable conveyor assembly 38 passes through conveyor cable inlet 28 , v-seal packings 18 , and conveyor outlet 14 . V-seal packings 18 are installed in the conveyor cable inlet 28 and conveyor outlet 14 so that the lip of each seal that make up packing is facing toward mixing chamber 26 and the “V” point shape of each seal is pointing outward from air lock assembly 20 . V-seal packing 18 is PTFE or similar fluoropolymer.
Air lock assembly 20 can be rotated 360 degrees around cable conveyor assembly 38 axes to facilitate plumbing of inlet port 22 and outlet port 24 to the completed dry ice blasting machine.
Inlet port 22 of air lock assembly 20 is supplied with regulated air pressure. Outlet port 24 is connected to a hose and blast nozzle (not shown) to receive the stream of air laden with dry ice particles from air lock assembly 20 .
A conventional switch to simultaneously start and stop the flow of regulated air pressure to inlet port 22 and rotation of adjustable speed motor 10 is provide on the blast nozzle (not shown) or other suitable location.
FIG. 3 Additional Embodiment
An additional vertical embodiment is described here and shown in FIG. 3 . The description is the same as the above-mentioned horizontal embodiment with the following differences. A vertical dry ice hopper 42 is mounted on frame 40 . Frame 40 supports adjustable speed motor 10 on the lower section and idler sprocket 32 on the top. Air lock assembly 20 is supported by vertical dry ice hopper 42 , but also can be alternately supported by frame 40 or plumbing that rigidly supports air lock assembly 20 between adjustable speed motor 10 , vertical hopper 42 and, idler sprocket 32 .
Conveyor cable assembly 38 is routed vertically in a path down through the center axis of vertical dry ice hopper 42 , through air lock assembly 20 , around drive sprocket 12 , up and around to idler sprocket 32 and back down into vertical hopper 42 . Vertical hopper 42 is an inverted pyramid or cone shape. The shape of vertical hopper 42 funnels down into conveyor cable inlet 28 of air lock assembly 20 .
FIGS. 4 and 5 Alternative Embodiments
There are numerous possibilities with regard to the relative layout of this invention and the routing of its conveyor cable assembly 38 . Two of these possibilities are described below and shown in FIG. 4 and 5 . An enlarged vertical dry ice hopper 43 or an angled dry ice hopper 44 may be used. Multiple idler sprockets 32 may be used. Adjustable speed motor 10 and drive sprocket 12 may be located anywhere along the route of conveyor cable assembly 38 .
FIG. 4 shows an alternative enlarged vertical embodiment of the invention with two idler sprockets 32 used to facilitate the use of enlarged vertical hopper 43 .
FIG. 5 shows an alternative angled embodiment of the invention. This embodiment of the invention routes conveyor cable assembly 38 at an angle down through angled dry ice hopper 44 and then into air lock assembly 38 . Angled dry ice hopper 44 is an inverted pyramid or cone shape. Conveyor cable assembly 38 enters angled hopper 44 through hopper port 31 . The shape of angled hopper 44 funnels down into conveyor cable inlet 28 of air lock assembly 20 .
FIGS. 1 and 2 Operation of Preferred Embodiment
Conveyor cable assembly 38 is pulled, by adjustable speed motor 10 via drive sprocket 12 , through a supply of dry ice particles that is contained in horizontal dry ice hopper 30 . A metered amount of dry ice particles is entrapped between conveyor airlock pistons 36 as conveyor cable assembly 38 is pulled through the dry ice. As conveyor cable assembly 38 leaves the hopper it enters conveyor cable inlet 28 of air lock assembly 20 bringing with it the metered amount of dry ice that is entrapped between pistons 36 .
A stream of regulated pressurized air is only supplied to inlet port 22 while adjustable speed motor 10 is running. Inlet port 22 supplies air to mixing chamber 26 .
As each of conveyor airlock pistons 36 enters conveyor cable inlet 28 and its v-seal packing 18 a seal is created to prevent pressurized air from escaping from mixing chamber 26 via conveyor cable inlet 28 . The seal is maintained as each conveyor airlock piston 36 travels through the v-seal packing 18 until the following conveyor airlock piston 36 on conveyor cable assembly 38 engages v-seal packing 18 , thereby creating an uninterrupted air lock seal. As each piston 36 leaves v-seal packing 18 of conveyor cable inlet 28 it exposes the dry ice entrapped between it and the following conveyor airlock piston 36 to the pressurized air stream in mixing chamber 26 . As the dry ice is exposed to the air stream it is mixed and carried away via the outlet port 24 .
As each conveyor airlock pistons 36 enters conveyor cable outlet 14 and its v-seal packing 18 from mixing chamber 26 a seal is created to prevent pressurized air from escaping from mixing chamber 26 via conveyor cable outlet 14 . The seal is maintained as each conveyor airlock piston 36 travels through v-seal packing 18 of conveyor cable outlet 14 until following conveyor airlock piston 36 on conveyor cable assembly 38 engages v-seal packing 18 thereby creating an uninterrupted air lock seal.
After conveyor cable assembly 38 leaves air lock assembly 20 it continues on a route around drive sprocket 12 and idler sprocket 32 before it re-enters horizontal dry ice hopper 30 via hopper port 31 .
FIGS. 3-5 Additional and Alternative Operation
The additional and alternative embodiments operate the same as the preferred embodiment described above with the exception of the following differences.
In the additional vertical embodiment shown in FIG. 3 after conveyor cable assembly 38 is pulled from air lock assembly 20 it continues on a route around drive sprocket 12 and idler sprocket 32 before it re-enters vertical dry ice hopper 42 via its open top.
In the alternative enlarged vertical embodiment shown in FIG. 4 after conveyor cable assembly 38 is pulled from air lock assembly 20 it continues on a route around drive sprocket 12 and two idler sprockets 32 before it re-enters enlarged vertical dry ice hopper 43 via its open top.
In the alternative angled embodiment shown in FIG. 5 after conveyor cable assembly 38 is pulled from air lock assembly 20 it continues on a route around drive sprocket 12 and idler sprocket 32 before it re-enters angled dry ice hopper 44 via hopper port 31 .
CONCLUSION, RAMIFICATION, AND SCOPE
Accordingly, the reader will see that the injecting apparatus of this invention is a simple design that has many advantages over all previous art including:
A design that can be adjusted to provide a large range of ratios of air to dry ice supplied to the blast hose and nozzle. No pulsation of dry ice in the blast hose and nozzle. Simple design that increases reliability and ease of manufacture by using significantly fewer elements then previous art. Only one drive motor is used in order to reserve the energy supplied to the machine for the cleaning action. A design that is significantly less expensive to manufacture then previous art. Resistant to being jammed or clogged by aggregated clumps of dry ice. Resistant to the effects of low temperatures. A design that is self-clearing of dry ice particles so that upon stoppage no dry ice will remain to clog or bind the system. A design that safely stops the flow of air and dry ice promptly when shut down.
Although the description above contains much specificity, these should not be construed as limiting the scope of this invention but as merely providing illustrations of some of the presently preferred embodiments of this invention. For example the conveyor cable assembly 38 can take many more paths then described, the sprockets can take different shapes, the hoppers can take many different shapes and sizes, and the over all layout can take on many different configurations.
Thus the scope of the invention should be determined by the appended claims and their legal equivalents, rather than by the examples given. | Apparatus and method to inject an air stream with dry ice or other sublimable particles to be blasted against a surface to be cleaned. An air lock assembly ( 20 ) with an air stream passage ( 21 ) and an intersecting conveyor passage ( 13 ) that has an endless cable conveyor assembly ( 38 ) passing through it. The conveyor ( 38 ) passes through a hopper ( 30 ) of dry ice particles before entering the air lock ( 20 ) and injecting the air stream with dry ice particles. V-seals packings ( 18 ) are provided as a means of limiting air form escaping from the points where the conveyor ( 38 ) enters and exits the air lock assembly ( 20 ). An adjustable speed motor ( 10 ) drives the conveyor ( 38 ) thereby giving an adjustable control of the ratio of dry ice to air. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a vehicle cargo restrainer intended to secure a variety of articles during transportation. More specifically, the present invention provides a convenient restrainer, which may be positioned in various locations within a vehicle, that prevents articles, parcels and so forth from slipping or being dislodged during transportation.
2. Description of the Prior Art
A common dilemma experienced by the drivers of automobiles are the problems associated with the transport of various articles and parcels. Typically, these objects become dislodged during portage, and the contents normally spill into the vehicle's compartment. Fragile items such as glass, plastic and so forth occasionally break or crack, causing the stored fluids to leak. As a result, drivers frequently resort to various, oftentimes futile, methods of providing support to ensure said articles and packages are secure during transport. In no instance is this problem more acute than during trips to and from department stores and supermarkets, where packages of goods and valuables often overturn during the journey. Displaced articles can also be a danger to drivers, as well as an inconvenience, where displaced articles roll under the gas pedal or brake. The present invention ensures a measure of relief for frustrated drivers by providing a portable restraining means which can safely secure a variety of articles and packages. When not in use, the device collapses readily to be conveniently stored behind the seat of pick-up trucks, under the seats of vans and sport vehicles or in the trunk or designated storage area of other types of vehicles. For use, it opens easily into a large, stable restraining fence which rests on the floor of the vehicle wherever desired.
Numerous innovations for an vehicle cargo restrainer have been provided in the prior art that are described as follows. Even though these innovations may be suitable for the specific individual purposes to which they address, they differ from the present invention as hereinafter contrasted.
U.S. Pat. No. 4,226,348 to Dottor et al. discloses an automobile contained grocery bag holder that provides a storage means in the trunk of a vehicle. A plurality of storage compartments are secured to a solid base intended to prevent the escape of liquids. The device includes attachment meas that enable the device to be secured to the floor of the trunk of the vehicle. This patent differs from the present invention because the vehicle cargo restrainer provides at least two handles, one on either side of the device, which allow the same to be repositioned to various locations within the vehicle. Moreover, the vehicle cargo restrainer provides a flexible base for more cumbersome objects, this feature is not disclosed in the present patent. In addition, the vehicle cargo restrainer provides an open storage facility, allowing for the placement of larger objects, whereas the present invention comprises smaller, individual compartments.
U.S. Pat. No. 5,379,906 to Levin et al. provides a foldable organizer located in the automobile's trunk which includes a plurality of compartments for storage purposes. This patent differs from the present invention because two handles for carrying purposes is not disclosed. Further, a the present invention comprises a generally open storage basin, allowing for the storage a large articles. This feature is not disclosed in the present patent.
U.S. Pat. No. 5,366,189 to Thomson provides a support means for grocery bags. The device comprises two intersecting panel members that form four chambers within which said bags are secured. This patent differs from the present invention because the vehicle cargo restrainer comprises a generally rectangular storage means having four walls and a base. This features are not disclosed in the present patent.
U.S. Pat. No. 5,234,116 to Kristinsson et al. provides a collapsible rack assembly intended to secure packages and other parcels. This patent differs from the present invention because a generally rectangular storage means comprising four adjustable walls and a flexible base is not disclosed.
U.S. Pat. No. 4,561,554 to Swincicki discloses a container intended for the storage of produce and other goods. The present invention provides an open, generally rectangular storage basin with a flexible base. These features are not disclosed in the present patent.
Numerous innovations for an vehicle cargo restrainer have been provided in the prior art that are adapted to be used. Even though these innovations may be suitable for the specific individual purposes to which they address, they would not be suitable for the purposes of the present invention as heretofore described.
SUMMARY OF THE INVENTION
In accordance with the present invention, a vehicle cargo restrainer comprises a generally rectangular, open storage fence which is preferably manufactured from plastic or plastic composite. The device may also be manufactured from rubber, wood, metal or metal alloy. The two shorter sides of said invention each include a hand-hold opening, which enable the device to be carried or moved. The two longer sides comprise two independent segments, of approximately equal lengths, one being slidably housed directly inside the other. A hinge located on each of the four corners of said device pivotally attach each of the four sides to one another. A plurality of longitudinally disposed slats, equidistantly spaced and integrally attached to the sides of said device, form the bottom of the device. Said slats are preferably manufactured from plastic, but may also be manufactured from rubber and plastic composite. In alternative embodiments, the slats are basket woven to form a more solid, stable base for the storage of smaller objects or replaced by woven netting which may be easily and interchangeably attached to either the bottom or top of the device by means of provided attachment points. As disclosed hereinbefore, the vehicle cargo restrainer is collapsible by means of the four hinges, which cooperate with the two segments of each of the longer sides to allow the device to be reduced to a generally flat configuration.
Accordingly, it is an object of the present invention to provide a vehicle cargo restrainer which provides a storage means for packages, articles, and various other objects during vehicular usage.
More particularly, it is an object of the present invention to provide an vehicle cargo restrainer which prevents the escape or dislodging of articles from packages and various other containers stored within the vehicle cargo restrainer.
Another feature of the present invention is that the vehicle cargo restrainer is collapsible, allowing for easy storage of the same when not in use.
Yet another feature of the present invention is that the device can be placed in a variety of locations within the vehicle depending on the particular storage needs of the user.
Still yet another feature of the present invention is the flexible base, reducing the risk that fragile items such as glass and ceramic will be dislodged and possibly broken or cracked during travel.
Yet another feature of the present invention is the generally large size of the restraining means, allowing for the storage of cumbersome or otherwise bulky objects.
Still yet another feature of the present invention is the interchangeable netting which is easily repositionable to and from the top and bottom of the device, preventing the escape of articles from open areas of a vehicle, such as the rear of a pick-up truck, during travel.
The novel features which are considered characteristic for the invention are set forth in the appended claims. The invention itself, however, both as to its construction and its method of operation, together with additional objects and advantages thereof, will be best understood from the following description of the specific embodiments when read and understood in connection with the accompanying drawings.
BRIEF LIST OF REFERENCE NUMERALS UTILIZED IN THE DRAWING
10--vehicle cargo restrainer (10)
12A--basin first member (12A)
12AL--basin first member left side (12AL)
12ALA--basin first member left border (12ALA)
12ALAA--basin first member left housing (12ALAA)
12ALAB--basin first member left edge (12ALAB)
12ALB--basin first member left hinge first bracket (12ALB)
12AM--basin first member front (12AM)
12AMA--basin first member front handle (12AMA)
12AML--basin first member front left hinge second bracket (12AML)
12AMR--basin first member right hinge second bracket (12AML)
12AR--basin first member right side (12AR)
12ARA--basin first member right border (12ARA)
12ARAA--basin first member right housing (12ARAA)
12ARAB--basin first member right edge (12ARAB)
12ARB--basin first member right hinge first bracket (12ARB)
12B--basin second member (12B)
12BL--basin second member left side (12BL)
12BLA--basin second member left border (12BLA)
12BLAA--basin second member left pin (12BLAA)
12BLAB--basin second member left edge (12BLAB)
12BLB--basin second member left hinge first bracket (12BLB)
12BM--basin second member front (12BM)
12BMA--basin second member front handle (12BMA)
12BML--basin second member front left hinge second bracket (12BML)
12BMR--basin second member right hinge second bracket (12BML)
12BR--basin second member right side (12BR)
12BRA--basin second member right border (12BRA)
12BRAA--basin second member right pin (12BRAA)
12BRAB--basin second member right edge (12BRAB)
12BRB--basin second member right hinge first bracket (12BRB)
12C--hinge peg (12C)
14A--basin first member slats (14A)
14B--basin second member slats (14B)
16--track assembly (16)
18--rolling means (18)
BRIEF DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 is a top perspective view of the vehicle cargo restrainer.
FIG. 1a is a side perspective view of the basin first and second members.
FIG. 2 is a top perspective view of the vehicle cargo restrainer in a collapsible position.
FIG. 3 is a top view of the vehicle cargo restrainer inside a vehicle.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Firstly, referring to FIG. 1 which is a is a top perspective view of the vehicle cargo restrainer (10) exhibiting the following features: basin first member (12A); basin first member left side (12AL); basin first member left border (12ALA); basin first member left housing (12ALAA); basin first member left edge (12ALAB); basin first member left hinge first bracket (12ALB); basin first member front (12AM); basin first member front handle (12AMA); basin first member front left hinge second bracket (12AML); basin first member right hinge second bracket (12AML); basin first member right side (12AR); basin first member right border (12ARA); basin first member right housing (12ARAA); basin first member right edge (12ARAB); basin first member right hinge first bracket (12ARB); basin second member (12B); basin second member left side (12BL); basin second member left border (12BLA); basin second member left pin (12BLAA); basin second member left edge (12BLAB); basin second member left hinge first bracket (12BLB); basin second member front (12BM); basin second member front handle (12BMA); basin second member front left hinge second bracket (12BML); basin second member right hinge second bracket (12BML); basin second member right side (12BR); basin second member right border (12BRA); basin second member right pin (12BRAA); basin second member right edge (12BRAB); basin second member right hinge first bracket (12BRB); hinge peg (12C); basin first member slats (14A); basin second member slats (14B); track assembly (16); and rolling means (18). The vehicle cargo restrainer (10) comprises a basin first member (12A) having a basin first member left side (12AL) and a basin first member right side (12AR) pivotally attached to a basin first member front (12AM). A basin first member left front hinge second bracket (12AML) and a basin first member right front hinge second bracket (12AMR) are pivotally mounted to a basin first member left hinge first bracket (12ALB) and a basin first member right hinge first bracket (12ARB), respectively, by means of two hinge pegs (12C) inserted therein. The basin first member (12A) further has a basin first member front handle (12AMA) hollowed through the basin first member front (12AM). The basin first member left side (12AL) further comprises a perpendicularly disposed basin first member left border (12ALA) on either end of said basin first member left side (12AL) and a basin first member left edge (12ALAB) which is perpendicularly disposed from the basin first member left border (12ALA), forming a hollow channel. At least two basin first member left housings (12ALAA) are bored through the basin first member left border (12ALA). The basin first member right side (12AR) further comprises a perpendicularly disposed basin first member right border (12ARA) on either end of said basin first member right side (12AR) and a basin first member right edge (12ARAB) which is perpendicularly disposed from the basin first member right border (12ARA), forming a hollow channel. At least two basin first member right housings (12ARAA) are bored through the basin first member right border (12ARA).
The basin first member (12A) further comprises a plurality of basin first member slats (14A) longitudinally disposed across the length of the basin first member (12A). The plurality of basin first member slats (14A) are equally spaced from another and are integrally attached to the basin first member right side (12AR) and the basin first member left side (12AL). In an alternative embodiment, the plurality of basin first member slats (14A) are both longitudinally and latitudinally disposed along the length of the basin first member (12A), forming a basket woven base for the vehicle cargo restrainer (10).
The vehicle cargo restrainer (10) further comprises a basin second member (12B) having a basin second member left side (12BL) and a basin second member right side (12BR) pivotally attached to a basin second member front (12BM). A basin second member left front hinge second bracket (12BML) and a basin second member right front hinge second bracket (12BMR) are pivotally mounted to a basin second member left hinge first bracket (12BLB) and a basin second member right hinge first bracket (12BRB), respectively, by means of two hinge pegs (12C) inserted therein. The basin second member (12B) further has a basin second member front handle (12BMA) hollowed through the basin second member front (12BM). The basin second member left side (12BL) further comprises a perpendicularly disposed basin second member left border (12BLA) on either end of said basin second member left side (12BL) and a basin second member left edge (12BLAB) which is perpendicularly disposed from the basin second member left border (12BLA), forming a hollow channel. At least two basin second member left pins (12BLAA), retractably attached to the upper basin second member left border (12BLA), extend upwardly from the basin second member left border (12BLA). The basin second member right side (12BR) further comprises a perpendicularly disposed basin second member right border (12BRA) on either end of said basin second member right side (12BR) and a basin second member right edge (12BRAB) which is perpendicularly disposed from the basin second member right border (12BRA), forming a hollow channel. At least two basin second member right pins (12BRAA), retractably attached to the upper basin second member right border (12BRA), project upwardly from the upper basin second member right border (12BRA).
The basin second member (12B) further comprises a plurality of basin second member slats (14B) longitudinally disposed across the length of the basin second member (12B). The plurality of basin second member slats (14B) are equally spaced from another and are integrally attached to the basin second member right side (12BR) and the basin second member left side (12BL). In an alternative embodiment, the plurality of basin second member slats (14B) are both longitudinally and latitudinally disposed along the length of the basin second member (12B), forming a basket woven base for the vehicle cargo restrainer (10).
Now, referring to FIG. 1a which is a side perspective view of the basin first member (12A) and the basin second member (12B). The basin second member (12B) is slidably housed within the basin first member (12A). A track assembly (16) horizontally displaced along the length of the basin first member left side (12AL) and the basin first member right side (12AR) comprises a slot through which a rolling means (18) is inserted. The rolling means is rotatably mounted to the basin second member left side (12AL) and the basin second member right side (12AR), and cooperates with the track assembly (16) to permit the movement of the of the basin first member (12A) within the basin second member (12B). The basin second member (12B) is prevented from escaping the basin first member (12A) by means of the basin second member left pins (12BLAA) and the basin second member right pins (12BRAA) which extend through the basin first member left housings (12ALAA) and the basin second member right housings (12ARAA), respectively.
Now referring to FIG. 2 which is a top perspective view of the vehicle cargo restrainer (10) displayed in a collapsible position. As discussed hereinbefore, each side of the device is pivotally connected be means of bracket assemblies situated on each of the four corners of the vehicle cargo restrainer (10). When the vehicle cargo restrainer (10) is in use, the device forms a generally rectangular or square configuration. When not in use, the device is collapsible to a generally flat configuration, enabling the vehicle cargo restrainer (10) to be easily stored in the trunk or under the seats of a vehicle.
Now referring to FIG. 3 which is a top view of the vehicle cargo restrainer (10) inside a vehicle. Because of the portable nature of the vehicle cargo restrainer (10), the device can be situated in various locations inside a vehicle.
It will be understood that each of the elements described above, or two or more together, may also find a useful application in other types of constructions differing from the type described above.
While the invention has been illustrated and described as embodied in a vehicle cargo restrainer, it is not intended to be limited to the details shown, since it will be understood that various omissions, modifications, substitutions and changes in the forms and details of the device illustrated and in its operation can be made by those skilled in the art without departing in any way from the spirit of the present invention.
Without further analysis, the foregoing will so fully reveal the gist of the present invention that others can, by applying current knowledge, readily adapt it for various applications without omitting features that, from the standpoint of prior art, fairly constitute essential characteristics of the generic or specific aspects of this invention.
What is claimed as new and desired to be protected by Letters Patent is set forth in the appended claims. | Apparatus is provided for a safe, convenient and practical method of securing goods and packages inside a vehicle. The device comprises a generally rectangular, open storage facility which is collapsible to an approximately flat configuration. The device can be situated in various locations inside the vehicle, and can be easily stored in the trunk or under the seats when not in use. Two handles on either side of the device allow the same to be carried or readily moved within the vehicle. A generally flexible netting functions as an alternative base for the device, reducing the risk that fragile items would become loose and break or crack. The netting is also adapted to fit over the top of the device, preventing the escape of articles from open areas of vehicles such as a pick-up truck. | 1 |
This application is a continuation-in-part of application Ser. No. 06/905,016, filed Sept. 8, 1986, now abandoned.
BACKGROUND OF THE INVENTION
The present invention comprises a method for sizing paper and similar products and further describes new classes of chemical materials suitable for sizing these products. The method and the new sizing compositions are particularly well suited for sizing in the pH range between about 6.5 and 10.5.
Sizes are used in virtually all finished paper products their primary purpose is to reduce the rate at which the paper sorbs moisture. Sizings fall into two categories: internal fiber treatments and surface treatment of papers. Internal sizes are added to the papermaking stock at some point before the fibers are formed into a web on the paper machine. In surface treatment, sizes are applied as a coating at some point in the dryer section of the paper machine. Sizes for surface treatment are composed of a great variety of natural materials, synthetic resins and mixtures of the two types of materials. They are important to impart liquid holdout in such applications as milk cartons or meat wrappings where the paper is in actual contact with liquids and must prevent their transmission for extended periods of time. They are also used on coated papers to give ink holdout and prevent blurring of printed material. Most papers which are surface treated are also internally sized. This enhances holdout and increases the resistance of the web to the penetration of water while the surface size is applied at the size press in order to minimize sheet breaks.
For several hundred years ink holdout was the only consideration which necessitated sizing papers. Animal derived gelatins and perhaps a few naturally derived gum materials served very successfully when most papers were hand made. With the advent of paper machines which increased the production rate by orders of magnitude, other materials had to be found. Rosin emulsion and soaps, precipitated by alum, came into use about 1830 and have been so successful that they are still the predominantly used internal sizing material. Despite a spectrum of other sizing compositions found in the patent literature, only two besides those based on rosins have achieved even limited commercial success. These are alkyl substituted ketene dimers and alkenyl substituted succinic anhydride. These latter materials are much more expensive than rosin but may successfully be used in the pH range between 6 and 8. Because of its chemical nature, rosin is not generally considered to be an effective sizing material above about pH 6.5 and the great bulk of it is used in the pH range of 4.5 to 5.5.
There are both advantages and disadvantages to forming papers under acidic conditions. One advantage is slightly faster drainage on the wire section of the paper machine. The disadvantages are numerous. Equipment corrosion is one. The relatively short life of paper products made with acidic sizing is another. Deterioration of the paper made under acidic conditions is causing millions of books and other documents to slowly turn to dust before the eyes of their owners. Libraries are spending extensive sums to neutralize the acidity in their books. But due to the expanse and time involved, only the most valuable volumes made from acidic paper can be treated.
In addition to the problems caused by corrosion and paper deterioration, there are other reasons why sheeting at neutral to slightly alkaline conditions is desirable. The papermaker has more choice to choose component materials and may use fillers such as calcium carbonate which are not compatible with acidic systems. However, the expense and difficulty of use of ketene dimer and succinic anhydride based products has greatly limited their use and the time is ripe for new products or techniques.
Conventional sizing theory has been predominantly developed around rosin. Traditional belief holds that sizing occurs when an ambipathic material such as rosin is distributed as uniformly as possible on the fibers with a material such as alum. It is implicit that the sizing material must be oriented with the hydrophobic "tail" outward. It has been assumed that the alum in the system forms a bridge between anionic carboxyl groups of the rosin and the anionic cellulose fibers. When heated in the dryer section of the paper machine, the rosin, under the influence of heat, is presumed to "flow" over the fibers to ensure thorough and uniform distribution. During the application of heat it is assumed that an aluminum ester of rosin is formed that serves to orient the rosin on the fiber with the hydrophobic tail outward.
It may be noted at this point that rosin size is normally available in one of two forms: as an emulsion where the rosin is in the form of rosin acid (acid size) or in solution as the sodium soap (neutral size). Normally both of these forms of size are chemically modified. Typically they will be reacted with formaldehyde to decrease the tendency of the rosin to crystallize and often they are reacted with either fumaric acid or maleic anhydride to improve their efficiency. In neutral sizes from 80-100% of the rosin is in saponified form. Only about 5% of the rosin is saponified in acid sizes. This small amount is sufficient to enable formation of a self-stabilized emulsion without significant need for other emulsifying agents. When neutral rosin soap is used as the sizing agent, it must be well distributed through the system before alum is added. With sizes of this type, it is believed that sizing predominantly occurs at the wet end of the machine with little further development of sizing during drying. In the case of rosin acid sizes, uniform wet end distribution is essential, but sizing continues to develop as the paper passes through the dryer section. Marton and Marton, Proceedings, Tappi Papermakers Conference, pp. 15-24 (1982) present a useful discussion of the difference between rosin acid and rosin soap sizes and the presumed mechanism by which they contribute to sizing.
The exact physical chemical mechanism by which sizing molecules bond to cellulosic fibers has been the subject of much debate and there is not a general consensus among experts. The mechanism explained earlier for rosin soap sizes has been fairly generally accepted. Controversy still exists as to the mechanism by which rosin acids, alkyl ketene dimers and alkenylsuccinic anhydride impart sizing. The manufacturers of these sizes generally support the idea of chemical reaction with the cellulose to form covalent bonds. Others insist that this is unlikely and that other attachment mechanisms prevail. An unpublished M.A. Thesis by Lund (University of Washington, Seattle, 1983) gives convincing evidence that alkyl ketene dimer sizes do not react with the fiber to form covalent bonds. These latter two materials differ in one important respect. Alkenylsuccinic anhydride materials develop sizing at the wet end of the machine and little change occurs through the dryer section. Contrary to this, alkyl ketene dimers continue to develop sizing as the paper is heated in the dryer section.
The question of what actually occurs during sizing appears to be even more complex as the process is carried out in near neutral to slightly alkaline environments in the range between pH 6 and 8. Here it is common to add small amounts of polycationic materials to the system. Cationic starch is one such material and polycationic materials normally used as wet strength resins are another. Among the latter group are polyalkylene polyamine epichlorohydrin compositions and cationic urea-formaldehyde condensation products. These are normally added with the size or subsequent to the addition of the sizing material although practice in this regard is not uniform. It is known that these materials help in some way, but the most generally held belief is that they serve to break the sizing emulsion and contribute a slightly cationic charge to the sizing particles so that they will be attracted to and attach to the anionic cellulose fiber surfaces. Various writers refer to these cationic materials, as well as to alum, as fortifying agents, retention agents, or fixatives.
The patent literature on sizing agents is extensive. Despite the many new compositions that have been described, only the three discussed earlier have achieved significant commercial importance. However, the patent literature is informative as to various materials which have been proposed as sizing and the manner in which these materials are presumed to operate. As one example, British Pat. No. 1,255,829 describes a rosin acid size having 80-98% free acid. This material is used with up to 0.5% alum based on fiber with up to 0.25%, based on fiber, of a water soluble cationic polyamide having a molecular weight in excess of 1,000. This system is said to be usable in the pH range of 6-7.5, unusually high for a rosin based size. The reason the system works at this high pH is that the size is added and precipitated before it can be fully neutralized. The additives can be introduced in any order, either with the size, before the size or after the size. Preferred practice would be to add the cationic material after the size and alum have been introduced into the system.
A technical leaflet by the firm BASF, Charlotte, N.C. describes fixing agent FP as a cationic synthetic resin particularly suitable for fixing rosin size in neutral media. This material, believed to be a polyethyleneimine-type, is added to the paper stock prior to the addition of size and alum.
Kulick, U.S. Pat. No. 3,526,524 describes a rosin paste size which includes a water soluble cationic polyalkylenepolyamine. The cationic material is stated to increase the effectiveness of the rosin.
In Canadian Pat. No. 1,008,609, Strazdins teaches that a polyvinylcycloamidine can be used to increase the effectiveness of a conventional rosin-based size. The polymeric material, alum, and size can be added to a pulp slurry in any order or premixed except that the alum and size must be added separately to avoid premature precipitation.
Harding et al, U.S. Pat. No. 4,505,775, teach a process for preparation of cellulosic fibers made cationic by reaction with a modified epichlorohydrin-dimethylamine reaction product. These fibers are said to have less tendency to repel anionic additives and to make possible the use of sizes such as alkyl ketene dimers under less acidic conditions.
Kowatani et al, U.S. Pat. No. 4,576,680, describe new sizes based on alkenylsuccinic anhydride. These inventors note that polyamide polyamine resins are useful as sizing "fixing agents." The inventors are somewhat unclear as to how these materials are used, but they are apparently added to the pulp slurry prior to the addition of the sizing material.
Japanese Kokai 53[1978]-45403 teaches sizing agents based on hydrocarbon O-(substituted carbonyl) oxime derivatives. Polyethyleneimine can be used both as an emulsifier and may be added to the pulp slurry subsequent to the addition of the sizing. These sizes presumably work by an acyl transfer mechanism to attach a long chain hydrophobic portion of the molecule to the cellulose hydroxyl groups.
Beck, U.S. Pat. No. 3,900,335, discloses N,N'-alkyl substituted aspartimide sizing compositions. Common wet end additives such as polyacrylamides and alum may be used with the sizing material. No order of addition of these adjuncts is specified.
In U.S. Pat. No. 3,993,640, Pickard et al describe cyclic N-substituted imide sizing agents in which the N-substituted group is preferably an electron withdrawing group; e.g., a long chain acyl group. The composition presumably imparts sizing by an acyl transfer mechanism to attach the long chain acyl group to the cellulose. Aqueous emulsions of the sizing agents preferably contain a retention aid such as a polyacrylamide. A goal of the invention is to provide a size which is chemically tied to the cellulose by covalent bonding.
In U.S. Pat. No. 3,726,822, von Bonin et al. disclose anionic paper sizes based on succinimide-type compounds mixed with polymeric latices. A retention aid such as a condensate of dicyandiamide and formaledhyde is added to the pulp slurry prior to adding the size. This material may also be applied as a surface size to an alum treated paper.
Bowman and Cuculo, Textile Res. J., 45:766-722 (1975), in discussing the reaction of phthalamic acid with cellulose, note that the phthalimide is formed in a competing reaction which lowers the efficiency of the esterification. These compounds are analogs of succinic anhydride sizes. The above observation would speak against the usefulness of cyclic imide compounds as sizing agents.
The documents cited above are intended to be exemplary rather that fully inclusive of the literature on various sizing materials. The sizing materials described in them are primarily types designed for use in the neutral range and with which a polycationic materials is employed or recommended as a sizing adjunct. It is worthy of note that there is no unanimity of opinion as to when or where the adjacent should be added. Different inventors make different recommendations even though the sizing materials may be chemically similar.
What has been lacking in the field of paper sizing is a full and clear understanding of the mechanism by which sizing compounds are transferred to and retained by the fiber and the mechanism by which sizing further develops in the dryer section of the paper machine. The present inventors now believe they have discovered and understand these mechanisms. This knowledge has, in turn, led to a definition of chemical criteria for sizing compositions, especially those to be used in the near neutral and alkaline ranges. Of equal importance, the knowledge of how sizing is transferred and developed has led to new process criteria which are generally applicable to a wide spectrum of heretofore unsuspected and undescribed paper sizing compositions.
SUMMARY OF THE INVENTION
The present invention is a method of sizing a cellulosic paper product and in particular products made under neutral to alkaline conditions. The invention further discloses entire new classes of chemical materials which give excellent sizing. The method of the invention has arisen out of new insights as to how sizing occurs in paper products and how sizing is transferred from the liquid phase of a papermaking slurry to the cellulose fibers comprising the ultimate product. Out of this knowledge has arisen the further understanding of the molecular architecture required for chemicals useful for sizing paper. Many of these new sizing compositions are effective at least as high as pH 10.5 when used with the methods of the present invention whereas conventional sizing technology and materials are ineffective above the range of pH 8-8.5.
As noted in the background of the invention, conventional wisdom holds that either the sizing chemical, which has been added to the papermaking stock as an emulsion, or the fiber surface, or both, must in some way have the ionic charge on their surface adjusted so that they are compatible and attractive to each other. With rosin sizes, alum is the single chemical most used to accomplish this modification. It serves the further purpose of breaking the emulsion and, under acidic conditions, causing the formation of minute rosin acid globules. These are ionically attracted to or in some other way contact the cellulose fibers. Here they are held in an aluminum complex of some type which may include aluminum esters. When rosin sizes are used under conditions which approximate neutrality, additional adjuvants are often added to the system. There is no consistency in practice or understanding as to when or where these materials should be included or even as to the function they perform.
It is also known that paper treated under relatively strongly acidic conditions with soap sizes and alum; i.e., about pH 4.5, has developed sizing by the time it leaves the wet end of the paper machine. Little further development occurs during the dryer section. On the other hand, it has further been observed that in paper sized under conditions when significant amounts of rosin acid are present, sizing develops as it passes over the dryers. This development has been attributed to the rosin acid physically "flowing" over the fibers under the influence of heat.
The above beliefs fail to explain many of the phenomena associated with sizing. For example, it is known that under some conditions there is decrease in sizing as one goes from the surface to the interior of a large roll of kraft linerboard. It has been further observed that satisfactorily sized sheets can be made of stock which is a mixture of previously sized with unsize fibers. It has also been observed that sizing regression occurs in some products; i.e., sizing decreases even at room temperature over time. Because of the above and other problems, it was felt that the currently accepted theories of sizing were too limited and lacked the scientific elegance to explain the above-noted discrepancies and many others. It was apparent that a modification of the currently accepted theory was needed to give a broad understanding of the overall mechanism by which sizing occurs in paper.
As the work developed, it appeared that previous workers had not understood that there were at least two separate processes involved in the development of sizing. They had assumed that materials which brought size down onto the fiber should also hold in on the fiber. Present work has shown that these concepts must be considered separately. This understanding has now evolved into what we will term the Strong Bond/Weak Bond theory. When size has been brought down onto the fibers from the papermaking slurry to a receptive fiber surface, the size begins to react in one of two ways to produce what is called for convenience either a "strongly bonded" or "weakly bonded" entity.
A strongly bonded entity is defined here as one where the bond between a cellulose fiber and a sizing chemical cannot be readily broken by energy available in the dryer section of a paper machine. This could include covalent bonds, aluminum esters, and ionic bonds of unit or greater charge.
A weakly bonded entity is here defined as one where the bond between a cellulose fiber and sizing chemical can be broken by the energy availabe in the dryer section of a paper machine. This, in turn, can include such bonds as certain electrostatic bonds of less than unit charge and van der Waals linkages.
In strong bond sizing the distribution of the sizing on the fiber will normally occur and be fixed prior to the time the fiber slurry flows onto the sheet former. Contrary to this, in a weak bond system, the distribution of the sizing chemical through the sheet can largely occur during drying.
Our data strongly support the earlier cited observations of Lund and others he cites that this distribution occurs by the vapor phase redistribution of the chemical rather than by a physical "flow" or sintering process as had been previously believed. This indicates that the chemical imparting the sizing to the fibers must have a positive vapor pressure of some minimum magnitude at the pH at which the paper is being manufactured if it is to ultimately be uniformly distributed through the fiber mass. The vapor pressure of the sizing material should be at least 1×10 -4 mm of mercury at dryer section temperatures of about 60° C. Preferably the vapor pressure will be at least 6×10 -4 mm at 60° C.
It is implicit to the development of sizing that the sizing molecule must be oriented with the hydrophobic "tail" outward. This need for a proper orientation mechanism has been little considered. In many systems inversion of the orientation of the size molecule will occur. This places the hydrophobic tail near the fiber and the hydrophilic polar group facing away from the fiber with a subsequent loss of sizing. With proper orientation of the sizing molecules on the fiber surface, the hydrophobe/hydrophile ratio of the polar and non-polar moieties comprising the the sizing molecule determines the ultimate hydrophobicity that can be given to that fiber. However, there also appears to be an optimum ratio of the hydrophobic to the hydrophilic moieties. When deviations from this ratio are too large, sizing will suffer. We have found that the hydrophobic portion should be a hydrocarbon or substituted hydrocarbon group with a total of at least 8 carbon atoms if the hydrophilic portion does not contain a ring structure and at least 6 carbon atoms if the hydrophilic portion of the molecule is associated with a ring structure. The hydrophilic portion in either case may have up to 40 carbon atoms but it preferably has between and 20 and most preferably between 12 and 20 carbon atoms.
A critically important aspect of sizing that has been readily overlooked before is the need for preparing a receptive fiber surface. This is a problem which can be considered and dealt with entirely separate from the matter of bringing the sizing onto the fiber surfaces. Experiments have shown that if the fiber surface is first made mildly cationic by treating it with either water soluble or water dispersible polyvalent metal ions or polycationic polymers, or some combination of these, the bond strength between the fiber and sizing can be controlled so that a desirable balance is achieved between strong bonds and weak bonds. We refer to the material used in this first treatment as a "catcher" or an "anchoring/orienting" agent. What is even more important, the anchoring/orienting agent can be chosen for the specific chemistry of the sizing materials so that sizing will be fully developed by dryer heat by the time the sheet reaches thesize press on the machine.
The question might be asked why are not strong bonds achieved at the wet end the most desirable. The answer to this is found in the dimensions of the size globules striking the fibers. If this occurred at a molecular level where the fibers would be completely coated with a monolayer of closely adjacent sizing molecules, there would be no need for subsequent sizing redistribution. However, this ideal situation is seldom approximated in practice. The sizing comes to the fiber as finite globules which attach to the fiber with significant space between adjacent globules. Unless the sizing chemical is somehow enabled to move into this space between the globules, and of equal importances, be retained by the fiber, good sizing is not possible. Stated simply, there may well be enough sizing present to adequately coat the fibers, but much of it is not located at the right places. If good sizing at high efficiency is to be developed, the two requirements stated above may be restated as essential criteria: (1) the size must be enabled to move unsized areas of the fiber surface, and (2) the unsized surface must be adequately receptive so that the sizing will be anchored and have the proper orientation. It is this last criterion which has been almost completely ignored by past workers in the field.
It has now become apparent why it is so difficult to achieve good sizing with rosin at a pH above about 6.5. The lower the pK of an acid, the more that material will be ionized at a given pH. Rosin fumarate has a measured pK of approximately 5.3 in water. The use of the Henderson-Hasselbach equation enables one to predict the pH at which a given ratio of anion to anion conjugate acid can exist. This equation is as follows:
pH=PK'+log(Anion/Anion H)
Using this equation, it is apparent that at pH 6.5, 94% of the acidic groups in rosin fumarate are saponified and in soap form at equilibrium and little acid form remains available for distribution. At pH 8.5 the acidic groups are 99.94% saponified at equilibrium. The salts of fatty acids for practical purposes have no volatility at all under dryer conditions. As noted previously, the evidence strongly points to a vapor phase redistribution of the sizing. Thus, at a pH above 6.5, when the rosin is largely in the soap form, little is available to move to unsized areas of the fiber. Unless the fiber surface is receptive, even that very small portion which remains unionized and in free acid form may simply disappear from the system instead of being captured by areas which lack sizing. It follows from what has just been stated that the higher the pK of the sizing compound the more will remain un-ionized at higher pH. This then leads to one of the criteria of the present invention. If a size is to be used under neutral to alkaline conditions, the pK should be 6 or greater. The range of pK may fall between about 6 and 14 in water, or even somewhat higher in some instances. Preferably, the pK of the sizing composition will be in the range between about 6 and 12 in water and most preferably in the range of about 9-10. Carboxylic acid types sizes, such as rosin, or materials which produce carboxylic species as the effective sizing agent, do not generally meet the pK requirement of the present invention.
A second criterion for the sizing material is directed to its molecular geometry. Extremely strong bonds, such as covalent bonds or bonds formed through aluminum esters, effectively prevent any redistribution of the sizing material. At the other end of the scale, extremely weak bonds, such as those given by van der Waals' forces, hold the sizing so loosely that much of it may be lost. The present invention is based on an alternative explanation of bonding between the sizing molecule and fiber. This has led to a new and more efficient method of applying sizing. It has also opened the door for many new and unexpected chemical materials to be used as sizes. It now appears that when the sizing molecule is tied to receptive sites on the fiber by coulombic forces the bond strength may be controlled by the chemistry of both the sizing molecule and the anchoring/ orienting agent used to bind it to the fiber. Coulombic forces are electrostatic forces created by adjacent oppositely charged molecules or, stated otherwise, molecules having opposite electrical polarity. To achieve this coulombic binding, the sizing molecule should hve a hydrophilic portion which provides a The word "bidentate" is used herein in an analogous manner to the way in which it is applied in the chemistry of polyvalent and transition metals which can form five or six membered rings with certain organic molecules having at least two hetero atoms. It is not implied here that such complexes are even involved in the current invention. However, the adoption of an analogous bidentate criterion, taken in conjunction with the pK criterion stated earlier, has proved to be powerfully predictive of new compounds which form highly effective sizing materials.
Another criterion of the sizing chemical is adequate volatility to redistribute over the fibers under conditions encountered in the paper machine dryer section. The vapor pressure should be at least 1×10 -4 mm of mercury at dryer section temperatures, typically about 60° C. Preferably it is at least 6×10 -4 mm of mercury at 60° C. and may be much higher. Salts and other compounds which are tightly ionically bonded normally fail to have a vapor pressure in the above range.
The sizing chemicals of the present invention are of form R 1 --B--C--D wherein R 1 is selected from nonpolar straight chain or branched alkyl, alkenyl, substituted alkyl, substituted alkenyl groups containing from 6-40 carbon atoms, and nitrophenyldiazo, wherein said substituent groups are selected from the group consisting of halogen, phenyl, alkylphenyl, halophenyl, alkoxyphenyl; B is absent from the sizing molecule or is a small polar moiety selected from the group consisting of carboxyl ester (--COO--), carbonyl, oxygen, sulfur, and --NR 2 --where R 2 is hydrogen or methyl; C is absent from the sizing molecule or is selected from aryl, alkylene, and cycloalkylene groups wherein the latter two groups may have from 1 to 6 carbon atoms; and D is a bidentate polar group possessing an acidic proton and having a pK >6 in water and is selected from the group consisting of o-dihydroxyaryls, hydroxamic acids, beta-diones, amides and cyclic imides.
In addition to the compounds just stated, the following materials, while not actually tried, would be predicted to form satisfactory sizing agents: 2-hydroxypyridines, 2-hydroxyquinolines, 8-hydroxyquinolines, sulfonamides, N-monoalkyl sulfonamides, N-monoaryl sulfonamides, oximes wherein the oxime group is vicinal to other heteroatoms, nitrolic acids, C-alkylsuccinicdiamides, C-alkylmalonicdiamides, N-oxo-2-hydroxypyridines, N-oxo-2-hydroxyquinolines, nitroalkyls with alpha hydrogen, 5-alkylthiazolidine-2,4-diones, 5-arylthiazolodine-2,4-diones, 5-alkylidene-2-thioxothiazolidine-4-one, 5-arylidene-2-thioxothiazolidine-4-one, 3-alkyl-1,2,4-thiadiazole-5(2H)-one, 3-aryl-1,2,4-thiadiazole-5(2H)-one, 5 or 6-alkyl-2-thiouracil, 5 or 6-aryl-2-thiouriacil, and 2,2-dialkyl-6,6,7,7,8,8-heptafluoro-3,5-octanediones.
Materials suitable for anchoring and orienting agents may be drawn from the wide variety of commercially available water soluble or water dispersible polycationic polymers. These are chosen from crosslinked or uncrosslinked polymeric reaction products of epichlorohydrin with a material selected from the group of aliphatic amines of the form R 4 --NH--R 5 , tertiary aliphatic diamines of the form
R.sub.6 N-R.sub.8 --N--R.sub.10
aliphatic diamides of the form ##STR1## and mixtures thereof, wherein the crosslinking agent if present is selected from ammonia, primary aliphatic amines containing up to 8 carbon atoms, polyalkylene polyamines, and mixtures thereof, with R 4 and R 5 being alkyl groups totaling not more than 8 carbon atoms, R 6 , R 7 , R 9 , and R 10 being methyl or ethyl groups, R 8 being an alkylene group having between 2 and 8 carbon atoms, and R 11 being an alkylene group having between 0 and 8 carbon atoms. Also useful are partially or wholly quaternized polyethylene-imines where the quaternary substituents are methyl or ethyl groups or are polyethyleneimine branches at tertiary nitrogen atoms. Especially useful among these are amine and polyamine reaction products with epichlorohydrin in both crosslinked and uncrosslinked form. Polymers which are polyamide-polyamine-epichlorohydrin reaction products are also generally suitable. One preferred anchoring and orienting agent is selected from crosslinked and uncrosslinked condensates of epichlorohydrin and dimethylamine wherein the crosslinking agent, if present, is selected from ammonia and a primary aliphatic diamine of the type H 2 N--R 3 --NH 2 where R 3 is an alkylene radical of from 2-8 carbon atoms. Polycationic metal salts, such as alum or Zr(IV), are also useful anchoring and orienting agents under some circumstances. Polyvalent metal salts may be employed in conjunction with a polycationic polymer as a means for increasing the bond strength between the anchoring agent and the size when the pK of the sizing material is quite high or the more polar form of the sizing agent is more slowly developed; e.g., by keto-enol tautomerism.
The usage of anchoring and orienting chemicals will vary depending on their nature and the type of sizing material used with them. This will generally be in the range of 0.5-10 kg/t d ry weight based on fiber. Many of the anchoring materials are supplied as solutions in water having about 50% solids. The exact solids content is often difficult to measure without causing decomposition. Preferred usage of those supplied in this manner is in the range of 2.5-5 kg/t on an as-received basis. Where alum is used as an adjuvant to the anchoring material, it will rarely be used in amounts as high as 10 kg/t. Preferred usage, if alum is used at all, is in the neighborhood of 2.5 kg/t. Optimum usages can be readily determined experimentally. Alum as used conventionally in paper sizing is rarely ever used in amounts less than 10 kg/t and frequently higher amounts are used.
The final component of the present invention is a precipitant added to the pulp suspension after the anchoring agent and after the sizing materials have been dispersed in the slurry. The precipitant should be used in the minimum amount necessary to break the sizing emulsion. The chief purpose of the precipitant is to break the emulsion and precipitate the sizing agent into the fibers, not to form attachment points for the globules on the fiber. The latter function is served by the anchoring/orienting agent. It is conceivable that under some circumstances the same material could be used as an anchoring/orienting agent and as a precipitant. However, it is inherent in the present invention that these would be added to the pulp slurry at different times, the anchoring agent before and the precipitant following the addition and dispersion of the sizing agent. Small quantities of alum are normally preferred as the precipitant. Usually, no more alum should be added at this point than is necessary to break the sizing emulsion. It is important to avoid the formation of of excess quantities of a strong bond complex that restricts redistribution of the size in the dryer section.
It is greatly preferred that sizing using the precedure of the present invention should be carried out at a system pH of at least 5.5 or higher, measured after addition of the emulsified size and precipitant.
The present inventors are unaware of any distinction made in the literature between the anchoring/orienting function and the precipitating function. While, as just noted, the same chemical entity may sometimes fill both roles, it will be frequently be too low or too high in efficiency in performing one of the functions. As an example, polycationic polymers frequently serve with low efficiency as precipitants whereas good precipitants such as alum, especially when used in excess, sometimes bind the initially precipitated size globules so tightly to the fiber that the material cannot redistribute on heating. The function of the precipitant is to bring the minute globules of size down onto the fiber. The function of the anchoring agent is to hold the sizing and assist in redistribution and orientation of the excess sizing molecules in the globules. The anchoring agent also controls the rate of redistribution and consequent increase in sizing. For most economic and efficient sizing the extent and rate of redistribution should be controlled by the anchoring/orienting material and not by the precipitant.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
A number of candidate chemicals from different chemical genera were arbitrarily selected to be tested as paper sizing agents using the procedures of the present method. With the exception of one group, these materials all met the criteria of having a bidentate hydrophilic portion with hydrophobic substituent groups and a pK in water greater than 6. All of the chemicals were evaluated in laboratory prepared handsheets.
GENERAL PROCEDURE FOR MAKING AND TESTING HANDSHEETS
Handsheets were made using a bleached mixed conifer, predominantly inland spruce, kraft pulp using standard Tappi procedures with a 15.2 cm (6 inch) diameter British sheet mold. Sheets were made at one of two basis weights as specified in the examples. Either 1.88 g or 2.50 g (dry weight) of the pulp was suspended in water at 0.5 to 1.0% consistency and dispersed for 2 minutes at high speed in a Waring Blendor. These pulp usages correspond to sheets having grammages of about 100 and 140 g/m 2 .
Those handsheets made according to the present invention were prepared by first adding the specified amount of the cationic size anchoring and orienting agent (the catcher) in an aqueous solution to the dispersed pulp furnish in the blender. This mixture was blended 30 seconds to permit the material to alter the electrical charge on the pulp fiber surface. Then the sizing agent was added. In some cases the size was prepared as an emulsion but more frequently it was used as a solution in alcohol or acetone, if a solid, or undiluted ("neat"), if the material was a liquid. While this procedure would not be preferred for production use it served well for screening new compositions.
After size addition the pulp slurry was blended for an additional 60 seconds. Finally, a solution of the size precipitant, typically papermaker's alum, was added and dispersed for 30 seconds. The pH was adjusted as required with dilute sodium hydroxide solution or sulfuric acid and then the slurry was sheeted. Sheets were couched and then either air dried at 50% R.H. or on a drum dryer at 105° C. as specified.
Sizing was measured using a modified Hercules Size Test procedure. (Hercules, Inc., Wilmington, Del., Bulletin PM 515). No lactic or formic acid were used in the wetting liquid. The sheet being tested was placed over a photocell and reflectance from the back of the sheet adjusted to 100%. A green anionic dye solution in water was added to the reservoir on top of the sheet. The time in seconds was measured for the dye solution to penetrate and decrease the reflectance to 80%. Tests were arbitrarily terminated at 600 seconds (sometimes 300 seconds) if dye penetration had not occurred prior to this time or when reflectance had dropped to 80%, whichever occurred first. Commercially made sized papers typically reach 80% reflectance in 15-50 seconds.
SIZING TRANSFER EXPERIMENTS
Heavily sized handsheets (150 kg/t of the sizing agent) were prepared. Receiving sheets were made of the same bleached spruce kraft pulp to a basis weight of 90-95 g/m 2 . These were treated only with 2.5 kg/t of a cationic size anchoring and orienting agent and then the slurry was adjusted to the desired pH. For all experiments reported here either alum or Nalco 7135, believed to be a hexamethylenediamine modified epichlorohydrin-dimethylamine condensation product was used as the anchoring/orienting agent. Nalco 7135 is available from Nalco Chemical Company, Oak Brook, Ill. Five of the unsized receiving sheets were placed over the heavily sized donor sheet. This sheet bundle was wrapped in aluminum foil and placed on a hot plate at 110° C. with the sized sheet adjacent to the hot surface. A weight is placed on top of the stack to keep the sheets flat and in contact. The sheet bundles were heated for varying times and temperatures as indicated in the examples. The receiving sheets were periodically tested for development of sizing.
SYNTHESIS OF CANDIDATE SIZING MATERIALS
The following chemicals were regarded from theoretical considerations as excellent candidate sizing materials representing three classes of bindentate molecules: 4-octanoylcatechol; stearoyl, N-methylstearoyl, and oleylhydroxamic acids; and 2,4-heptadecadione. None of these could be found from commercial sources. Therefore, they were synthesized by the following procedures.
4-Octanoylcatechol was prepared from catechol and octanoyl chloride by the method of Miller et al, J. Am Chem Soc, 60:7-10 (1938). The product was distilled and a broad fraction collected which boiled from 200°-220° C. at 2 mm Hg. Attempts to recrystalize the oily material proceeded poorly. The oil was then separated into two fractions on a neutral aluminum oxide column packed in ethyl acetate. Ethyl acetate containing 15% methanol washed off a non-phenolic fraction. Ethyl acetate containing 10% acetic acid then was used to wash off a phenolic fraction. Recrystallization of the latter from hot cyclohexane gave material with m.p. 87°-88° C. 13 C-NMR of the product was consistent with the structure of 4-octanoylcatechol.
The hydroxamic acids were prepared from the corresponding carboxylic esters, the appropriate hydroxylamine hydrochloride, and potassium hydroxide using the method of Hauser and Renfrow, Organic Synthesis, Coll. Vol. II, p.67 (1943). Solutions of hydroxylamine HCl or N-methylhydroxylamine HCl in methanol were each combined with solutions of KOH in methanol. The precipitated KCl was filtered off and each solution treated with 0.5 equivalent of methyl stearate in isopropanol or with liquid methyl oleate. The N-methylstearoylhydroxamic acid was recrystallized from toluene and had a m.p. 102°-104° C. The oleoylhydroxamic acid was recrystallized from ethyl acetate and melted at 78°-79° C. Infrared spectra were consistent with a hydroxamic acid structure for each material.
2,4-Heptadecadione was prepared from 1-bromododecane, 2,4-pentanedione, and sodium amide in liquid ammonia using the method of Hampton and Harris, Organic Synthesis, Coll. Vol. V, p.848 (1973). The product was extracted into ether, washed with water, dried with magnesium sulfate, and the ether removed. The remaining solid residue was recrystallized from ethanol to give a solid with m.p. 46°-47° C. The 13 C NMR spectrum was consistent with the structure of 2,4-heptadecadione.
SCREENING TESTS
A series of samples was made using a commercially available acid rosin emulsion size. All tests were carried out at pH 6.5, a condition normally regarded as the extreme upper limit for use of a rosin size. Three different polycationic polymers, each at two levels, were used as anchoring/orienting materials. These materials were Nalco 7135, Nalco 7655 and Monsanto SR-31. The Nalco materials are available from Nalco Chemical Company, Oak Brook, Ill. The N-7135 is believed to be a hexamethylenediamine (HMDA) modified epichlorohydrin dimethylamine reaction product. N-7655 is believed to be the unmodified reaction product of epichlorohydrin and dimethylamine.
SR-31 is available from Monsanto Chemical Company, St. Louis, Mo. and is believed to be an amine-epoxy adduct, sold primarily for use as a wet strength agent. All of the handsheets were prepared as described under the general procedure with the anchoring/orienting agent being added first, then the rosin acid size, and finally the alum precipitant. In all cases 2.5 kg/t of the sizing agent was used. The reported usage of cationic polymers was on an as received basis; i.e., containing approximately 50% polymer in water solution. The results of these tests are reported in Table 1. Alum and rosin were added on a 100% solids basis.
TABLE 1______________________________________Polymer Polymer Usage Alum Usage Sizing, secondsUsed kg/t kg/t Unheated Heated______________________________________N-7135 1 2.5 61 600+N-7135 4 2.5 314 600+SR-31 2 2.5 23 278SR-31 4 2.5 46 600+N-7655 1 2.5 58 173N-7655 4 2.5 1.3 1.6None -- 10 0 0.2______________________________________
Referring to the sizing data in Table 1, two results stand out clearly. It is indeed possible to get excellent sizing with rosin at a pH as high as 6.5 using the method of the present invention. This is shown with the samples made at that pH using the Nalco 7135 as an anchoring agent. The seconde thing that stands out are the obvious differences in performance of the various polymers. The N-7135 is presumed to form relatively weak bonds with the sizing permitting ready redistribution on heating. In contrast the N-7655 may form strong bonds with the sizing agent, or size may have been lost from the sheet on heating due to an excessively weak bond between the size and sheet. Relatively little additional sizing developed on heating. This shows the opportunity for tailoring the anchoring/orienting agent to the sizing material, based on their relative polarity. The poor sizing results obtained when no anchoring agent was used are interpreted to indicate that original distribution of sizing on the fibers was non-uniform and/or little or no redistribution occurred under the test conditions used.
Commercially sold rosin sizes are very reliable when used according to manufacturers' recommendations. When these materials were used for screening tests, it can be assumed that failure to give sizing represents a problem in the chemistry of the system. This assumption may not by made for the new materials reported here. Emulsification studies to prepare optimally dispersed sizes are very time consuming and are impractical when a large number of chemicals are being screened. For this reason most of the new sizing materials were used unemulsified. In this situation, failure of a material to give sizing must be considered an ambiguous result. It could indicate that the material was ineffective under the conditions used or it could simply be a technical failure to properly precipitate and hold the candidate material on the fiber. Nevertheless, clear patterns developed. Some generic classes of materials repeatedly failed to produce sizing while others consistently produced excellent sizing. In many of the screening tests results with the same sizing compound were either maximum or zero sizing.
Candidate sizing materials were first screened at the very high (and commercially impractical) usage of 150 kg/t, based on dry fiber. Those that showed sizing at this level were then screened at 10 and 2.5 kg/t, the latter being a typical level of commercial usage.
Based on the criteria developed from the Strong Bond/Weak Bond sizing theory presented earlier, representatives of four generic classes of chemical materials expected to be suitable were screened at pH values generally in the 6.5-10.5 range. The three genera from which candidates were drawn were catechols, beta-diketones, hydroxamic acids, and imides. A number of monophenols and non-vicinal diphenols were screened. No members of these classes gave sizing. This led to the conclusion that the bidentate polar structure was essential for proper anchoring and orientation in the higher pH ranges. While it is unlikely that paper would be made at pH 10, trials made at this high pH were indicative of the bond strength between sizing and fiber, and it is presumed that this information can be translated into new classes of sizing materials and sizing agents which exhibit improved efficiency.
Handsheets were tested for sizing development as made after air drying at room temperature and 50% RH, and after being heated to 105°-110° C. for about one hour.
A control series was made using a commercially available rosin acid emulsion size. This was used well above the pH range recommended by the manufacturer. Any poor performance noted here for this material should not be considered as an indication of performance expected when used as recommended at lower pH.
EXAMPLE 1
Handsheets were made using Monsize, a very fine particle rosin acid emulsion size. Monsize is a registered trademark of and is available from Monsanto Corp., St. Louis, Mo. This was used in conjunction with Nalco 7135 as an anchoring/orienting agent and alum as a precipitating agent. Sheets were made at a basis weight of about 140 g/m 2 . The following sizing results were obtained.
TABLE 2______________________________________ AnchorSize Load Mat'l. Alum Sheeting Sizing, seckg/t kg/t kg/t pH Unheated Heated______________________________________150 5 10 6.0 73 --*150 5 10 6.8 44 --150 5 10 8.8 0 --150 5 10 10.4 0 --10 2.5 20 6.5 600+ 600+10 2.5 20 7.5 600+ 600+10 2.5 20 8.5 600+ 1182.5 5 10 5.5 600+ --2.5 5 10 5.5 600+ --2.5 2.5 20 6.5 600+ 502.5 2.5 20 8.5 47 02.5 2.5 20 10.5 0 0______________________________________ *Missing values indicate that the samples were not tested.
The data indicate that, given the use of an anchoring/orienting agent and sufficient alum in the system, at least some sizing can be obtained with rosin up to pH 8.5 but no sizing was found at pH 10.5. The data further show that when commercial quantities of size were used (i.e., ˜2.5 kg/t) in the pH range of 6.8-8.5, the sizing was essentially lost when the samples were heated.
These data are fully in accord with results that would be expected from many years of experience with rosin sizes. They are also in accord with results predicted by the Strong Bond/Weak Bond theory described earlier. The work also illustrates a way to remarkably improve sizing by rosin acid at pH 6.5 using separate anchoring/orienting agents and precipitant.
EXAMPLE 2
A number of monophenols and non-vicinal dihydroxy phenols were tested. These produced no sizing at all, leading to the requirement for a bidentate structure of the hydrophilic portion of the molecule. Nonylphenol, dinonylphenol, 2-chlorophenol, 4-chlorophenol, 2-hydroxyacetaphenone, salicylaldehyde, 4-dodecylresorcinol, dihydroxyanthraquinone, and 2,2-bis-(4-hydroxyphenyl) butane all failed to produce any sizing under the conditions of testing. Tests were primarily made in the pH 4.5-5.5 range although nonyl and dinonylphenol were tested over the range of 4.5-10.8. Either 5 or 10 kg/t Nalco 7135 was used as an anchoring orienting agent and alum precipitator usage varied between 2.5 and 40 kg/ton, most typically about 10 kg/t.
EXAMPLE 3
A group of catechol-type compounds were tested for sizing efficiency. The term "catechol-type" refers to compounds including an aromatic moiety with two adjacent hydroxyl groups. There may be additional hydroxyl groups present in adjacent or non-adjacent positions. In light of the Strong Bond/Weak Bond theory catechols were predicted to be suitable sizes when properly substituted with a hydrophobic moiety. They meet the bidentate criterion, have the requisite vapor pressure, and generally have a pK falling within the range of 7-10. A number of materials commercially available as laboratory reagents were chosen for testing. One, 4-octanoylcatechol was synthesized in the laboratory using standard published methods as described earlier. The chemicals selected for screening included materials believed to be suitable sizing agents and those expected to be unsuitable due to a low ratio of hydrophobic to hydrophilic portions of the molecule. Results of tests and a list of materials tested is found in Table 3.
In general, those substituted catechols having side moiety substitution totalling at least six carbon atoms contributed excellent sizing. Those with smaller substituent groups, in general, performed poorly or did not size at all. It is significant that good sizing was obtained over the broad pH range of 6.5-10.5. Again, it should be kept in mind that no attempt was made here to optimize either the chemical material or the system in which it was used.
TABLE 3__________________________________________________________________________Catechols Used as Sizing Agents Sizing Anchor Load Mat'l Alum Sheeting Sizing, sec.Material Used kg/t kg/t kg/t pH Unheated Heated__________________________________________________________________________4-Octanoylcatechol 150 5 10 11.3 --* 600+4-Octanoylcatechol 10 2.5 20 6.5-8.5 600+ 600+4-Octanoylcatechol 2.5 2.5 20 6.5-8.5 600+ 600+4-Octanoylcatechol 2.5 2.5 20 10.5 680 4904-Octanoylcatechol 12 2.5 20 5.5 300+ 300+3,5-Di-t-butylcatechol 150 5 10 10.0 600+3,5-Di-t-butylcatechol 2.5 5 10 10.2 -- --4-t-Octylcatechol 150 5 10 10.0 600+ 600+4-t-Octylcatechol 2.5 5 10 10.2 83 600+4-(4 Nitrophenylazo)catechol 150 5 10 10.8 0 600+4-(4 Nitrophenylazo)catechol 2.5 5 10 11.0 0 0Tetrabromocatechol 150 5 10 10.2 0 0Lauryl gallate 150 5 10 11.0 600+ 600+Lauryl gallate 2.5 5 10 10.2-10.7 0 0Octyl gallate 150 5 10 10.5 600+ 250Octyl gallate 2.5 5 10 10.8 600+ 300+Methyl gallate 150 5 10 11.0 0 532,3,4-Trihydroxybenzophenone 150 5 10 11.0 0 532,3,4-Trihydroxybenzophenone 2.5 5 10 10.2 600+ 44-Chlorocatechol 5 10 2.5 6.9 0 --Methyl-3,4,5-trihydroxy-benzoate 150 5 10 10.4 0 0Ethyl-3,4-dihydroxy-benzoate 2.5 5 10 10.0 0 04-(4-Nitrophenylazo)resorcinol 150 5 10 9.7 0 0(4-Nitrophenylazo)benzenetriol 150 5 10 10.2 0 0R-(-)Isoproterenol-HCl 150 5 10 10.9 0 0__________________________________________________________________________ *Missing values indicate samples were not tested.
EXAMPLE 4
Three hydroxamic (HA) acid materials were synthesized in the laboratory, as described earlier, for sizing screening tests. These compounds were N-methylstearoyl HA, stearoyl HA, and oleyl HA. They were tested similarly to the catechols described in the previous example. Results are reported in Table 4.
All of the materials proved to be effective sizes although results were quite variable. This appears to be an indication of lack of optimization of the system rather than an inherent deficiency in the chemical materials themselves. In particular, the loss of sizing on heating at the lower usages of N-methylstearoyl HA seems to indicate that a stronger anchoring/orienting agent may be required.
TABLE 4__________________________________________________________________________Hydroxamic Acids as Sizing Agents Sizing Anchor Load Mat'l Alum Sheeting Sizing, sec.Material Used kg/t kg/t kg/t pH Unheated Heated__________________________________________________________________________N--Methylstearoyl HA 150 5 10 6.3-10.5 -- 600+N--Methylstearoyl HA 10 2.5 20 6.5-8.5 600+ 600+N--Methylstearoyl HA 10 2.5 20 7.5 600+ --N--Methylstearoyl HA 10 2.5 20 5.5 300+ 300+N--Methylstearoyl HA 7.5 2.5 20 8.5 600+ 2N--Methylstearoyl HA 5 2.5 20 8.0 400+ 6N--Methylstearoyl HA 2.5 2.5 20 6.5 18 0N--Methylstearoyl HA 2.5 2.5 20 8.5 & 10.5 0 0Oleyl HA 150 5 10 6.5 -- 171Oleyl HA 150 5 10 8.3 -- 162Oleyl HA 150 5 10 10.5 -- 488Oleyl HA 10 2.5 20 6.5 0 --Oleyl HA 10 2.5 20 7.5 & 8.5 11 --Oleyl HA 2.5 25. 20 6.3-10.5 -- 600+Stearoyl HA 150 5 10 6.3- 10.5 -- 600+Stearoyl HA 10 2.5 20 6.5 & 8.5 600+ 0Stearoyl HA 10 2.5 20 7.5 10 0Stearoyl HA 2.5 2.5 20 6.5-10.5 0 0Stearoyl HA 12 2.5 20 5.6 300+ 300+__________________________________________________________________________
EXAMPLE 5
A number of beta-dione sizing candidates were obtained from commercial sources. One, 2,4-heptadicadione was synthesized as described earlier. Screening tests were conducted as described in the two previous examples.
Table 5 shows that sizing was obtained from all of the materials having adequate substitution of hydrophobic moieties. No sizing was noted for three materials having shorter hydrophobic groups. As before, it is evident that systems are not optimum but this would not be expected, nor was it a goal, in the screening tests.
TABLE 5__________________________________________________________________________Beta-Diones as Sizing Agents Sizing Anchor Load Mat'l Alum Sheeting Sizing, sec.Material Used kg/t kg/t kg/t pH Unheated Heated__________________________________________________________________________2,4-Heptadicadone 150 5 10 6.5 -- 1082,4-Heptadicadione 150 5 10 8.4-10.5 -- 600+2,4-Heptadicadione 14 2.5 20 5.4 59 --2,4-Heptadicadione 12 2.5 20 5.7 300+ 300+2,4-Heptadicadione 10 2.5 20 6.5-8.5 600+ 600+2,4-Heptadicadione 2.5 2.5 20 6.5 750 132,4-Heptadicadione 2.5 2.5 20 8.5 6 02,4-Heptadicadione 2.5 2.5 20 10.5 600+ 0Dibenzoylmethane 150 5 10 10.7 600+ 600+Dibenzoylmethane 2.5 5 10 10.5 0 02,2-Dimethyl-6,6,7,7,8,8,8-heptafluoro-3,5ocadiione 150 5 10 10.0 3 650+2,2-Dimethyl-6,6,7,7,8,8,8-heptafluoro-3,5ocadiione 2.5 5 10 11.0 0 02,2,6,6,-Tetramethyl-3,5-heptanedione 150 5 10 9.5 33 600+2,2,6,6-Tetramethyl-3,5-heptanedione 150 5 10 10.5 119 700+2,2,6,6-Tetramethyl-3,5-heptanedione 2.5 5 10 11 3 02-Acetylcyclohexanone 150 5 10 10.1 0 01-Benzoylacetone 150 5 10 11.1 0 24,4,4-Trifluoro-1-phenyl-1,3-butanedione 150 5 10 10.3 0 0__________________________________________________________________________
EXAMPLE 6
One of the salient points of the Strong Bond/Weak Bond sizing theory is the recognition of redistribution of initially weakly bonded sizing by heat energy on the dryer section of the paper machine. The test for this effect was described earlier. Essentially, the test poses the question as to whether sizing can move from one location on a fiber (or sheet) to an unsized site made receptive by the presence of a catcher molecule. To test for this effect a heavily sized donor sheet is placed in contact with a stack of unsized sheets treated with an anchoring agent. The assembly is then heated and sizing tests are periodically run on the receptor sheets.
Four materials were tested for sizing transfer: N-methylstearoylhydroxamic acid, stearoylhydroxamic acid, oleoylhydroxamic acid, and Monsize rosin acid emulsion. All donor sheets, including those with the rosin size, were made using 5 kg/t Nalco 7135 anchoring/orienting agent, 150 kg/t sizing agent, and 10 kg/t alum precipitating agent. Receptor sheets all had 2.5 kg/t Nalco 7135 as the only additive. Donor and receptor sheets were made in narrow ranges around pH 6.5, 8.5, and 10.5. All sheets were air dried at room temperature and 50% RH. Receptor sheets were tested for sizing after the sheet packs had been heated 1, 3 and 7 days at 110° C.
In the tests made using N-methylstearoylhydroxamic acid and stearoylhydroxamic acid the donor and all five receptor sheets showed a sizing level of 600+seconds after 1, 3 and 7 days at each of pH 6.5, 8.5 and 10.5. This plainly shows sizing agent migration from the donor sheet and capture by the previously unsized receptor sheets.
Results with oleylhydroxamic acid were somewhat different from the above. Earlier reported screening tests (Table 4) did not show particularly good results with this material. The reasons for this are not known, since on theoretical considerations the material should be an excellent sizing agent. It is suspected that the problem was in the initial distribution of the oleyl HA on the fiber. Reference to Table 6, showing results of the transfer tests, shows that oleyl HA can size quite well. It also shows that the system is pH sensitive. The higher the pH, the tighter the sizing appears to be bound to the donor sheet. This suggests that an anchoring/orienting agent that does not bind the material so tightly to the fiber should be selected.
TABLE 6______________________________________Oleylhydroxamic Acid Transfer Experiments Sizing Sec.Sheet 1 Day 3 Days 7 Days______________________________________pH 6.6R5* 2 290 600+R4 2 600+ 600+R3 2 40 600+R2 2 600+ 600+R1 6 600+ 600+D 600+ 341 600+pH 8.3R5 1 3 9R4 3 12 33R3 7 36 115R2 19 88 84R1 34 228 600+D 600+ 600+ 600+pH 10.2R5 5 3 6R4 29 7 28R3 571 573 55R2 199 324 151R1 155 158 166D 600+ 600+ 600______________________________________ *R indicates a receptor sheet and D the donor sheet
The transfer experiements made with rosin acid size, particularly those made at the higher pH range are supportive of our interpretation of the sizing mechanism. The data are given in Table 7. Above pH 6.5 rosin acid converts principally to rosin soaps. These are hard to bring down and attach to the fiber and essentially lack volatility. Sizing transfer did occur to receptor sheets at pH 6.5 but did not occur to a significant extent at the higher pH values. Sizing of the donor sheets was also poor at higher pH.
TABLE 7______________________________________Rosin Acid Transfer Experiments Sizing Sec.Sheet 1 Day 3 Days 7 Days______________________________________pH 6.5R5* 3 10 600+R4 2 77 600+R3 15 600+ 600+R2 491 600+ 600+R1 600+ 600+ 600+D 600+ 600+ 333pH 8.5R5 3R4 4R3 7R2 39R1 600D 37pH 10.5R5 0R4 0R3 0R2 0R1 0D 3______________________________________ *R indicates a receptor sheet and D the donor sheet.
EXAMPLE 7
Transfer experiments on samples made with 2,4-heptadecadione were made in similar fashion to those reported in the previous example. Very little sizing was imparted to the receptor sheets. This indicated that either sizing was not being transferred or that a stronger, more aggressive anchor/orienting material was needed in the receptor sheets. We have discovered that as the polarity of the sizing molecule increases and/or the volatility decreases, weaker anchoring agents are needed. The converse of this is also true. Aliphatic beta-diketones are among the least polar materials screened, suggesting that they would need the strongest anchoring agents. To test the assumption, receptor sheets were made containing 5 kg/t alum in addition to the 2.5 kg/t of Nalco 7135 anchoring material. Tests were conducted only on sheets formed at pH 6.5.
Results seen in Table 8 appear to confirm the need for the stronger anchoring/orienting material with excellent sizing being imparted to the receptor sheets after 1 day at 110° C. It is also interesting to note the apparent development of sizing over time in the donor sheet. The relatively low initial value may have been due to poor initial distribution of the sizing material on the fiber.
TABLE 8______________________________________2,4-Heptadecadione Transfer Experiments Sizing Sec.Sheet 1 Day 4 Days 7 Days______________________________________R5.sup.1 419 -- --R4 590 -- --R3 600+ -- --R2 600+ -- --R1 0.sup.3 1700+ --D --.sup.2 -- 600______________________________________ .sup.1 R indicates a receptor sheet and D the donor sheet. .sup.2 Initial unheated value was 108 sec. .sup.3 This value is unexplained and is presumed due to poor initial distribution of the dione on the fiber.
EXAMPLE 8
Despite the comments in the literature that would discourage a skilled investigator from their use as sizing agents, cyclic imides were found to be effective sizing materials when used according to the teachings of the present invention. A commercially available alkenyl succinic anhydride sizing agent was reacted in water with between 1 and 2 equivalents of ammonia under heated conditions. The resulting product was examined by 13 C NMR spectroscopy and found to contain alkenyl succinimide and diamide and less than 3% of amic acid. The mixed product was screened for sizing effectiveness as described earlier. A commercially available rosin size (Monsize) was used as a control. Results of tests on unheated samples are reported below.
TABLE 9______________________________________ SizingSizing Hood Anchor Alum Sheeting Sizing,Agent kg/t kg/t kg/t pH Sec.______________________________________Rosin 2.5 5 10 5.5 600+Rosin 2.5 2.5 20 6.5 650+Rosin 2.5 2.5 20 8.5 47Rosin 2.5 2.5 20 10.5 0Imide/Diamide 300 5 10 8.7 940 20 5 10 10.5 600+ 5 5 10 10.5 600+______________________________________
While both the succinimide and diamide derivations may be contributing to sizing, it is more likely that the alkenyl succinimide is the more effective sizing agent because of its significantly lower pK.
By analogy we would expect alkyl and alkenyl substituted phthalimides and phthalic diamide compounds, and rosin ester malimides, to be effective sizing materials.
Having thus disclosed the best mode known to the inventors of carrying out their invention, it will be readily evident to those skilled in the art that many changes can be made without departing from the spirit of the invention. The invention is considered to be limited only as it is defined by the following claims. | The invention is a method of sizing paper and, in particular, paper made under neutral to alkaline conditions at least as high as 10.5. The papermaking stock is first treated with a polycationic material to provide sizing receptive sites uniformly distributed over the fiber surface. The presence of the anchoring points is critical to the later redistribution of the sizing material in the dryer section of the paper machine. The sizing material is then added to the slurry. This is then brought down onto the fibers by addition of a small amount of a size precipitant such as alum. The sizing molecule should have a hydrophilic portion with two hetero atoms forming a bidentate analog structure. This must have a pK in water of 6.0 or higher and a vapor pressure preferably at least 0.0006 mm Hg at 60° C. The polycationic material provides anchoring/orienting sites on the fiber to which the small globules of sizing attach when the emulsion is broken by the precipitant. Sizing will develop in the dryer section of the paper machine, presumably by vapor phase redistribtution of sizing from the attached globules to unfilled sites where an anchoring point is present. Alkyl and alkenyl substituted catechols, beta-diones, hydroxamic acids and imides are among the new classes of sizing materials disclosed. | 3 |
CROSS-REFERENCE TO RELATED APPLICATIONS
Not Applicable
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
Not Applicable
REFERENCE TO SEQUENCE LISTING, A TABLE, OR A COMPUTER PROGRAM LISTING COMPACT DISK APPENDIX
Not Applicable
BACKGROUND OF THE INVENTION
Knife blocks for storing cutlery typically consist of a solid block of material with a number of parallel slots that hold the knife blades. The handles stick up, which leaves the knives exposed for small children to grab and potentially hurt themselves. This invention is a knife block that can be locked to safeguard knives and other sharp objects (e.g., kitchen shears) from small children. In addition, this invention uses a locking mechanism that does not require any alterations to the knives, a drawback of other lockable knife blocks. Finally, this knife block has few parts, which makes it easy to manufacture.
BRIEF SUMMARY OF THE INVENTION
This invention is a knife block that can be locked to safeguard knives and other sharp objects (e.g., kitchen shears). In the unlocked position, a cap with holes in the top fits down snugly on the block base. In this position, the holes in the cap are aligned with the knife handles such that they protrude through the cap and the knives are available for use. To lock the knife block, the user raises the cap above the knife handles and rotates it, confining the knives within the cap and rendering them inaccessible because of the changed orientation of the holes in the cap, i.e., perpendicular to the knife handles. Depressible catch pieces lock the cap in place. To unlock it, the user depresses the catch pieces and rotates and lowers the cap.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
FIG. 1 is a perspective view of the base.
FIG. 2 is a perspective view of the cap piece.
FIG. 3 is a perspective view of this lockable knife block in the unlocked position with cap down snugly over the base and a knife handle sticking out through a hole in the cap.
FIG. 4 is a perspective view of this lockable knife block in the locked position with the cap up, confining the cutlery.
FIG. 5 is a side elevation of FIG. 4 .
FIG. 6 is a side elevation of FIG. 1 .
FIG. 7A is an elevation of the top of the cap piece in the locked position and is indicated by the I—I line in FIG. 5 .
FIG. 7B is similar to FIG. 7A but shows the cap piece and base in the unlocked position.
FIG. 8A is a cross section through the base and cap when the knife block assembly is in the locked position and is indicated by the II—II line in FIG. 6 .
FIG. 8B is similar to FIG. 8A but the catch piece is depressed so it does not block the movement of the cap, which is rotating toward the unlocked position.
FIG. 8C is similar to FIG. 8A but the knife block assembly is in the unlocked position.
FIG. 8D is similar to FIG. 8A but the cap piece is rotating toward the locked position and has partially depressed the catch piece.
DETAILED DESCRIPTION OF THE INVENTION
Referring to FIG. 1 , the base 1 of the knife block is made of pressed wood or a plastics polymer. The base 1 has slots 8 for the knives' blades like most knife blocks. The upper part of the base 1 is cylindrical. A “foot” 5 projects from the front of the base 1 for stability. On the sides of the base 1 are three narrow grooves 3 oriented close to the vertical, which will be referred to as “vertical grooves”. Only one of the vertical grooves 3 is visible in FIG. 1 . Also on the sides of the base 1 are three grooves 10 oriented close to the horizontal, which will be referred to as “horizontal grooves”. Only one horizontal groove 10 and part of another are visible in FIG. 1 . Each vertical groove 3 meets one of the horizontal grooves 10 to create an L-shaped configuration. Each of the horizontal grooves 10 has another groove 11 branching off from it that runs up to the top of the base 1 . Catch pieces 4 cross two of the horizontal grooves 10 . The catch pieces 4 consist of a long flat stick of the same material as the base 1 and an angled portion at the top 13 . Each catch 4 is fixed to the base 1 at the bottom and is flexible. The two catch pieces 4 rest in two additional grooves parallel to the vertical grooves 3 . The two catch pieces are located 120 degrees from each other and are on the back half of the base, opposite the foot 5 (see FIG. 8 A).
Referring to FIG. 2 , the second part of the knife block is the cap piece 2 , and it is made of a clear or translucent plastic polymer of a depth and circumference to fit snugly around the cylindrical part of the base. The cap has holes 6 in its top that are designed to allow the knife handles to pass through when the holes and handles align. Three protrusions 12 are located at the bottom of the cap 2 . The protrusions 12 are spaced equally around the bottom of the cap 2 . If the bottom of the cap 2 is visualized as a clock, the protrusions 12 are placed at two o'clock, six o'clock and ten o'clock.
Referring to FIGS. 1 and 2 , the protrusions 12 fit into the vertical grooves 3 and horizontal grooves 10 in the base 1 to guide the motion of the cap 2 . The rising and lowering motion of the cap 2 is guided by the protrusions 12 moving in the vertical grooves 3 . The rotating motion of the cap 2 is guided by the protrusions 12 moving along the horizontal grooves. The short groove 11 allows the cap 2 to be removed from the base 1 for the purpose of cleaning.
FIG. 3 shows the unlocked knife block assembly. In this position, the cap 2 fits down over the base 1 with the knife handle 7 protruding through the holes 6 in the cap 2 . The holes 6 in the cap 2 are aligned with the knife handle 7 and the slots 8 in the base 1 , and the knives are accessible to the user (see FIG. 7 B). In addition, the protrusions in the cap 2 are at the bottom of the vertical grooves in the base 1 , although this is not visible in FIG. 3 .
FIG. 4 shows the locked knife block assembly. In this position, the cap 2 is raised so that the knife handle 7 is completely inside the cap 2 . In addition, the cap 2 is rotated 90 degrees from the unlocked position so the holes 6 are oriented to block the knife handle 7 from passing through them (see FIG. 7 A). When the cap 2 is in the locked position, two catch pieces 4 hold the protrusions in place and restrict the movement of the cap 2 . To unlock the knife block assembly, the user depresses the catch pieces 4 with thumb and forefinger and rotates the cap 2 ninety degrees with the other hand. The protrusions in the cap 2 follow the horizontal grooves 10 until they reach the vertical grooves 3 , and then the user lowers the cap 2 down onto the base 1 and the knife block assembly is unlocked as shown in FIG. 3 .
FIG. 5 shows the knife block assembly in the locked position. The back 9 of the base 1 , opposite the foot 5 , is truncated to allow the knife block assembly to be placed against the back wall of a kitchen countertop.
FIG. 6 shows the base of the knife block assembly.
FIG. 7A shows the knife block assembly in the locked position. The orientation of the holes 6 in the cap 2 are 90 degrees away from the orientation of the knife handles 7 and the slots 8 in the base 1 , confining the knives within the cap 2 .
FIG. 7B shows the knife block assembly in the unlocked position. The orientation of the holes 6 in the cap 2 matches the knife handles 7 and the slots 8 in the base 1 , making the knives accessible.
FIG. 8A shows the locked position. The catch pieces 4 block the protrusions 12 of the cap 2 , thus preventing the motion of the cap. Specifically, it is the wider sides of the angled top portions 13 of the catch pieces 4 that block the movement of the protrusions 12 . The narrower side of the angled top portion 13 of the catch piece 4 is flush with the inside of the horizontal groove 10 . The main body of the catch piece 4 is flush with the outside surface of the base 1 .
FIG. 8B shows the catch piece 4 when depressed by the thumb or index finger of the user, which frees the protrusion 12 to allow rotation of the cap 2 . The protrusions are shown moving along the horizontal grooves 10 as the cap 2 rotates.
FIG. 8C shows the cap in the unlocked position. The protrusions are not shown because they are at the bottom of the vertical grooves 3 , and the section is cut near the top of the base as shown in FIG. 6 line II—II. The catch 4 is in its normal un-depressed position.
FIG. 8D shows the cap 2 rotating toward the locked position. The angle of the catch top portions 13 causes the catch pieces 4 to depress as the protrusions 12 of the cap 2 rotate. The next thing to happen after what is shown in FIG. 8D is that the protrusions 12 pass the angled portions 13 , and the catch pieces 4 return to their normal un-depressed positions, blocking the movement of the protrusion 12 , and locking the knife block assembly as shown in FIG. 8 A. | This invention is a knife block for storing cutlery that can be locked to prevent the removal of the knives. An adjustable cap piece rests in one of two positions. In the unlocked position, the cap fits snugly over the base and the knives project up through holes in the cap. In the locked position, the cap is raised and rotated so the knives are inside the cap and inaccessible. The locking mechanism requires adult understanding and hand size to operate, greatly enhancing kitchen safety. In addition, this locking knife block requires no alteration of the knives. | 0 |
BACKGROUND OF THE INVENTION
The invention is directed to an apparatus for cleaning the clips of a web transporting machine. In particular, the invention is directed to an apparatus for cleaning the clips of web transporting machines of the variety where there can be significant chemical and debris buildup on the clips, such as a tenter frame.
A variety of apparatus exist for transporting and processing webs of material, such as textile fabric webs and the like. Such machines typically include devices for holding the sides of the web, and a means for transporting the web along a predetermined pathway, which is generally through one or more processing stations. One example of such a web processing apparatus is a tenter frame. As will be appreciated by those of ordinary skill in the art, tenter frames are used to dry textile materials, and can be used to control the fabric width by controlling the amount the fabric can shrink when heated during the drying process. Typically, tenter frames include a pair of endless chains on horizontal tracks, which hold the fabric at its edges by pins or clips on the two chains, to thereby hold the fabric at the desired width during drying. Similarly, other web processing machines use clips to retain the edges of the web during processing, to maintain it in a desired position for processing and/or control its width.
The clips typically used on these kinds of machines generally have a lower, flat web supporting portion that is adapted to support the web being processed beneath the web edges (or selvages, as they are known in the textile industry.) The clips also typically have a hinged flap that pivots downwardly toward the web supporting portion, to capture the web edge and retain it tightly in position. The hinged flap is desirably designed to pivot in the direction such that the more a fabric is pulled away from the clip, the more tightly the flap is pulled toward the web supporting portion. In this way, the hinged flap is enabled to tightly secure the web edges, while being relatively easy to open when so desired, by pivoting it in the opposite direction.
One difficulty experienced with such apparatus is that the foreign matter can tend to build up on the clips, and in particular, on the surface of the web supporting portion. Not only can this interfere with the proper closing of the flap and securement of the web (leading to miss-clips and inadequate dimensional setting of the web), but the foreign matter can soil the web being processed, thereby causing off-quality or defects. The problem of clip contamination build-up can be particularly aggregious in the processing of textile materials, where a variety of chemistries and finishes are often provided on the fabrics. Furthermore, since tenter frames are typically operated at elevated temperatures (e.g. from about 150° F. and upwards), it often results that the chemicals and finishes are “baked on”, which can make them extremely difficult to remove. As a result, it is generally required that clip contaminants in the textile environment be removed by the manual scraping of the clips with a putty knife. As will be readily appreciated by those of ordinary skill in the art, this has disadvantages in terms of safety, speed, manufacturing efficiencies, and the like.
Attempts have been made to automate clip cleaning. For example, U.S. Pat. No. 4,176,429 to Rottensteiner describes a brush system for cleaning the clips on a tenter frame. The brush cleaning device is designed to move between an operative, clip contacting position, and an inoperative position. While such brushes may be sufficient for certain end uses where the clip contamination is in “free flake” form, it would be insufficient to remove chemistry and finishes in many applications, and in fact, would tend to make it more difficult to remove, in that it has been brushed and compacted onto the clip surface.
Other attempts to free obstructions in tenter clips are described in U.S. Pat. No. 3,789,975 to Ida et al, and U.S. Pat. No. 5,771,547 to Hommes et al. Those patents describe the use of streams of pressurized air to eject foreign matter from the tenter clips. Like the brushing technique described in the Rottensteiner patent, this method would be insufficient for removing baked-on material of the variety described above.
Other methods have generally accepted that clip contamination cannot be sufficiently avoided, and have focused on the identification of contaminant build-up. For example, U.S. Pat. No. 5,159,733 to Fleming, Jr. et al describes a tenter machine having a mechanical arm or a light beam for detecting foreign matter on the clips, in order that the machine operation can be ceased.
With the foregoing in mind, it is therefore an object of the invention to provide an apparatus for the automated cleaning of clips on a web processing apparatus, which will enable the removal of chemicals and finishes such as those encountered in a textile processing environment.
It is also an object of the invention to provide a means for cleaning the clips of a web processing apparatus that can be readily applied to existing equipment, without requiring redesign or modification of the equipment.
It is another advantage of the invention to provide an apparatus that can effectively clean the clips of a web processing machine while the machine is in operation and the clips are moving at high rates of speed.
SUMMARY
To this end, the present invention is directed to an apparatus for cleaning the clips of a web processing apparatus which can be easily applied to any of a variety of web processing devices, and which can remove securely attached debris and contaminants from the web supporting surface of the clips. The apparatus includes a scraper for scraping the web supporting surface of the clips on the web transporting machine, and also desirably includes a clip opener, for facilitating opening of the clips to enable the scraper to easily access the web supporting surface of the clip. The scraper is desirably supported in a manner that enables it to move upwards and downwards relative to the clips in order to accommodate variations in clip positioning.
The clip cleaner is also desirably designed so that it can clean the clips while the web processing device is in operation, and operating at the high speeds typically used during a commercial processing operation.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a partially cut-away environmental view of one embodiment of the present invention;
FIG. 2 is a top view of a clip cleaner of the invention shown in FIG. 1, in its operative position with respect to a web processing device;
FIG. 3 is a side plan view of the apparatus illustrated in FIGS. 1 and 2;
FIG. 4 is a top view of the apparatus illustrated in FIG. 1, showing the clip cleaner in its withdrawn, or non-cleaning position;
FIG. 5 is a side plan view of the apparatus shown in FIG. 4;
FIGS. 6 and 7 are illustrations of a portion of a clip cleaner made according to the invention, illustrated in FIG. 6 with the clip cleaner withdrawn from the clip and in FIG. 7, with the clip cleaner in its operative position; and
FIG. 8 is an enlarged perspective view of the underside of a scraper that can be used in connection with the instant invention.
DETAILED DESCRIPTION
In the following detailed description of the invention, specific preferred embodiments of the invention are described to enable a full and complete understanding of the invention. It will be recognized that it is not intended to limit the invention to the particular preferred embodiment described, and although specific terms are employed in describing the invention, such terms are used in a descriptive sense for the purpose of illustration and not for the purpose of limitation. Like numbers are intended to illustrate like elements throughout the figures.
The apparatus has a scraper having a substantially planar edge for contacting the web supporting portions of the clips of a web processing machine, and clearing them of debris and the like. The apparatus also desirably includes a means for facilitating opening of the clips, in order to make the surfaces of the web supporting portions available for the clearing of debris.
The apparatus also is desirably mounted so that it can move slightly as needed to accommodate for slight variations in the position of the web supporting portions of the clips. Also, the clip cleaning apparatus can desirably be selectively moved from an operative clip cleaning position to an inoperative position, where it is not in contact with the clips.
In one aspect of the invention, the means for opening the clips is in the form of an angled ram (not shown) which contacts and pivots the hinged flap F of the clip to its open position, so that the scraper can contact the surface of the web supporting portion S of the clips C without hindrance from the hinged flap portion F. In a preferred embodiment of the invention, the means for opening the clips comprises a rotating wheel 18 (which rotates about a pin or axis 19 ), as this has been found to provide gentle opening of the clips, and to be more durable than a stationary ram.
With reference to the drawings, FIG. 1 shows a partially cutaway environmental view of an embodiment of the apparatus according to the invention, shown generally at 10 . The web processing device in which the clip cleaner 10 is used is shown in partially cut-away form, in order to fully explain the environment of the apparatus. The web processing device in this illustration includes a plurality of clips C, which follow an endless path of travel to transport a web W of material through a processing operation. In the instant case, the clips follow a generally oval-shaped path of travel in which they transport the web along a first path length P 1 , release the fabric, then turn and return back to a web receiving position via a second path length P 2 that parallels the first path length.
The apparatus has a support 12 for supporting the clip cleaner adjacent the web processing apparatus. In the illustrated embodiment of the invention, the support is in the form of a light weight frame on which the clip cleaner can be readily moved from an operative position to an inoperative position, in a manner that will be discussed more completely below. The support 12 is desirably positioned along the return path P 2 of the clips, such that cleaning occurs while clips are traveling along the second path length. In this way, the cleaning can be performed while the web processing machine is engaged in the processing of a web, without risking damage to the web as a result of the cleaning process. Furthermore, this enables cleaning to be performed at the process operating speeds, rather than requiring the machine to be taken out of operation for the performance of the clip cleaning function.
In the illustrated embodiment of the invention, the support 12 comprises a horizontal support member 12 a and a vertical support member 12 b . These support members can be secured directly to the frame of the web processing apparatus, or can be positioned separately, yet proximate the web processing apparatus so as to enable support of the clip cleaning mechanism in a position contacting the clips to be cleaned. (Although described as being “horizontal” and “vertical” support members, it is noted that alternatively oriented supports can be used within the scope of the invention, such as where the clips run in a direction other than horizontally, such as vertical.)
In the illustrated embodiment of the invention, the clip cleaning mechanism and vertical support member 12 b are adapted to slide along the horizontal support member 12 a by way of handle H. In this way, the clip cleaning mechanism can be slid from an inoperative position, in which it is moved away from the clips to be cleaned, to an operative position, in which the clip cleaning mechanism contacts the clips. It is to be noted, however, that other arrangements for supporting the clip cleaning mechanism are contemplated within the scope of the instant invention; however, it is preferable that the support will enable the selective movement of the clip cleaning mechanism from an operative position to an inoperative position. In addition, it is noted that the support can be constructed in such a way that a single clip cleaner device can be transferred from one web processing machine to another. Furthermore, it is noted that a because a typical web processing machine will have two clip assemblies (i.e. one to hold each side of the web being processed), that it may be desirable to provide an individual clip cleaning mechanism to each of the sides of the web processing machine. Also, the clip cleaner can include means for moving the clip cleaner into an operative position automatically (e.g. for a set period of time), and then moving it to an inoperative position automatically.
The clip cleaning mechanism also desirably includes a means for biasing it against the upper surface of the web supporting portion of the clips when the clip cleaning mechanism is in its operative position, yet allows the mechanism to move upwardly and/or downwardly to a slight extent in order to allow it to account for minor variations in height of the clip lower surfaces. In the illustrated embodiment, the biasing means is in the form of a spring 16 , which biases the mechanism downwardly toward the web supporting surfaces of the clips, while enabling it to move within a small range, to account for variations in the height of the clips and the like.
As noted above, the clip cleaning mechanism 14 desirably includes a means for opening the clips, and includes a means for scraping debris from the web supporting portion of the clip. In a preferred form of the invention, the means for opening the clips is in the form of a rotatable wheel 18 , which contacts the hinged flap F of a clip as it proceeds along its path of travel and pivots it inwardly to its open position. Alternatively, an angular ram can be used to open the clip hinged flap, though it has been found that the wheel construction has greater durability and provides more gentle clip opening. The clip opener can be manufactured of any type of material desired; however, it is desirable to select a material that will not adversely affect the clips. For example, it has been found that clip openers made from high melt temperature thermoplastics such as nylon, phenolic resin materials, and the like perform well, without damaging the material of the clips themselves. However, the use of other materials in the manufacture of the clip opener are contemplated within the scope of the invention.
As used herein, the term “scraper” is intended to describe a rough, hard and/or sharp device designed to contact the upper surface of the web supporting portion of the clips so as to, chisel off debris which may have become attached to that surface (e.g., in the manner in which old paint is typically scraped off a surface in order to prepare it for painting.) The scraper 20 desirably includes a substantially planar edge, so that complete scraping and cleaning of the surface of the web supporting portion of the clip can be achieved. In a preferred form of the invention, the scraper 20 is in the form of a relatively dull blade of a flexible material. In a particularly preferred form of the invention, the scraper has a bent edge as illustrated in FIG. 8, as this facilitates complete scraping by providing a good flat edge-to-surface contact. The scraper can be made from any type of material desired, but is preferably made from a material designed to be durable and provide good scraping of the clip surfaces, while at the same time minimizing damage and wear to the clips themselves. Where the scraper is made from flexible material, this enables the blade to accommodate for variations in clip positioning while also providing good debris cleaning by virtue of the downward spring force it applies onto the cleaner edge of the scraper. Examples of materials that can be used include, but are not limited to spring steel, annealed steel, stainless steel, and the like.
The scraper 20 is desirably secured on the clip cleaning mechanism such that it is angled with respect to the front edge of the clips to be cleaned, such that the full width of the scraper contacts and scrapes across the upper surface of the web supporting portion of the clips.
The clip cleaning function using the clip cleaner of the instant invention is performed as follows: The clip cleaning mechanism is moved from its inoperative position (such as shown in FIGS. 4 and 5) toward the web processing apparatus (as shown in FIGS. 2 and 3.) As illustrated more clearly in FIGS. 6 and 7, the horizontal support 12 a is desirably provided with a lift for lifting the scraper onto the clips. In a preferred form of the invention, the lift is in the form of a ramp 22 , which peaks proximate the upper surface of the clips of the web processing apparatus. When the clip cleaner mechanism is moved toward its operative position, the ramp 22 serves to ensure that the scraper 20 is pushed to a level high enough that it can clear the front edge of the clip web supporting portion. However, other types of lifts (such as a mechanical lift that lifts the cleaner upward over the clip edge, then lowers it downward onto the clip surface) can be used within the scope of the invention. In this way, it can be ensured that the scraper 20 is properly positioned within the clip so that effective cleaning can be achieved.
The clip opener 18 serves to pivot the hinged flap F of the clip to its open position (as shown in FIG. 7 ), and the scraper 20 thus contacts the upper surface of the web supporting portion of the clip. As the clips C travel past the clip cleaning mechanism, the scraper 20 thereby scrapes debris and contaminants off of the surface. As noted above, the movement of the clips C can be effected by normal operation of the web processing operation, or it could be performed when the web processing apparatus is not in operation of processing a web. In either event, it has been found that cleaning can be performed at a high rate of speed and efficiency.
In the specification there has been set forth a preferred embodiment of the invention, and although specific terms are employed, they are used in a generic and descriptive sense only and not for purpose of limitation, the scope of the invention being defined in the claims. | An apparatus for automatically cleaning the clips on a web processing apparatus is described. The apparatus includes a scraper for scraping the web supporting surface of the clips on the web transporting machine, and also desirably includes a clip opener, for facilitating opening of the clip to enable the scraper to easily access the clip web support surface. The scraper is desirably supported in a manner that enables it to move upwards and downwards relative to the web supporting surface of the clips, to account for variations in clip height and positioning. The clip cleaner can be readily applied to existing web processing apparatus, such as tenter frames, and desirably can be selectively moved from an operative position to an inoperative position. | 1 |
BACKGROUND
The trend of convergence between mobile devices and the Internet is accelerating. More Internet services, including video purchasing/renting services, are migrating to mobile devices as smartphones and tablets become more popular among consumers.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an illustration of a concept described herein;
FIG. 2 is a diagram of an exemplary network in which systems and/or methods described herein may be implemented;
FIG. 3 is a diagram of exemplary components of one or more of the devices of the network depicted in FIG. 2 ;
FIG. 4 is a diagram of exemplary functional components of an orchestration server of the network depicted in FIG. 2 ;
FIG. 5 is a diagram of exemplary communications among a portion of the network of FIG. 2 to relay requests from mobile devices;
FIG. 6 is a diagram of exemplary communications among another portion of the network of FIG. 2 ;
FIG. 7 is a diagram of additional exemplary communications among the portion of the network of FIG. 6 ;
FIG. 8 is a diagram of further exemplary communications among the portion of the network of FIG. 6 ;
FIG. 9 is a diagram of exemplary communications among yet another portion of the network of FIG. 2 ; and
FIGS. 10 and 11 are flow charts of exemplary processes for providing a proxy service that links client applications to backend services according to an implementation described herein.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The following detailed description refers to the accompanying drawings. The same reference numbers in different drawings may identify the same or similar elements.
Systems, and/or methods/or described herein may provide a server layer linking the application client programs to backend services in a video services network. The systems and/or methods may receive, from a user device, a data call, and may forward the data call to a backend network device. The systems and/or methods may receive, from the backend network device, a response to the data call in a first format. The systems and/or methods may identify a type of user device and may convert the response from the first format into a second format to create a reformatted response. In one implementation, the reformatted response may address compatibility issues and/or simplify processing by the user device. The systems and/or methods may send the reformatted response to the user device.
FIG. 1 provides an illustration of concepts described herein. Referring to FIG. 1 , different types of user devices (e.g., a tablet device 110 and a laptop computer 120 ) may use different protocols and/or operating systems. Backend systems 130 may provide services (e.g., Internet-based services, such as video content distribution services) to the user devices. Some Internet services were designed before the mobile era and were designed for computer users. These services may be based on assumptions that a user device's web browser is sophisticated enough to handle heavy processing loads; and some of these services might even require an agent installation on the user devices. While these assumptions may provide adequate performance for some user devices (e.g., laptop PC 120 ), performance on other user devices (e.g., tablet device 110 ) may suffer. To obtain optimal performance, and due to the variations in hardware and software of user devices, it is beneficial to shift heavy processing requirements for these services to the server side and let user devices handle only a front end user interface.
In an implementation described herein, an orchestration sever 140 may provide a proxy service (e.g., a server layer) linking the client application on the user devices with backend systems 130 . Backend systems 130 can communicate with orchestration server 140 using any preferred format, and orchestration server 140 may communicate with the respective user devices (e.g., tablet device 110 and laptop computer 120 ) using protocols appropriate for the particular user device. Additionally, orchestration server 140 may provide a unified interface for the user device to communicate with different devices in backend systems 130 .
As used herein, the term “user” is intended to be broadly interpreted to include a user device (e.g., a mobile communication device) or a user of a user device.
FIG. 2 is an exemplary network 200 in which an embodiment described herein may be implemented. Network 200 may generally represent user devices connected to a video content distribution network. As illustrated, network 200 may include a video content management system (VCMS) 210 , a data center 220 , a profile server 230 , a billing server 240 , a physical asset distribution system 250 , user devices 260 , a private network 270 , and a public network 280 . The particular arrangement and number of components of network 200 shown in FIG. 2 are illustrated for simplicity. In practice there may be more VCMSs 210 , data centers 220 , profile servers 230 , billing servers 224 , physical asset distribution systems 250 , orchestration servers 140 , user devices 260 , and/or networks 270 / 280 . Components of network 200 may be connected via wired and/or wireless links
VCMS 210 may include one or more network devices, or other types of computation or communication devices, to aggregate content and content metadata, process content, and distribute content. In one implementation, VCMS 210 may include a content delivery system 212 and a digital rights management (DRM) server 214 . VCMS 210 may aggregate content and transcode content into a digital format suitable for consumption on particular user devices 260 . For example, VCMS 210 may include a transcoding device to convert a video file from one format to another (e.g., from one bit rate to another bit rate, from one resolution to another, from one standard to another, from one file size to another, etc). VCMS 210 may also encrypt data and communicate with DRM server 214 to enforce digital rights.
Content delivery system 212 may include one or more network devices, or other types of computation or communication devices, to deliver digital content from a backend server to user devices 260 . In one implementation, content delivery system 212 may include a streaming server that provides streaming data packets (e.g., via a streaming URL) to user devices 260 (e.g., via network 270 ). In one implementation, a streaming URL may be session-based, such that each URL can be used only once for one user device 260 for security purposes.
DRM server 214 may include one or more network devices, or other types of computation or communication devices, to issue, validate, and/or enforce DRM licenses to a client, such as an application running on one of user devices 260 . In implementations herein, DRM server 214 may communicate with user device 260 to authenticate a user of user device 260 , the particular user device 260 , and/or an application residing on user device 260 . For example, DRM server 214 may request/receive login information associated with the user, and compare the login information with stored information to authenticate the user. Additionally, or alternatively, DRM server 214 may request/receive device information (e.g., a unique device identifier) associated with user device 260 , and may compare the device information with stored information to authenticate user device 260 .
Data center 220 may include one or more network devices, or other types of computation or communication devices, to manage the authorization, selection, and/or purchase of multimedia content by a user of user devices 260 . As shown in FIG. 2 , data center 220 may include orchestration server 140 , a catalog server 222 and an application server 224 . In one implementation, data center 220 may be accessed by user devices 260 via public network 280 .
Catalog server 222 may include one or more network devices, or other types of computation or communication devices (e.g., a server device, an application server device, a Web server device, a database server device, a computer, etc.), to provide a unified catalog of both digital and physical content for users (e.g., of user devices 260 ) to consume (e.g., buy, rent, or subscribe). In one implementation, catalog server 222 may collect and/or present listings of video content available to user devices 260 . For example, catalog server 222 may receive digital and/or physical content metadata, such as lists or categories of content, from VCMS 210 and/or physical asset distribution system 250 . Catalog server 222 may use the content metadata to provide currently-available content options to user devices 260 . Catalog server 222 may provide the content metadata to user device 260 directly or may communicate with user device 260 via application server 224 .
Application server 224 may include one or more network devices, or other types of computation or communication devices (e.g., a server device, an application server device, a Web server device, a database server device, a computer, etc.), to provide a backend support system for mobile applications residing on user devices 260 . For example, application server 224 may permit user device 260 to download a video application that may permit a user to find content of interest or play downloaded or streaming content. The video application may enable user device 260 to present to a user of user device 260 information received from data center 220 in an interactive format to allow selection of particular digital or physical content. Additionally, or alternatively, application server 224 may provide content metadata, such as lists or categories of content. Also, application server 224 may authenticate a user who desires to purchase, rent, or subscribe to digital or physical content. In one implementation, the interactions between application server 224 and user device 260 may be performed using hypertext transfer protocol (HTTP) or secure HTTP (HTTPS) via public network 280 .
Orchestration server 140 may include one or more network devices, or other types of computation or communication devices (e.g., a server device, an application server device, a Web server device, a database server device, a computer, etc.), to link user devices 260 with other devices in network 200 , such as catalog server 222 , application server 224 , profile server 230 , billing server 240 , etc. Orchestration server 140 is described further in connection with, for example, FIGS. 3-9 .
Profile server 230 may include one or more network devices, or other types of computation or communication devices, to store user profile information for users (e.g., users of user devices 260 ). The user profile information may include various information regarding a user, such as login information (e.g., a user identifier and a password), billing information, address information, types of services to which the user has subscribed, a list of digital/physical content purchased by the user, a list of video content rented by the user, a list of video content to which the user has subscribed, a user device identifier (e.g., a media player identifier, a mobile device identifier, a set top box identifier, a personal computer identifier) for user device 260 , a video application identifier associated with the video application obtained from application server 224 , or the like. Application server 224 may use the user profile information from profile server 230 to authenticate a user and may update the user profile information based on the user's activity (e.g., with a user's express permission).
Billing server 240 may include one or more network devices, or other types of computation or communication devices, to manage charging users for services provided via network 200 . Billing server 240 may include, for example, a payment processing component, a billing component, and/or a settlement component.
Physical asset distribution system 250 may include one or more network devices, or other types of computation or communication devices, to track availability of physical content (e.g., DVDs, Blu-ray discs, memory cards, etc.) and provide metadata of physical content for inclusion in catalog information provided to users of user devices 260 . In one implementation, physical asset distribution system 250 may also provide physical asset information, such as location information, so that when a user wants to buy a physical asset, the system can direct the user to the nearest geographic location (e.g., to retrieve the physical asset).
VCMS 210 , content delivery system 212 , DRM server 214 , data center 220 , catalog server 222 , application server 224 , profile server 230 , billing server 240 , physical asset distribution system 250 , and orchestration server 140 may be referred to herein generally as backend servers.
User device 260 may include a computation or communication device to enable a user to view video content or interact with another user device 260 or a video display device (e.g., a set-top box and/or television). User device 260 may include, for example, a personal communications system (PCS) terminal (e.g., a smart phone that may combine a cellular radiotelephone with data processing and data communications capabilities), a tablet computer, a smart phone, a personal computer, a laptop computer, a gaming console, a vehicular communication system, an Internet television, a digital video recorder (DVR) rental terminal, or other types of computation or communication devices. In one implementation, user device 260 may include a client-side application that enables user device 260 to communicate with, for example, VCMS 210 or data center 220 and present information received from VCMS 210 /data center 220 to a user. The client-side application may permit a user of user device 260 to log into an account (e.g., via application server 224 ), access catalog information (e.g., from catalog server 222 ), submit an order, and/or consume live streaming or downloaded video content (e.g., from VCMS 210 ).
Private network 270 may include, for example, one or more private IP networks that use a private IP address space. Private network 270 may include a local area network (LAN), an intranet, a private wide area network (WAN), etc. In one implementation, private network 270 may implement one or more Virtual Private Networks (VPNs) for providing communication between, for example, any of VCMS 210 , data center 220 , profile server 230 , billing server 240 , and/or physical asset distribution system 250 . Private network 270 may be protected and/or separated from other networks, such as public network 280 , by a firewall. Although shown as a single element in FIG. 2 , private network 270 may include a number of separate networks.
Public network 280 may include a local area network (LAN), a wide area network (WAN), such as a cellular network, a satellite network, a fiber optic network, or a combination of the Internet and a private WAN, etc. that is used to transport data. Although shown as a single element in FIG. 2 , public network 280 may include a number of separate networks that provide services to user devices 260 .
Although FIG. 2 shows exemplary components of network 200 , in other implementations, network 200 may include fewer components, different components, differently-arranged components, and/or additional components than those depicted in FIG. 2 . Alternatively, or additionally, one or more components of network 200 may perform one or more tasks described as being performed by one or more other components of network 200 . For example, in one implementation, the functions of orchestration server 140 , catalog server 222 , and/or application server 224 may be combined in a single device or distributed among a group of devices.
FIG. 3 is a diagram of example components of a device 300 that may correspond to any one of the components of network 200 . As illustrated, device 300 may include a bus 310 , a processing unit 320 , a memory 330 , an input device 340 , an output device 350 , and a communication interface 360 .
Bus 310 may permit communication among the components of device 300 . Processing unit 320 may include one or more processors or microprocessors that interpret and execute instructions. In other implementations, processing unit 320 may be implemented as or include one or more application specific integrated circuits (ASICs), field programmable gate arrays (FPGAs), or the like.
Memory 330 may include a random access memory (RAM) or another type of dynamic storage medium that stores information and instructions for execution by processing unit 320 , a read only memory (ROM) or another type of static storage medium that stores static information and instructions for processing unit 320 , and/or some other type of magnetic or optical recording medium and its corresponding drive for storing information and/or instructions.
Input device 340 may include a device that permits an operator to input information to device 300 , such as a keyboard, a keypad, a mouse, a pen, a microphone, one or more biometric mechanisms, and the like. Output device 350 may include a device that outputs information to the operator, such as a display, a speaker, etc.
Communication interface 360 may include any transceiver-like mechanism that enables device 300 to communicate with other devices and/or systems. For example, communication interface 360 may include mechanisms for communicating with other devices, such as other components of network 200 .
As described herein, device 300 may perform certain operations in response to processing unit 320 executing software instructions contained in a computer-readable medium, such as memory 330 . A computer-readable medium may be defined as a non-transitory memory device. A memory device may include space within a single physical memory device or spread across multiple physical memory devices. The software instructions may be read into memory 330 from another computer-readable medium or from another device via communication interface 360 . The software instructions contained in memory 330 may cause processing unit 320 to perform processes described herein. Alternatively, hardwired circuitry may be used in place of or in combination with software instructions to implement processes described herein. Thus, implementations described herein are not limited to any specific combination of hardware circuitry and software.
Although FIG. 3 shows exemplary components of device 300 , in other implementations, device 300 may include fewer components, different components, differently arranged components, or additional components than depicted in FIG. 3 . As an example, in some implementations, input device 340 and/or output device 350 may not be implemented by device 300 . In these situations, device 300 may be a “headless” device that does not explicitly include an input or an output device. Alternatively, or additionally, one or more components of device 300 may perform one or more other tasks described as being performed by one or more other components of device 300 .
FIG. 4 is a diagram of example functional components of orchestration server 140 . In one implementation, the functions described in connection with FIG. 4 may be performed by one or more components of device 300 ( FIG. 3 ). As shown in FIG. 4 , orchestration server 140 may include a formatting module 410 , a distribution module 420 , an aggregation module 430 , a cache module 440 , and a client profile module 450 .
Formatting module 410 may receive information (e.g., responses to data calls initiated by user devices 260 ) from backend servers in network 200 (e.g., content delivery system 212 , DRM server 214 , catalog server 222 , application server 224 , profile server 230 , billing server 240 , and/or physical asset distribution system 250 ). For example, formatting module 410 may receive a Web service response (e.g., a video catalog listing responsive to a data call from one of user devices 260 ) from a backend server (e.g., catalog server 222 ). Formatting module 410 may identify a type of device (or operating system) being used on user device 260 . Formatting module 410 may determine the type of user device, for example, based on information in the data call, or information previously provided by user device 260 (such as login information and/or account profile information associated with user device 260 ). In one implementation, formatting module 410 may include a table, database, or another data structure that maps types of devices to operating systems and/or other information. In another implementation, device type information obtained during a login or registration process may include operating system and/or application version information.
Based on the type of user device 260 , formatting module 410 may reformat the contents of the Web service response according to the user device needs to ensure compatibility and/or simplify processing by user device 260 . For example, if the Web service response is provided from a backend server in SOAP (e.g., formerly defined as Simple Object Access Protocol) format as a default, formatting module 410 may reformat the Web services response to Extensible Markup Language (XML) format, JavaScript Object Notation (JSON) format, or another format; or pass through the SOAP format, depending on the type of user device 260 . Additionally, or alternatively, formatting module 410 may receive client requests (e.g., data calls) from user devices 260 and, if necessary, may reformat the client requests into a unified format before forwarding to backend servers in network 200 .
Distribution module 420 may provide a unified interface to user device 260 and call multiple backend servers based on a single data call from user device 260 . For example, distribution module 420 may receive a data call (e.g., from one of user devices 260 ) and identify multiple backend servers that need to respond to the call. Distribution module 420 may forward the data call (e.g., either simultaneously or serially, depending on the context) to each of the multiple backend servers. Thus, distribution module 420 may allow a user device to make a single data call and access multiple responsible backend servers. Furthermore, backend servers (e.g., backend servers 510 ) may have different formats; orchestration server 140 (e.g., distribution module 420 in conjunction with formatting module 410 ) handles these different formats and converts the different formats to provide one unified format to user device 260 .
Aggregation module 430 may provide aggregated results to user device 260 in a uniformed format. In one implementation, if a response to user device 260 involves input from multiple backend servers, aggregation module 430 may receive the input from each backend server, compile the input, and provide the input to user device 260 . For example, if user device 260 provides a keyword search request (e.g., for a video catalog) that spans multiple forms of content, the search may require a query by multiple catalog servers (e.g., catalog servers 222 ). Each of the catalog servers may provide search results to orchestration server 140 , which may, in turn, compile the search results into a single file. In one implementation, aggregation module 430 may provide the file to formatting module 410 for distribution to user device 260 in the appropriate format (e.g., consistent with the particular type of user device 260 ).
Cache module 440 may provide a short-term cache for relatively static results from backend servers. For example, cache module may temporarily store responses from backend servers and/or aggregated results (e.g., from aggregation module 430 ). Cache module 440 may respond to subsequent identical requests using data stored in cache module 440 to provide better response rates (e.g., better than if additional communications with backend servers were required). Cache module 440 may delete or overwrite data from temporary storage after a predetermined time, which may correspond to, for example, a refresh rate of data accessed by backend servers in network 200 .
Client profile module 450 may collect client behavior data that may be used for multiple business purposes. In one implementation, client profile module 450 may include an “opt in” requirement to enable a user of user device 260 to permit collection of client behavior data. Client behavior data may include, for example, content viewed on a particular user device 260 , viewing times of content on a particular user device, applications used, catalog usage data (e.g., searches performed, items browsed), user feedback, etc. Client profile module 450 may collect client behavior data and provide the data (or subsets of the data) to one or more data collection servers.
Although FIG. 4 shows example functional components of orchestration server 140 , in other implementations, orchestration server 140 may include fewer functional components, different functional components, differently-arranged functional components, and/or additional functional components than depicted in FIG. 4 . Alternatively, or additionally, one or more functional components of orchestration server 140 may perform one or more tasks described as being performed by one or more other functional components of orchestration server 140 .
FIG. 5 is a diagram of exemplary communications among a portion 500 of network 200 . As shown in FIG. 5 , network portion 500 may include three user devices 260 (indicated as user devices 260 - 1 , 260 - 2 and 260 - 3 ), orchestration server 140 , and a backend server 510 . The particular arrangement and number of components of network portion 500 are illustrated for simplicity. In practice there may be more user devices 260 , orchestration servers 140 , and/or backend servers 510 .
Communications in FIG. 5 may include communications to relay requests between user devices 260 and a backend server 510 . User devices 260 may each include different front-end client applications. In examples described herein, user device 260 - 1 may include a mobile device operating system (e.g., Google's Android OS, Apple's iOS, etc.); user device 260 - 2 may include a laptop computer using a full-featured web browser/operating system; and user device 260 - 3 may include a device using a Microsoft Windows CE operating system. Backend server 510 may include, for example, one or more of VCMS 210 , content delivery system 212 , DRM server 214 , data center 220 , catalog server 222 , application server 224 , profile server 230 , billing server 240 , and physical asset distribution system 250 .
As shown in FIG. 5 , backend server 510 may generate request/response communications 520 . Request/response communications 520 may include, for example, communications to support an application (e.g., a front-end application for a video content delivery system) running on one of user devices 260 . In one implementation, request/response 520 may include a Web services exchange in conformance with standards of the World Wide Web Consortium. For example, request/response communications 520 may include a remote call (e.g., a SOAP over HTTP call) to invoke a set of application programing interfaces (APIs) for backend server 510 to extract and return video catalog information. Backend server 510 may receive request/response communications 520 in any format, such as XML, SOAP, JSON, or another format. Request/response communications 520 may also include responsive communications from backend server 510 to orchestration server 140 in any format.
XML communications 530 may include communications between an application (e.g., a front-end application for a video content delivery system) running on user device 260 - 1 and orchestration server 140 . XML communications 530 may provide, for example, a data-exchange format (e.g., XML-RPC) optimally supported by a mobile device operating system running on user device 260 - 1 .
SOAP communications 540 may include communications between an application (e.g., a front-end application for a video content delivery system) running on user device 260 - 2 and orchestration server 140 . SOAP communications 540 may provide, for example a data-exchange format (e.g., SOAP) optimally supported by a full-featured web browser interface running on user device 260 - 2 .
JSON communications 550 may include communications between an application (e.g., a front-end application for a video content delivery system) running on user device 260 - 3 and orchestration server 140 . JSON communications 550 may provide, for example, a data-exchange format (e.g., JSON) optimally supported by a Window CE operating system running on user device 260 - 3 .
In one implementation, orchestration server 140 (e.g., formatting module 410 ) may receive request/response communications 520 and may reformat the contents of request/response communications 520 , depending on the type of client operating system employed by user devices 260 , before forwarding the response to the respective user device 260 . As shown in FIG. 5 , orchestration server 140 may reformat request/response communication 520 into XML communications 530 for user device 260 - 1 (assuming request/response communications 520 are directed to user device 260 - 1 ). Similarly, orchestration server 140 may reformat request/response communication 520 into SOAP communications 540 for user device 260 - 2 (assuming request/response communications 520 are directed to user device 260 - 2 ) and may reformat request/response communications 520 into JSON communications 550 for user device 260 - 3 (assuming request/response communications 520 are directed to user device 260 - 3 ). Thus, orchestration server 140 may reformat or pass through the contents of request/response 520 based on needs of the particular user device 260 to simplify the processing needs of user devices 260 .
In another implementation, orchestration server 140 (e.g., formatting module 410 ) may receive XML communications 530 , SOAP communications 540 , and/or JSON communications 550 from user devices 260 and may reformat the contents of XML communications 530 , SOAP communications 540 , and/or JSON communications 550 into a different format depending on the type of communications format employed by backend servers 510 . Thus, orchestration server 140 may reformat or pass through the contents of XML communications 530 , SOAP communications 540 , and/or JSON communications 550 in a unified format as request/response communications 520 to reduce the processing burden on backend servers 510 .
FIG. 6 is a diagram of exemplary communications among a portion 600 of network 200 . As shown in FIG. 6 , network portion 600 may include one user device 260 , orchestration server 140 , and three backend servers 510 (indicated as backend servers 510 - 1 , 510 - 2 and 510 - 3 ). The particular arrangement and number of components of network portion 600 are illustrated for simplicity. In practice there may be more user devices 260 , proxy servers 140 , and/or backend servers 510 .
Communications in FIG. 6 may include communications to provide a unified interface between a user device 260 and multiple backend servers 510 . User device 260 and backend servers 510 may include features described above in connection with any of FIGS. 1-5 .
As shown in FIG. 6 , orchestration server 140 (e.g., distribution module 420 ) may receive a data call 610 (e.g., an HTTP data call that may correspond to any of XML communications 530 , SOAP communications 540 , and/or JSON communications 550 from user devices 260 ) using a format supported by a type of client operating system employed by user devices 260 . For example, data call 610 may include XML-RPC, SOAP, JSON, or another format. Data call 610 may require processing/responses by different backend servers 510 . For example, data call 610 may include a search query (e.g., for a video catalog, profile data, etc.) that may require searches by multiple servers (e.g., multiple catalog servers 222 , catalog server 222 and application server 224 , etc.) or one of multiple possible servers.
Orchestration server 140 (e.g., distribution module 420 ) may distribute data call 610 to backend servers 510 - 1 , 510 - 2 , and/or 510 - 3 , as indicated by reference numbers 620 , 630 , and 640 , respectively. Orchestration server 140 may, for example, identify the requirements of data call 610 and forward data call 610 to one or more particular backend servers 510 that are configured to process data call 610 . For example, if a data call includes search criteria indicating two separate database systems, orchestration server 140 may forward data call 610 to a backend servers 510 associated with each database system. Thus, orchestration server 140 may provide a unified interface to user device 260 and can call different backend servers 510 depending on the content of data call 610 . In one implementation, orchestration server 140 may reformat the content of data call 610 , as described above with respect to FIG. 5 , before forwarding the content of data call 610 .
FIG. 7 is a diagram of further exemplary communications among portion 600 of network 200 . Communications in FIG. 7 may include communications to provide results aggregation from multiple backend servers 510 to user device 260 .
As shown in FIG. 7 , orchestration server 140 (e.g., aggregation module 430 ) may receive a data call response 710 from backend server 510 - 1 , a data call response 720 from backend server 510 - 2 , and a data call response 730 from backend server 510 - 3 . Each of data call responses 710 , 720 , and 730 may include, for example, a response to a data call (e.g., data call 610 of FIG. 6 ) generated by user device 260 . Orchestration server 140 may aggregate information from data call responses 710 , 720 , and 730 , may process the aggregated information, and may pack the aggregated information for an application client on user device 260 to consume. Orchestration server 140 may format the packed information into a unified format (e.g., XML-RPC, SOAP, JSON, or another format suitable for the application client on user device 260 ) and may forward the aggregated information to user device 260 as an aggregated data call response 740 . In instances when user device 260 is communicating over a connection with limited bandwidth (e.g., a wireless access network), use of orchestration server 140 may reduce the number of data calls and/or data call responses exchanged over the wireless access network (e.g., when compared to requiring multiple separate data calls between user device 260 and backend servers 510 - 1 , 510 - 2 , and 510 - 3 ).
In one implementation, aggregation by orchestration server 140 may involve sequential and multiple data calls to backend servers 510 in order to form the final unified results (e.g., aggregated data call response 740 ). For example, data call response 710 may return search results corresponding to a keyword search from user device 260 . Data call 720 may correspond to retrieving a user profile and preferences. Backend server 510 - 3 may be a recommendation engine. Thus, the search results obtained from data call response 710 and user preferences from data call response 720 may be passed to backend server 510 - 3 , and orchestration server 140 may receive back the recommended search results through data call response 730 . Finally, the response to the keyword search is sent back to user device 260 as the aggregated data call response 740 .
FIG. 8 is a diagram of further exemplary communications among portion 600 of network 200 . Communications in FIG. 8 may include communications to implement a short term cache. In response to a data call (not shown), orchestration server 140 may receive data call responses 810 , 820 , and 830 from backend servers 510 - 1 , 510 - 2 , and 510 - 3 , respectively. In one implementation, orchestration server 140 may aggregate data call responses 810 , 820 , and 830 (e.g., as shown in FIG. 7 ). Orchestration server 140 may forward data call responses 810 , 820 , and 830 (e.g., either aggregated or separately) to user device 260 . Orchestration server 140 (e.g., cache module 440 ) may also temporarily store certain types of data from data call responses 810 , 820 , and 830 in a local cache (e.g., memory 330 of FIG. 3 ). In one implementation, orchestration server 140 may store data from data call responses 810 , 820 , and 830 for a set time period that is less than or equal to a refresh rate of the corresponding data stored on backend servers 510 - 1 , 510 - 2 , and 510 - 3 .
As shown in FIG. 8 , user device 260 may generate a subsequent data call 840 . Assuming subsequent data call 840 requests data originally included in data call responses 810 , 820 , or 830 , and further assuming that subsequent data call 840 is provided before an expiration period for the local cache, orchestration server 140 (e.g., cache module 440 ) may retrieve responsive data from the local cache and provide a response from cache 850 to user device 260 . Use of the local cache may provide a faster response time and improved user experience for user device 260 .
FIG. 9 is a diagram of exemplary communications among portion 900 of network 200 . As shown in FIG. 9 , network portion 900 may include three user devices 260 (indicated as user devices 260 - 1 , 260 - 2 , and 260 - 3 ), orchestration server 140 , and two data collection servers 910 (indicated as data collection servers 910 - 1 and 910 - 2 ). The particular arrangement and number of components of network portion 900 are illustrated for simplicity. In practice there may be more user devices 260 , orchestration servers 140 , and/or data collection servers 910 .
Communications in FIG. 9 may include communications to collect client profile data. Data collection servers 910 may be implemented by, for example, one or more devices associated with VCMS 210 , data center 220 , profile server 230 , billing server 240 , and physical asset distribution system 250 . In another implementation, data collection server 910 may be associated with another network (e.g., other than network 200 ) and/or other business uses.
As shown in FIG. 9 , orchestration server 140 may receive XML communications 530 , SOAP communications 540 , and/or JSON communications 550 . Orchestration server 140 may reformat or pass through the contents of XML communications 530 , SOAP communications 540 , and/or JSON communications 550 to one or more backend servers (not shown in FIG. 9 ). Based on XML communications 530 , SOAP communications 540 , and/or JSON communications 550 , orchestration server 140 (e.g., client profile module 450 ) may collect client behavior data associated with user devices 260 . For example, orchestration server 140 may extract information from data calls in XML communications 530 , SOAP communications 540 , and/or JSON communications 550 that reflect user input, such as requests for video catalog data, catalog browsing activities, video content orders, user ratings/feedback, etc.
Orchestration server 140 may provide the collected client behavior data to one or more of data collection servers 910 , as indicated by references numbers 920 and 930 . In one implementation, profile data 920 and profile data 930 may include the same data distributed to different data collection servers 910 (e.g., data collection servers 910 - 1 and 910 - 2 , respectively). In another implementation, orchestration server 140 may parse the collected client behavior data such that profile data 920 and profile data 930 include different (and possibly overlapping) subsets of the collected client behavior data.
FIGS. 10 and 11 are flow charts of an exemplary process 1000 for providing a proxy service that links client applications to backend services according to an implementation described herein. In one implementation, process 1000 may be performed by orchestration server 140 . In another implementation, some or all of process 1000 may be performed by another device or group of devices, including or excluding orchestration server 140 .
As illustrated in FIG. 10 , process 1000 may include receiving a data call from a user device (block 1010 ), forwarding the data call to a backend server (block 1020 ), and receiving, from the backend server, a response to the data call in a first format (block 1030 ). For example, orchestration server 140 may receive a data call from user devices 260 that may correspond to any of XML communications 530 , SOAP communications 540 , and/or JSON communications 550 . Orchestration server 140 may forward the data call to backend server 510 , and may receive a response to the data call from backend server 510 (e.g., via request/response communications 520 ) in a format such as SOAP, XML, or JSON.
As further shown in FIG. 10 , process 1000 may include identifying a type of the user device (block 1040 ), and determining if the first format is compatible with the type of user device ( 1050 ). For example, orchestration server 140 may (e.g., formatting module 410 ) may identify a type of device (an operating system, a client application, a version thereof, etc.) being used on user device 260 and may reformat the contents of the Web service response according to the device needs to simplify processing by user device 260 . Orchestration server 140 may determine the type of device, the operating system, etc., for example, based on information in the data call, or information previously provided by user device 260 (such as login information and/or account profile information associated with user device 260 ).
If the first format is not compatible with the type of user device ( 1050 —NO), process 1000 may also include converting the response from the first format to a format compatible with the type of user device (block 1060 ). After the response is converted, or if the first format is compatible with the type of user device ( 1050 —YES), process 1000 may include sending the response to the data call to the user device in the format compatible with the type of user device (block 1070 ). For example, in implementations described above in connection with FIG. 5 , orchestration server 140 (e.g., formatting module 410 ) may receive request/response communications 520 and may reformat the contents of request/response communications 520 , depending on the type of client operating system employed by user devices 260 , before forwarding the response to the respective user device 260 .
Process blocks 1020 and 1030 may include the process blocks depicted in FIG. 11 . As shown in FIG. 11 , process blocks 1020 / 1030 may include identifying multiple backend severs to process the data call (block 1110 ) and sending the data call to each identified backend server (block 1120 ). For example, orchestration server 140 (e.g., distribution module 420 ) may receive a data call 610 (e.g., an HTTP data call that may correspond to any of XML communications 530 , SOAP communications 540 , and/or JSON communications 550 from user devices 260 ). Orchestration server 140 may, for example, identify the requirements of data call 610 and forward data call 610 to one or more particular backend servers 510 that are configured to process data call 610 , as indicated by reference numbers 620 , 630 , and 640 , respectively.
Process blocks 1020 / 1030 may also include receiving separate responses to the data call from each of the multiple backend servers (block 1130 ), and aggregating the separate responses into a single response to the data call (block 1140 ). For example, orchestration server 140 (e.g., aggregation module 430 ) may receive a data call response 710 from backend server 510 - 1 , a data call response 720 from backend server 510 - 2 , and a data call response 730 from backend server 510 - 3 . Each of data call responses 710 , 720 , and 730 may include, for example, a response to a data call (e.g., data call 610 of FIG. 6 ) generated by user device 260 . Orchestration server 140 may aggregate information from data call responses 710 , 720 , and 730 , may process the aggregated information, and may pack the aggregated information for an application client on user device 260 to consume.
Systems and/or methods described herein may provide a server layer that links client applications with backend services of a video content distribution system. The systems and/or methods may relay client requests between backend servers and client user devices to improve overall performance. The systems and/or methods may provide different message formats for different client user devices and may reformat contents based on the type of user device to simplify the processing needs from the user devices. The systems and/or methods may provide a unified interface to the client user devices and may provide results aggregation for requests directed to multiple backend servers. The systems and/or methods may provide a short term cache for relatively static results from backend servers. The systems and/or methods may also collect client behavior data for other business uses.
The foregoing description of exemplary implementations provides illustration and description, but is not intended to be exhaustive or to limit the embodiments described herein to the precise form disclosed. Modifications and variations are possible in light of the above teachings or may be acquired from practice of the embodiments. Further, while series of acts have been described with respect to FIGS. 10 and 11 , the order of the acts may be varied in other implementations. Moreover, non-dependent acts may be implemented in parallel. Additionally, other processes described in this description may be varied and/or acts performed in parallel.
It will also be apparent that various features described above may be implemented in many different forms of software, firmware, and hardware in the implementations illustrated in the figures. The actual software code or specialized control hardware used to implement the various features is not limiting. Thus, the operation and behavior of the features of the invention were described without reference to the specific software code—it being understood that one would be able to design software and control hardware to implement the various features based on the description herein.
Further, certain features described above may be implemented as “logic” that performs one or more functions. This logic may include hardware, such as one or more processors, microprocessors, application specific integrated circuits, or field programmable gate arrays, software, or a combination of hardware and software.
In the preceding specification, various preferred embodiments have been described with reference to the accompanying drawings. It will, however, be evident that various modifications and changes may be made thereto, and additional embodiments may be implemented, without departing from the broader scope of the invention as set forth in the claims that follow. The specification and drawings are accordingly to be regarded in an illustrative rather than restrictive sense.
No element, act, or instruction used in the description of the present application should be construed as critical or essential to the invention unless explicitly described as such. Also, as used herein, the article “a” is intended to include one or more items. Where only one item is intended, the term “one” or similar language is used. Further, the phrase “based on” is intended to mean “based, at least in part, on” unless explicitly stated otherwise. | A computing device receives, from a user device, a data call, and forwards the data call to a backend network device. The computing device receives, from the backend network device, a response to the data call in a first format. The computing device identifies a type of the user device and converts the response from the first format into a second format to create a reformatted response. The reformatted response addresses compatibility issues or simplifies processing by the user device. The computing device sends the reformatted response to the user device. | 7 |
CITED REFERENCES
[0001] Bibliographies of the references cited can be found at the end of the specifications for this patent application.
FIELD OF THE INVENTION
[0002] This invention relates to methods of treating animals for stress by administration of therapeutic levels of species-specific microorganisms, electrolytes with glutamine and energy from glucose and medium chain triglycerides as nutritional support.
DESCRIPTION OF THE PRIOR ART
[0003] Nutritional support has become an important therapeutic intervention for improving outcomes in animals undergoing stress. Discoveries about nutritional therapy indicate the importance of providing supplements to animals undergoing normal medical treatment, as well as any comprehensive treatment strategy. Current research reveals that good nutrition can prevent many disease states, and it has also made clear that proper supplementation, if given by the veterinarian, can actually reduce the recovery time during the medical treatment of various diseases, injury or other stressful situations. It is now known that specific nutrients can be used to reduce the effects of these generalized stresses that can include dehydration, loss of energy and imbalance of beneficial bacteria in animals. Addressing these stresses can enhance healing subsequent to surgery and disease and help drugs work more effectively.
[0004] Numerous studies have documented the effects of a patient's nutritional status and outcome during infections or stress. Stress can result from many sources, including travel, cold weather, rigorous exercise or the more drastic medical emergencies of infections and injury. Regardless of the source, the animal will go through similar stages in reacting to stress. These stress stages in animals has been recognized since the early half of the twentieth century (Selye 1946). For example, horses and cattle suffer similar stresses during transportation (Friend 2000). When these animals are transported, they can become dehydrated, depleted of energy and have imbalances of bacteria in the gut. Small animals can also be affected in a similar manner during transportation. As such, the reaction to these general stresses for all animal species appears to be quite similar. Other stress factors such as diseases, trauma or surgery can produce a hypermetabolic state characterized by an increase in protein catabolism, and impairment of immune defenses (Center 1998). A sick or injured animal that does not receive sufficient calories will lose muscle in contrast to a healthy animal that will lose primarily fat. Muscles do more than just move animals. Muscles are also stored energy and animals will “cannibalize” this tissue during stress to get at that stored energy. This loss of muscle or lean body mass in the sick or injured patient adversely affects wound healing, immune function, strength (both skeletal and respiratory muscle), and ultimately, prognosis. While it takes time, ultimately, a goal is to correct this muscle loss through stimulation of the appetite by using appropriate methods, although this may be a problem if the gastrointestinal tract (GI) tract is not functioning properly.
[0005] Other stresses from digestive disorders are also or problem in animals and can lead to many serious problems for the animal. It could be said that the health of an animal starts with the digestive tract. The gastrointestinal tract has two main purposes: to act as a barrier to the external environment and pathogenic microorganisms, and to act the main portal of entry for nutrients. Nutritional support can be provided by either parenteral or enteral routes. Whenever possible, enteral nutrition is the method of choice, as it reduces complication rates and is known to improve outcome. The benefits of enteral nutritional support go beyond simply meeting basic energy requirements of the animal. It is known that the digestive system modulates the immune system and subsequent inflammatory responses but the digestive system also modulates endocrine/hormonal systems. As such, direct support of the digestive system via enteral nutrition can be a valuable support tool for a variety of important aspects in the treatment regimen of critically ill patients.
[0006] One of the generalized responses to stress by animals occurs in the GI tract whereby a decrease in mucosal blood flow can occur and thereby compromise the integrity of the mucosal barrier. This can lead to numerous issues including hemorrhage and sepsis in the animal and it may be difficult to achieve the goal of stimulating appetite without repairing the GI tract first.
[0007] There are other aspects to consider in dealing with extended stress on the animal during an infection, surgery etc. The whole digestive system has a delicate balance between bacteria that have numerous beneficial roles in the animal and pathogenic bacteria that are deleterious. This balance will be lost during periods of stress. The way to quickly correct this imbalance is by adding back beneficial bacteria as a supplement to recolonize the gut. Stress also leads to electrolyte and water loss in the body. This dehydration of the animal is another key factor that needs to be corrected quickly if recovery of the animal is to be ensured. The way to correct this dehydration is through supplementation with electrolytes, using specific water enhancing re-absorption mechanisms. Stress can also lead to impairment of the immune response. One way to improve the immune response is to stimulate the immune system with appropriate factors now found in leading nutritional supplements.
[0008] Studies have documented the effects of cattle nutritional status and outcome during infections or stress. Some details have been determined on some of the effects in transporting cattle. Dehydration, loss of energy, imbalances of beneficial bacteria and weakened immune systems are common problems in transported animals. Studies on transportation stress on feeder calves have determined that loss of 5-15% body weight commonly occurs depending on rail or truck transport (Hutcheson, 1984). In addition, it is not unusual for calves to arrive at the feedlot with only 10-25% of a normal rumen microorganism's population (Price 1984, Loerch and Fluharty 1999). Loss of water, loss of energy, a reduced microorganism population in the animal, and a weakened immune system are just a few of the contributing factors that lead animals to the sick pen.
[0009] These consequences of relocation/shipping can result in increased susceptibility to viral infection in cattle. Viral infection weakens the immunity of the already stressed animals, which, in turn, leads to secondary bacterial infections and further complications for the sick pen. An example of this type of stress for transported cattle is one of the major problems in the beef industry, bovine respiratory disease complex (BRD). BRD is the leading cause of illness and death in feedlots (APHIS 2001). A typical scenario for the development of BRD begins with weaning followed by the transportation of the cattle to the feedlot. The stress of transportation for long distances in crowded conditions, possibly through inclement weather without feed or water, causes the animal to become dehydrated and deprived of energy. As new animals are mixed together in transport they become exposed to new microorganisms that they haven't had a chance to develop immunity against. The defining characteristic of BRD occurs in a group of bacteria and viral organisms known as commensals that normally inhabit the respiratory tract without risk to the animal as long as the animal is healthy and well nourished. Transportation places stresses on the cattle, which will result in alterations in the populations of the commensals in the respiratory tract of cattle. This alteration of commensal population leads to BRD. If the animal is pulled in the early stages of BRD and treated with antibiotics, the prognosis is good for the animal. However if the infection has been allowed to progress further, the animals may not respond as well to antibiotics and may even die.
[0010] BRD has a huge economic impact on the cattle industry worldwide. It is called a disease complex because it involves many different components including environmental factors, host factors, viruses, bacteria and other infectious agents. There is no one single cause of BRD. Pathogens identified in BRD include Pasturella, Haemophilus, Actinomyces, Parainfluenza, Bovine respiratory syncitial virus, Bovine herpes virus (IBR), Bovine viral diarrhea, other viruses, Mycoplasma and Chlamydia. Cows that are affected will show respiratory signs such as fever, depression, anorexia, difficulty breathing, nasal and ocular discharge, coughing, sneezing, gasping, grunting, recumbence and death. Animals may stand with their elbows abducted and their necks extended in an attempt to breath.
[0011] Treatment consists of appropriate antibiotic therapy to eliminate the bacterial pathogens and supportive therapy or care. Prevention includes vaccinating the dams about 3-4 weeks prior to calving so that calves will have good colostral antibodies when they nurse. Calves should be vaccinated again prior to weaning and being placed in same-age groups. Environmental factors should be controlled such as proper ventilation, humidity, presence of dust and debris, overcrowding, cleanliness, etc. Quarantine of new arrivals should be practiced whenever feasible or an all-in all-out method of management should be adopted.
[0012] If the animal requires multiple antibiotic treatments, the value of the animal decreases. It has been reported that the gross value of the carcass is decreased by about $4 for heifer that have undergone one treatment for BRD and $19 for heifers receiving more than one treatment for BRD (Stover et al 2000). Even if these animals do recover and are put back into the regular pen, they usually do not perform well as regular healthy animals. These animals have lower average daily gain and lower marbling scores, resulting in a 37.9% reduction in the percentage of carcasses graded U.S.D.A Choice, or above. Approximately 5 million cattle a year are placed in sick pens due to BRD alone, costing feedlot owners more than $500 million per year to treat them. Depending on the time of year, mortality among the animals can range from 10-15%. This means feedlot owners are losing $50-75 million dollars per year due to mortality alone for BRD, and that money will never be recouped by feedlot owners. Not only that, this financial problem is only going to be worse in the future for feedlot owners because BRD incidences are increasing. To compound matters, it is known that stressed and fatigued cattle don't produce as much immunity as rested cattle when vaccinated (Thorn 1985) despite the availability of better drugs to treat infections. The cost of repulling cattle is going to be even more financially costly. Any supportive therapy in the form of a nutritional supplement to help the drugs and medical treatments for BRD work more efficiently in sick pen cattle will be a welcomed asset to feedlot owners who want to reduce this currently irrevocable $50-75 million dollar yearly financial loss to BRD mortality alone.
[0013] These studies have indicated that cattle arriving at the feedlot may not be in the best of shape to allow vaccinations to work properly since they have lost weight, are catabolizing muscle to get more energy, are dehydrated and no longer have the proper balance of microorganisms. The animals in the sick pen are treated with drugs but really should have additional supportive nutritional therapy to address the dehydration, energy, bacterial imbalances issues that also need correction. If these other issues are addressed, then recovery time in the sick pen will be reduced thus putting more animals back into the regular pen and cutting overall cost to the feedlot owner.
[0014] It is known that nutrients and nutritional status can affect medication absorption, elimination and tolerance of drugs (Spada 2002, Damle, 2002, Kenyon 1998). Potent antibiotics and other drugs will not function properly if the animal is dehydrated and severely depleted of energy. One of the most important steps in allowing drugs to effectively work in critically ill patients is the establishment of adequate volume status (Meier-Hellmann 2001). If the animal is given replacement fluids and electrolytes and provided with adequate energy, the animal will respond better to the drug therapy. Adequate hydration status allows for vasoactive drugs to circulate properly and become available to the animal and allow for effective action of the drug. In addition, insufficient energy intake will complicate an animal's condition by impairing tissue regeneration and recovery from disease (Center 1998). A primary goal after surgery in horses is to initiate the enteric energy and nutrient uptake (Coenen 2001). This is also true in dogs and cats that contract cancer. It has been shown that diet plays an important role for influencing responses to chemotherapy in dogs (Ogilvie 2003). Among the reasons given for why drugs and vaccines don't always work is related the drugs' inability to work in animals with general overall poor immune and health status. Clearly, it is evident that adequate energy, hydration status and immune status are important in the ability of drugs to function properly.
[0015] The current veterinarian approach to dealing with the issues of dehydration, energy loss, bacterial imbalance and immune system for animals in the sick pen or hospital is to treat each of the issues as a separate issue. However this approach is limiting since all of these issues are interconnected. The issues of dehydration, energy loss, imbalance of beneficial bacteria and impaired immune responses resulting from generalized stress or infection need to be addressed as whole concept rather than as individual issues. The new comprehensive approach for the veterinarian to achieve an enhanced rapid recovery and to prevent relapses with specific antibiotics, drug therapy, surgery or other stress should now be to include a supportive nutritional therapy that addresses effective rehydration of the animal, increases in energy, and adding back beneficial bacteria to the gut. This comprehensive approach is going to hold true for small and large animals. This kind of therapeutic approach will help the drugs or antibiotics work more effectively and put the animal back onto a rapid path to recovery along with reducing financial costs incurred by prolonged treatment.
[0000] Nutrient Support
[0016] There are a number of effective nutrients that play important protective roles in the gastrointestinal tract in animals. Amino acids such as glutamine and arginine, vitamins A, zinc, prebiotics and probiotics have been shown to support a strong role as enteral nutrients in the gastrointestinal health of many animals studies (Duggan 2002). It is clearly evident that proper supplementation with the appropriate nutrients will lead to a functional gut in shorter times for stressed animals and thus faster overall recovery times as the animal regains use of the GI tract. These supplements help accomplish this by addressing adequate energy, hydration status, and the immune status of the stressed animals.
[0017] The specific kinds of support that are normally desired with this supplemental nutritional therapy should include rehydration and reenergization of the animal along with the recolonization of the gut with beneficial bacteria. These are the key elements that are most affected during infections or other stressful situations for the animal such as injury, surgery, vaccination, and deworming. It is known in that in these stressful situations a variety of problems can occur including damage to intestinal villi, severe dehydration, inability to absorb nutrients with loss of appetite, overall loss of energy and imbalances of beneficial bacterial normally found in the gut. To treat only the immediate cause with an antibiotic or drug for these problems is not enough. A comprehensive nutritional supplementation approach should be used to: 1) rehydrate the animal by replacing lost fluids and electrolytes in an efficient manner; 2) reenergize the animal with glucose and other energy sources to give the sick animal an energy boost to help fight off the infection and get back to feed and water; 3) recolonize the gut with beneficial bacteria to help restore normal appetite and digestion. If these support issues are addressed, then a number of important steps will occur in the animal naturally, with the help of the drugs, to reduce (i) the severity and length of the initial infection, (ii) the probability of relapse, and (iii) slow weight gain after recovery.
[0000] Probiotics
[0018] The digestive system of animals contains billions of bacteria, some of which are beneficial, or “good bacteria”, and some of which are pathogenic, or “bad bacteria” capable of harming the animal. In a normal healthy animal there is a delicate balance between beneficial and pathogenic bacteria. Normally beneficial bacteria grow more rapidly than pathogenic bacteria viruses, fungi and parasites, depriving these of needed nutrients. Thus, a large majority of the bacteria in the gut are beneficial bacteria which, in turn, make certain important B-complex vitamins, help improve certain normal digestive processes including fermentation of carbohydrates to lactic acid, reduce blood ammonia levels, stimulate the immune system and thus lead to a healthy life in many domesticated animals (Pizzorno, 1996, Friend 1984). However, when there is extended stress on the animal, such as during an infection, surgery etc., the whole system is upset and the delicate balance is lost. The number of beneficial bacteria declines rapidly and the pathogenic bacteria increase in number several fold. Pathogenic bacteria secrete toxins, which lead to illness in the animal, which leads to further stress and further imbalance of the beneficial bacteria. This imbalance will need to be corrected by adding back beneficial bacteria to recolonize the gut.
[0019] Direct Fed Microbial (DFM) supplements contain these beneficial bacteria in a stable, viable form. When given as directed they will recolonize the gut by adhering to the intestinal epithelial cells and or in the mucus, thereby helping to increase the number of beneficial bacteria there. Once the beneficial bacteria have begun to recolonize the gut, they will begin competing with the pathogenic bacteria to bring back the normal balance. Several mechanisms have been proposed to be responsible for this interaction, including competition for the adherence sites on the epithelial cells lining the GI tract by the beneficial bacteria that crowd out the pathogenic bacteria or out compete for nutrients. Other mechanisms include poisoning the pathogenic bacteria with antibiotic-like growth-inhibiting factors such as bacteriocins (Klaenhammer 1988) or production of hydrogen peroxide, produced by the beneficial bacteria. As the production of toxins from pathogenic bacteria declines with decline in pathogenic bacteria to tolerable levels, the animal recovers normal appetite and digestion leading to weight gains.
[0020] Regardless of the actual mechanisms involved, supplementing with naturally occurring bacteria has been shown to reduce the reinfection rate and intensity for respiratory pathogens in animals. Both aerobic and anaerobic bacteria of the normal flora in the upper respiratory tract can hinder the growth of pathogens and the establishment of a renewed infection. Lack of interfering bacteria facilitates recurrence of these diseases. Recolonizing with naturally occurring beneficial bacteria significantly lowered the reinfections of the upper respiratory tract.
[0021] In numerous large animal studies, it has been shown that probiotics have helped cattle with bovine respiratory disease and also gained weight in feedlot situations. Direct fed microbials have been shown in numerous industry and academic studies to be beneficial to both incoming cattle and cattle in sick pens. Industry data on the use of probiotics in incoming cattle generally examines daily weight gain, the number of animals that would get sick, and the cost/benefit ratio (net return) of the product compared to control animals that do not receive probiotics. The preponderance of industry data clearly favors the use of probiotics. For example, studies conducted at Rocky Top Cattle Company (Gerald, 1983) in Oklahoma showed clear daily weight gain and fewer sick animals compared to controls with the use of probiotics. Probiotics at the rate of 10 cc (PROBIOS BOVINE ONE ORAL GEL) was administered to the treatment cattle (N=114) at time of processing. Control animals (N=123) did not receive the probiotic supplement. At the end of 30 days of treatment, the results showed average daily gain (ADG) for the treated animals was 0.72 lb. higher than the control animals. In addition, the probiotic treated animals had far fewer pulled animals than the control group for reasons of health (6 pulls in probiotic group vs. 30 pulls in control group). This study clearly shows that probiotic supplemented animals performed better with greater early gains and much less illness. The typical net return for PROBIOS in 1989 was shown to range anywhere from $13 to $18 per animal, depending on when the use of the probiotics started.
[0022] Academic and field studies have also showed the ability of probiotics to reduce the number of times sick pen animals actually have to be treated. In an academic trial (Stewart) when PROBIOS oral gel was administered to cattle at the rate of 10 cc/head, one dose only to incoming cattle, he observed improved weight gain and lower mortality over a period of 30 days. This clearly is a big financial advantage to feedlot owners since treatment and labor costs are reduced and animals will rejoin the general population much sooner. Other studies have also shown similar advantages of using probiotics to enhance weight gain in stressed cattle (Anderson 1992). There are also added advantages of giving direct fed microbials to feedlot cattle which result in decreased fecal shedding of pathogenic E. coli 0157:H7 and lowering overall herd susceptibility (Brashears 2003). Clearly the use of probiotics has a place in the feedlot and sickpen.
[0023] To maximize the benefits of probiotics, substances known as prebiotics are given as a supplement. Inulin, a complex carbohydrate, is one such prebiotic. Inulin serves as a nutrient for probiotic to stimulate probiotic growth and survival in the gut. The beneficial effects of probiotics may be enhanced and extended by simultaneous administration of a prebiotic (Rolfe, 2000). Prebiotics such as inulin also have additional advantages in that they can also stimulate the immune system. Inulin has been shown to modulate gut associated lymphoid tissue in such a way that antitumoral immunity was stimulated (Pierre 1997). The use of probiotics in other animal species besides cattle has been shown to have beneficial effects for treating stressful events such as transportation, surgery, and antibiotic treatment. In horses, use of probiotics has been shown to be useful for the prevention and treatment of enteric diseases (Weese 2004), reduce pathogenic shedding of pathogenic organisms (Ward, 2004), and enhance growth in neonatal foals and decrease the incidence of diarrhea (Yuyama 2004). While currently available commercial dog and cat foods containing probiotics may not be the best source of probiotics for dogs and cats (Weese 2003), probiotics have been shown to improve digestion in dogs (Biourge, 1998), stimulate specific immune functions in dogs (See table 1: Benyacoup, 2003) and have quicker recovery times for both hospitalized dogs and cats (Barrows 1985, Rastall 2004). The use of probiotics and prebiotics supplementation in small and large animals to help reduce the problems of imbalances of bacteria and to stimulate the immune system are clearly justified in a comprehensive approach to treating stress.
TABLE 1 Probiotic ( Enterococcus facecium ) stimulation of immune system in dogs Control Probiotic CD21 + /MHCII + B cells (%) 10.2 ± 1.2 17.6 ± 1.8 specific IgA (OD 405 nm) 0.2 ± 0.01 0.35 ± 0.03 specific IgG (OD 405 nm) 0.5 ± 0.1 0.8 ± 0.1 (Based on Benyacoub, Jr. Nutrition 133: 1158, 2003).
Energy Issues
[0024] When large animals are transported by truck or rail, they must expand more energy to maintain their normal homeostasis (Friend 2000, Marahrens 2003). As animals may have been deprived of food and water during transport or don't want to eat during transport, they can arrive at feedlots being dehydrated and depleted of energy. Upon arrival at the feedlots the animals are subjected castration, dehorning vaccination, deworming, branding, etc. that cause further stress to the animal and even more energy expenditure. This can lead to immune system depression and when the animals come in contact with new animals, the possibility occurs of coming in contact with new infectious agents for which they have no immunity. While most infectious agents may not cause detectable disease in healthy animals, they can express their virulence when the host animal is subjected to severe or prolonged stress, particularly in co-infection with other disease agents. Small animals that are transported to hospitals for surgery can also become stressed and be subject to energy loss. The surgical procedure itself adds stress, and this stress depresses the normal immunological defense mechanisms. These animals can also be exposed to new pathogens to which they have no immunity as they come in contact with other animals at the hospital. It is necessary to treat these animals in a way that will help prevent the spread of disease and also give back energy in the animal.
[0025] An easy way to provide quick energy to stressed animals is from an energy supplement containing precursor sources of ATP, which are readily bioavailable for rapid absorption and utilization in the gut. The key to rapid bioavailability is to use the correct kinds of fuel sources in the first place. Nature has seen fit to be use fats, polysaccharides and proteins as the three major starting sources in generating ATP in animals. Glucose is a simple carbohydrate sugar broken down from polysaccharides that has traditionally been, and continues to be, used as a good source of energy in supplements. It is absorbed fast and much is known about the conversion of glucose to ATP. While nature has always been good about using the right sources at the right place, only relatively recently has it been recognized that other fuels besides glucose are utilized even more efficiently in the gut. While using traditional glucose is good, it seems quite reasonable to be using energy sources from the other major starting points of fats and proteins in generating ATP in an energy supplement as well.
[0026] Adding a unique energy source of medium chain triglycerides (MCT) to a supplement that takes also advantage of energy from fat sources has also been examined. Fatty acids consist of hydrocarbon chains and a carboxylic acid. They are stored within cells as triglycerides and later released though the blood stream to meet energy demands of various tissues. Long chain fatty acids of 16-20 carbons are normally used by animals for fuels and have been traditionally used in animal feed supplements. However, another chain length exists that will be more effectively utilized for energy production called medium chain fatty acids (MCFA). Medium Chain triglycerides of 6-12 carbons atoms are a fuel source more efficient for ATP production than the long chain fatty acids for some of the following reasons. MCT's are smaller in size and more ionized than the long chain fatty acids and therefore are more soluble and easily absorb in the body by readily crossing cell membranes into the blood stream without any specialized biochemical transport systems that are required by the long chains. As such, when MCTs are hydrolyzed, they are more rapidly and more completely hydrolyzed than long chain fatty acids in the generation of ATP. In addition, MCTs can provide twice as much energy compared to carbohydrate metabolism. MCTs produce 8.3 calories per gram compared to 4 calories per gram of carbohydrates. (Bach 1996).
[0027] Because of these unique digestive and metabolic properties MCTs have been examined as energy sources for a number of nutritional settings to give animals additional energy. In neonatal calves (Sata 1994) and adult steers (Sata, 1993) have been shown to be advantageous for increasing ketone and energy levels with the use of MCTs in appropriate concentrations. MCTs have been examined in other animal species studies as well. Dietary MCTs have been effectively absorbed and oxidized by neonatal pigs to improve energy status (Lee and Chiang 1994) and blood glucose (Lepine, 1989), rats (Crozier 1988), chicks (Chiang 1990), and humans (Van Zyl 1996). MCTs have been shown in a number of different animal species to be absorbed, digested and converted to ATP for energy use more efficiently than long chain fatty acids (See Table 2). MCTs are well tolerated by dogs (Grancher D, 1987) and appear to be better caloric source in dogs than long chain triglycerides (Cotter R 1987).
TABLE 2 Medium Chain Triglycerides (MCT) absorption 1 , digestiblity 2 , and conversion to ATP 3 in horses 1 , stressed dogs 2 , and stressed piglets 3 compared to control diets with long chain fatty acids Control diet MCT diet Plasma triglycerides (mmol/l) 1 196.7 ± 30.2 427.3 ± 85.7 Apparent Digestibility of fat (%) 2 27.7 ± 1.3 76.8 ± 8.6 Maximal utilization rate (mmol ATP/ 0.370.11 1.45 ± 0.11 kg 0.75 /min) 3 Extent of utilization (mol ATP/kg 0.75 ) 3 0.23 ± 0.04 0.91 ± 0.04 1 Based on Hallebeek, Arch. Tierernahr. 54: 159, 2001. 2 Based on Laflamme, Purina Research Report, 1998. 3 Based on Heo, Jr. Nutrition 132: 1989, 2002.
[0028] The third principle source of fuel for ATP generation in animals is from protein. Of all of the amino acids that make up proteins, glutamine is the principle circulating amino acid accounting for around 50% of the total exchangeable amino acid pool (Souba. et al. 1985). It had been demonstrated (Gardemann, et al. 1992) that luminal (or enteral) administration of Glutamine enhances glucose absorption. But more importantly it also appears to be the major energy source for the intestinal epithelium (Windmuellar, 1982). Metabolism of Glutamine to alpha-ketoglutarate and subsequent complete oxidation via Kreb's cycle yields 30 moles of ATP per mole of Glutamine. Glutamine is now believed to be a key energy-yielding substrate in reducing stress generating situations of hypoxia, anoxia and dysoxia (Young 2001). In dogs, it is believed that heavy exercise (Halseth 1998), infection, surgery and trauma can deplete the body's glutamine reserves, particularly in muscle cells. In dogs and cats with cancer, it is believed that the addition of glutamine to the diet can be helpful in preventing cancer-induced muscle wasting (Jank, 2004). Glutamine supplementation in dogs appears to preserve body protein from hypercatabolism (Humbert 2002). Glutamine supplementation is now believed to be useful for patients undergoing recovery from major surgery or critical illness (Griffiths R D 1997). There is some evidence for an effect of glutamine supplements in promoting glycogen synthesis in the first few hours of recovery after exercise (Bowtell 1999).
[0029] The use of readily absorbed and digestible sources of energy precursors should be the goal of any nutritional supplement. The inclusion of energy sources from carbohydrates, fats and proteins in a predigested format such as glucose, medium chain triglycerides and glutamine is a more comprehensive approach to provide energy to the gut rather than getting it from single source.
[0000] Hydration
[0030] Glutamine also plays a number of other and perhaps more important roles in animals besides serving as an energy source. The transport of water and electrolytes such as sodium, potassium, chloride and bicarbonate is a key function of the intestinal tract and are fundamental to the hydration status of the animal. Animals in the stressful situations such as antibiotic therapy or surgery require rehydration to enhance and speed up recovery. Traditionally, oral rehydration therapies have used glucose or glycine to promote sodium and water absorption from the gut, which helps combat dehydration and maintain normal acid-base balance. However, a new approach is emerging that it also includes the use of glutamine to promote sodium absorption. One of the important aspects of dehydration [due to diarrhea] in animals is destruction of the intestinal villi tips where sodium absorption normally occurs in an electrogenic manner when using glucose or glycine supplements. Fortunately, nature has provided an alternative electroneutral way of getting sodium into the epithelial cells of the intestinal villus crypts that are not destroyed. Glutamine has the ability and been shown to stimulate sodium uptake and subsequent rehydration using this alternative sodium absorption method in a variety of animals. For example, the use of glutamine in oral rehydration solutions (ORS) has shown positive clinical outcomes for water and electrolyte reabsorption in diarrheic calves compared to conventional ORS. The use of glutamine in an ORS improved plasma volume significantly, corrected packed-cell volume and avoided significant weight loss compared to pre-diarrheic values in an E. Coli model of calf diarrhea. (See Table 3: Brooks, 1997). Similar effects have been observed in other animals including rabbits (See Table 3: Silva 1998) and piglets (Rhoads 1991). Glutamine appears to stimulate sodium uptake in calves via crypt cells despite severe villus atrophy in the intestine (Blikslager 2001). Glutamine also increases intestinal villus height in stressed animals (See Table 4), stimulates gut mucosal cellular proliferation and maintains mucosal integrity (Miller, 1999). This regeneration of villi is vital for nutrient absorption and subsequent recovery of the animal. Glutamine has been also been shown to alleviate the detrimental effects of villus form caused by conventional oral rehydration solutions in calves (See Table 4: Brooks 1998). Glutamine treatment has also been shown to be beneficial in repairing oxidant-injured mucosal in horses (Rotting 2004) and oral supplementation of glutamine offers protection to the intestine after surgery in animals (Ramamoorthy, 2003). The addition of glutamine along with electrolytes in the presence of a mixture of amino acids promises to be an effective ingredient beyond the traditional approaches to rehydration.
TABLE 3 Response to Oral Rehydration Solutions (ORS) with or without glutamine in calf 1 and rabbit 2 experimental induced diarrhea. Control ORS Glutamine ORS Plasma Volume (L) 1 0.1 ± 0.1 0.3 ± 0.1 Blood Volume (L) 1 0.0 ± 0.1 0.3 ± 0.1 Plasma Sodium (mmol/L) 1 2.6 ± 0.7 3.8 ± 1.4 Sodium absorption (uEq/g/min) 2 −0.5 ± .48 10.3 ± 1.2 Plasma Volume (L )1 −0.012 ± .012 0.08 ± 0.008 1 Based on Brooks, Vet. J. 153: 163-170 1997. 2 Based on Silva, J. Pediatr. Gastroenterol. Nutr. 26: 533 1998.
[0031] TABLE 4 Effect of glutamine on intestinal morphology in stressed animals (pigs 1 , rats 2 , calves 3 ). Control Enteral With Target Treatment Glutamine value Jejunum Villus Height (um) 1 270 358 ≧339 Jejunum Crypt depth (um) 2 244 134 ≦150 Mid plus Distal small intestinal 111.3 92.2 ≦100 Crypt width (mean % of baseline control )3 1 Based on G. Wu, Jr. of Nutrition 126: 2578, 1996 (Weaning of pigs). 2 Based on U. Tannuri, Rev. Hosp. Clin. Fac. Med S. Paulo 55: 87, 2000 (malnourished rats). 3 Based on HW Brooks, Vet. Jr. 155: 263, 1998 ( E. coli induced diarrhea in calves).
Immune Stimulation
[0032] One of the important factors in rapid recovery from injury, surgery, infections and burns is the adequate nutrition of the immune system and the implications of this for whole body metabolism. Cells in the immune system such as lymphocytes and macrophages undergo increased rates of productions and rapidly increase during inflammatory immune responses. These cells have unique nutritional requirements that require glutamine for purine and pyrimidine nucleotide synthesis needed in cell division (Newsholme 1985) It has become evident that glutamine is used a very high rate by lymphocytes and macrophages (Ardawi 1985, Newsholme 1987). The requirement for glutamine will increase dramatically after injury, surgery, infection and bums since there will be increased activity of the immune system and an increased number of cells will participate in cell division and hence will require glutamine. Glutamine levels in the plasma and tissues pools decline markedly in the course of many different catabolic diseases (Smith 1990) and has been suggested to be a conditionally essential dietary amino acid under conditions of stress (Wischmeyer 2003). It has been shown that glutamine provision corrects or improves the function of some tissues when that function has been impaired in a number of stress generating situations. Glutamine infusion in dairy cows has been shown to result in an increase of blood plasma glutamine (Plaiser 2001). In post-operative dogs (Roth 1988) glutamine-containing dipeptides attenuated or reversed the injury-associated decrease in the concentration of glutamine and in muscle and plasma. In other animals, including man, glutamine provision has been shown to be beneficial for the immune system (Burke 1989, Kweon 1991, Yoshida, 1992, Scheltinga, 1991).
[0033] Glutamine promotes secretory IgA production in a way that will improve the immune defense of the gut lining and help prevent infections (Pastores 1994, Souba 1993). Secretory IgA, produced in cells around the mucin secreting glands of the intestinal mucosa, plays a role in binding and inactivating foreign antigens such as virus, fungi, protozoa and pathogenic bacteria. In animals fed a glutamine free diet, secretory IgA falls of dramatically (Averdy, 1990). The overall benefit of providing glutamine supplements to all metabolically compromised animals arises from the multiple anabolic and host protective effects of this amino acid and immunomodulation is only one important facet (Wilmore 1998).
[0034] There are a number of other factors for enhancing the immune system. Besides glutamine and probiotics, carbohydrates, lipids, amino acids, minerals, supplemental vitamins and electrolytes should also be provided. Nockels (1996) reported that antioxidants improve immunity in animals following stress. Vitamins act as co-factors in several metabolic pathways and can be depleted in stress generating situations. These should be given back to the animal as a supplement, to provide the immune system the proper building materials for proper function. Addition of Vitamin E, along with other fat and water-soluble vitamins, will help in better utilization of energy and speed up recovery. The natural immunity will start working, leading to much faster recovery from the stress-generating situations. It has been shown that vitamin E and B-complex supplementation results in significant daily gain and improved feed conversion in steer calves starting and receiving diets (Feedlot Management 1986). Hays et al. (1987) found that when Vitamin E was supplemented to newly received steers, it increased daily gain and decreased morbidity and sick days per calf. Galyean et al. (1999) reported that Vitamin E added to receiving diets was beneficial to increasing gain and decreasing BRD Mortality. In another study, Rivera et al. (2002) also concluded that supplemental vitamin E might be beneficial for helping stressed cattle recover from BRD. Vitamin A is a fat-soluble vitamin that plays a vital role in maintaining normal health. It was observed that vitamin A should be increased in stressful conditions like low environmental temperatures or exposure to infective bacteria (Eaton 1972).
[0035] Vitamins and minerals work together in a synergistic manner and are essential to life by working in many biochemical functions, thereby contributing to normal and overall health. Deficiencies of specific minerals can result in various metabolic disorders but supplementation can help correct these problems. Galyean et. al. (1999) reported that supplemental Zinc and Copper can alter immune function of newly received calves and some field trials have shown decreases in BRD morbidity rate.
[0036] Immune enhancing diets (IED) have been shown to improve wound healing, modulate vascular reactivity, affect gut blood flow, alter endothelia activation, modulate cytokine response and alter neurohormonal signaling and reduce hospital time (Zaloga, 2005). Nutritional management of chronic lung disease been a major medical challenge in humans but guidelines have now been established that show a need for energy, electrolytes vitamins and minerals when treating these cases (Carlson 2004). Pig and rat models of acute respiratory distress syndrome have shown a beneficial role of these types of supplementation to decrease lung inflammation (Mizock 2004). These IEDs have demonstrated beneficial positive clinical effects and yielded economic advantages for health care costs as reduction in hospital time occurs (See Table 5).
TABLE 5 Effect of Immune Enhancing diets on clinical outcomes in critically ill patients. Meta analysis of 26 primary studies of surgical, burn, trauma and medical cases. Parameter Reduced Time p Value Mechanical ventilation time (−2.3 days) 0.009 ICU stay (−1.6 days) <.0001 Hospital stay (−3.4 days) <.0001 (Based on Zaloga JPEN 29: S49, 2005).
[0037] The supplements that have been discussed are known to have efficacy in cattle, horses, pigs, sheep dogs, cats and other animals when used by themselves. The concept of using probiotics to treat animals that have been stressed by transport or have been place in the sick pen or hospital appears to be valid and accepted by many veterinarians. The clinical studies have shown that cattle fed probiotics gain more weight, have significantly faster recovery time from sick pens and significantly lower reinfection rates than cattle not fed probiotics. The concept of using glutamine with electrolytes in calves and other animals to treat dehydration has been shown to be more effective than standard oral rehydration solutions containing glucose or glycine. In addition, there are other multiple benefits of glutamine for animals under stress situations including intestinal villi repair and serving as an energy source for the GI tract and immune system. The concept of supplementing vitamins and minerals to incoming cattle at feedlots to improve performance, reduce morbidity, and stimulate the immune system is now accepted. In addition, the concept of using glucose, medium chain triglyceride as an energy source has been demonstrated to be an effective way to increase energy levels in cattle, dogs and other animals.
SUMMARY OF THE INVENTION
[0038] While all of these supplements appear to be effective by themselves, a new concept has emerged that indicates there are synergistic effects of these supplements when combined together. The issues of dehydration, energy loss, imbalance of beneficial bacteria and impaired immune responses in cattle, horses, dogs and other animals resulting from generalized stress needs to be addressed together rather than as individual issues. In this new approach, the veterinarian achieves enhanced rapid recovery and prevention of relapses by combining specific antibiotics or drug therapy with supportive nutritional therapy, particularly supplements that address effective rehydration of the animal, increases in energy and adding back beneficial bacteria to the gut in a synergistic approach. This kind of therapeutic approach will enhance the therapeutic effect of the drugs or antibiotic by making them work more effectively and putting the animal back onto a rapid path to complete recovery.
[0039] By providing the supplemental nutritional support for specific therapies for injury, infections and stress it is known that animals are able to respond to antibiotics and drugs better, the reinfection rate is lower, and animals will regain strength along with normal appetite faster. Use of antibiotics is a key to successfully controlling infections. But, for an antibiotic to perform well and work as intended, helping out the immune system, the overall energy level, the hydration status and balance of beneficial bacteria in the gut of the animal is a must. A comprehensive approach of a supportive nutrition that addresses all of the issues of hydration, energy and the general health of the gut is indicated. It will lead to positive outcomes of antibiotic therapy, surgery or other stressful situations for the animal that will be much faster than if not employed at all.
[0040] The present inventors have developed improved nutrient compositions that will reduce recovery time for animals that have had stress placed on them from various sources. In view of the foregoing, it will be appreciated that a composition for improving the outcome of animals undergoing medical treatments of drugs, antibiotic therapy, surgery or other forms of stress would be a significant advancement in the art. It is an object of the present invention to provide compositions for use as a dietary supplement that, when ingested, enhances antibiotic or drug treatment of ailments in the gastrointestinal tract from pathogens such as bacteria, viruses, fungi or protozoa or other causes. It is an object of this invention to provide a composition for uses as a dietary supplement that provides energy for the intestinal enterocytes and immune system lymphocytes turnover. It is an object of this invention to provide as a dietary supplement a composition that effectively rehydrates animals.
[0041] The invention provides administration of probiotics and prebiotics, glutamine with electrolytes, glucose and medium chain triglycerides, along with vitamins and minerals in effective amounts to animals that are exhibiting stress. It is expected that this invention will benefit stressed or sick animals by effective rehydration, correcting bacterial imbalances, adding additional energy to the animal, improve the immune system and allow drug or antibiotic therapy a chance to work more effectively. This will result in shorter recovery times for animals under stress or being treated for specific diseases or conditions such as surgery.
[0042] It is already known that use of species specific probiotics by themselves will cause weight gain in cattle, and reduce recovery time in the sick pen, and improve overall herd health by reducing fecal shedding of pathogenic organisms. Similar beneficial effects are seen in with the use of probiotics in other animals. The administration of species specific probiotics in horses have been shown to enhance growth in neonatal foals and young horses, be useful in treatment of enteric disease and decrease the incidence of diarrhea, prevent the spread of diseases by reducing shedding of pathogenic organisms in the environment. Likewise, in hospitalized dogs and cats a reduction of digestive disorders and reduced shedding of pathogenic organisms occur, better appetite and faster recovery times also occur with the use of probiotics. In addition, enhanced specific immune functions and intestinal health occur when administrating species specific probiotics in dogs and cats. The use of probiotics in these animal species has clearly been shown to be effective and beneficial in correcting imbalances in intestinal microorganisms, helping animals improve digestive issues and regain homeostasis for faster recovery in stress situations.
[0043] The objects and advantages of the invention will appear more fully from the following detailed description of the preferred embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0044] The nutritive compositions for the present invention are a novel combination of probiotics, prebiotics, glutamine, glucose, glycine electrolytes, vitamins and minerals. These ingredients in combination have a prophylactic and therapeutic effect in maintaining and enhancing gastrointestinal microflora, the rehydration status, energy balance and the immune system. A healthy intestinal environment will enhance the overall health of the mammal since many diseases, no matter what part of the body they manifest themselves, actually start in the GI tract. The nutritive supplement compositions of the present invention contain ingredients in a form that is bioavailable and thus accomplish their important nutritive functions. The nutritive compositions of the present invention function as source of growth and energy factors for the repair and growth of healthy intestinal tissue and cells found in the immune system. These compositions are understood to contain components that enhance the probiotic colonization of the intestinal tracts of animals.
[0000] Probiotics
[0045] There are a variety of probiotic microorganisms, which are suitable for use in this invention including yeast, such as Saccharomyces and bacteria such as the genera Bifidobacterium, Enterococcus, and Lactobacillus. The invention is not, however limited to these particular organisms. The person skilled in the art would understand and recognize those microorganisms, which may be included in the composition of the invention.
[0046] The preferred form for the probiotic composition in this invention for any animal species is to use species of microorganisms that normally inhabit the gut of that particular animal species. For example, in a preferred form the probiotic composition for cattle and calves are selected from Enterococcus and Lactobacillus species. In a preferred probiotic composition for dogs and cats is Lactobacillus species include but not limited to Lactobacillus acidophilus, Lactobacillus plantrum, Lactobacillus casei and Enterococcus species include Enterococcus faecium. The preferred probiotic composition for horses includes but not limited to Lactobacillus acidophilus, Lactobacillus plantrum, Lactobacillus casei and Enterococcus faecium. The preferred probiotic composition for pigs is Lactobacillus acidophilus, Lactobacillus plantrum, Lactobacillus casei and Enterococcus faecium. The preferred probiotic composition for sheep is Lactobacillus acidophilus, Lactobacillus plantrum, Lactobacillus casei and Enterococcus faecium. The probiotics are administered at doses of 10 7 to 10 11 colony forming units (CFU) per day.
[0000] Probiotics and Inulin
[0047] The use of inulin or other prebiotic components help enhance the survival rate of the probiotics in the gut of the animal by adding a source of energy specifically designed for the probiotic. This maintains the vitality of the probiotic itself but can have other synergistic and protective effects in the animal when used in combination with a probiotic. The use of prebiotics such as inulin and fructo-oligosaccharides have shown positive effects on the microflora balance in dogs, cats and other animal species and can also help stimulate the immune system. The use of prebiotics like inulin will be quite beneficial to both the probiotic and the animal as well.
[0000] Fructo-oligosaccharides
[0048] Fructo-oligosaccharides suitable for the present invention may include any fructo-oligosaccharide available for consumption. Preferably the fructo-oligosaccharide may be selected from inulin or soy fructo-oligosaccharide. It will be appreciated by one skilled in the art, however, that other oligosaccharides would also be suitable for inclusion. This would include oligosaccharides including galacto-, malto-, isomalto-, gentio-, xylo-, palantinose-, chito-, agaro-, neoagaro-, alpha-, beta-, gluco-, cyclo-inulo-, glycosylsucrose, lactulose, lactosucrose and xylsucrose. The oligosaccharide can be used in the compositions from concentrations of about 0.01 to 10% (w/w).
[0000] Electrolytes
[0049] The administration of electrolytes such as sodium chloride and potassium chloride with water is well established to promote rehydration in all animals that have become dehydrated due to scours and diarrhea or from other stress generating situations. The use of glucose or glycine has been proven to promote modest amounts of sodium uptake the animal. However it has been found that glutamine promotes even more effective sodium uptake in a number of animals including pigs and calves. The beneficial effects of glutamine for sodium uptake are even more pronounced by working synergistically in the presence of additional glucose or glycine. The advantages of glutamine to promote sodium uptake in oral rehydration solutions in calves has previously been the subject of an approved patent. Preferably the concentration of sodium per dose for animals is from 5 mg to 100 mg/kilogram of body weight. Preferably the concentration of potassium is from 5 mg to 100 mg/kilogram of body weight. The preferable concentration per dose of glucose is from 10 to 50 grams/kilogram of body weight. The preferable concentration of glycine is 66 mg to 264 mg/kilogram of body weight. The preferable concentration of glutamine is from 44 mg to 100 mg grams/kilogram of body weight.
[0050] There are other advantages of glutamine in this invention. Glutamine has been shown to increase intestinal villus height, stimulate gut mucosal proliferation or maintain mucosal integrity in a number of animal species including cattle, horses, pigs, sheep, and dogs. Glutamine provision can protect the GI tract and help repair the GI tract in times of stress for animals. As the GI tract becomes repaired or protected from stress, the ability of the gut will be improved to maintain normal digestive functions. The improved ability of the GI tract to digest food will lead to faster recovery times in during times of stress, whatever the cause may be. This will be become quite beneficial to the overall health of the animal.
[0000] Energy Sources
[0051] This invention utilizes a comprehensive approach to supplying energy to the stressed animal. Glutamine is the major energy source for the intestinal epithelium, which helps account for some of its important and beneficial actions in the GI tract. However, the other sources of energy come from carbohydrates and fatty acids that help animals quickly regain the energy lost in stress generating situations. This invention uses glucose to help quickly put energy back into stressed animals. Glucose is a simple carbohydrate that animals can quickly and efficiently absorb and utilize to generate ATP required by the animal to carry out biochemical functions. Another source of energy that this invention uses is from medium chain triglycerides. Medium chain triglycerides have an important advantage compared to carbohydrates for ATP production in that considerably more energy is made per molecule. MCTs can provide twice as much energy compared to carbohydrate metabolism. MCT administration has been shown to be beneficial in cattle, calves, dogs and other animal species for readily supplying required energy. This invention will utilize the three sources of energy that nature uses to provide a more balance approach to providing stressed animals required energy. The fatty acids found in the medium chain triglycerides that are preferred in this invention are from 8 to 10 carbon chains in length. The preferable concentration of MCT in this composition is from 100 mg to 600 mg/kilogram bodyweight.
[0052] This invention uses glutamine, vitamins and minerals to help stimulate the immune system. Glutamine is known to be required rapidly in dividing cells of the immune system and help reinforce the immune system. Under times of stress, a loss of available glutamine occurs in the animal even as the immune system attempts to respond rapidly. Provision of glutamine in this invention will be beneficial to the immune system by supplementing the requirements of the stressed animal for additional glutamine. This additional glutamine has been shown to be beneficial to cattle, rats, humans, dogs and other species in many types of stress situations.
[0000] Vitamins
[0053] This invention also uses vitamins to help stimulate the immune system. The use of vitamin A, vitamin E, and folic acid are known make the immune system work in an optimal manner. Deficiencies of vitamin A in animals will lead to degeneration of the mucosa while deficiencies of vitamin E can lead to muscular dystrophy. Deficiencies of folic acid can lead to a reduction in red cell production and subsequent anemias. Deficiencies of vitamin D can lead to problems in absorbing calcium. Provision of vitamins A, D 3 and E along with folic acid will benefit stressed animals by enhanced cell-mediated and humoral immune responses and better GI tract maintenance. The per dose preferred concentration for vitamin A is from 50-300 IU/kilogram bodyweight; for vitamin E 0.5 IU/kilogram and folic acid is from 0.5 to 2 IU/kilogram bodyweight. The preferred concentration of vitamin D 3 is from 5-30 IU/kilogram.
[0000] Minerals
[0054] Minerals play important roles in many biochemical functions in the body. Deficiencies of minerals can lead to problems in the immune system. However supplementation of zinc and copper can help correct these problems. As absorption of chelated minerals to amino acids or other substances is enhanced, this invention uses chelated minerals. This invention uses chelated copper, zinc, and manganese to benefit the immune system. The preferred concentration of copper is from 0.1 mg to 2 mg/kilogram; for zinc is from 100 mg to 300 mg/kilogram; and for manganese is from 0.05 mg to 0.2 mg/kilogram.
[0055] The synergistic effects of adding the additional components of glutamine with electrolytes, the energy sources of glucose with medium chain triglycerides, and vitamins with minerals will further increase the chances of the animal to gain lost weight and have shorter recovery times. This will result in significant additional profits to animal owners because of the cost effectiveness of this product should result in at least a 3:1 ratio in benefit returned to cost of use.
I. A typical formulation for adult cattle is: Glycine 1000 mg Glutamine 100 mg Sodium(min) 3.5% Sodium (max) 3.8% Potassium 250 mg Vitamin A 5,000 IU Vitamin D 3 750 IU Vitamin E 75 IU Glucose 3000 mg Zinc 90 mg Inulin 2000 mg Lactic Acid Bacteria 1 49 million CFU 1Consisting of a combination of Enterococcus faecium , Lactobacillus acidophilus , Lactobacillus plantarum and Lactobacillus casei .
[0056]
II. A typical formulation for calves is:
Glycine
500 mg
Glutamine
50 mg
Sodium (min)
3.5%
Sodium (max)
3.85%
Potassium
125 mg
Vitamin A
2,000 IU
Vitamin D 3
375 IU
Vitamin E
37 IU
Glucose
1500 mg
Zinc
45 mg
Inulin
1000 mg
Lactic Acid Bacteria 1
49 million CFU
1 Consisting of a combination of Enterococcus faecium , Lactobacillus acidophilus , Lactobacillus plantarum and Lactobacillus casei .
[0057]
III. A typical formulation for dogs and cats is:
Glycine
10 mg
Glutamine
20 mg
MCT Fatty acids
3.0%
Sodium (min)
3.25%
Sodium (max)
3.85%
Calcium (min)
11.0%
Potassium
0.0005%
Vitamin A
1,000 IU
Vitamin D 3
100 IU
Vitamin E
10 IU
Ascorbic Acid
10 mg
Riboflavin
0.5 mg
Glucose
530 mg
Zinc
11.25 mg
Inulin
200 mg
Lactic Acid Bacteria 1
10 million CFU
1 Consisting of a combination of Enterococcus faecium , Lactobacillus acidophilus , Lactobacillus plantarum and Lactobacillus casei .
[0058]
IV. A typical formulation for horses is:
Glycine
20 mg
Glutamine
100 mg
MCT Fatty acids
11.4%
Sodium (min)
5.0%
Sodium (max)
5.75%
Potassium
2.0%
Magnesium
1.8%
Vitamin A
20,000 IU
Vitamin E
200 IU
Thiamine HCl
500 mg
Pyridoxine HCl
400 mg
Glucose
8000 mg
Zinc
90 mg
Inulin
1400 mg
Lactic Acid Bacteria 1
300 million CFU
1 Consisting of a combination of Enterococcus faecium , Lactobacillus acidophilus , Lactobacillus plantarum and Lactobacillus casei .
[0059]
V. A typical formulation for sheep and goats is:
Glycine
500 mg
Glutamine
50 mg
Sodium (min)
3.5%
Sodium (max)
3.85%
Potassium
125 mg
Vitamin A
2,000 IU
Vitamin D 3
375 IU
Vitamin E
37 IU
Glucose
1500 mg
Zinc
45 mg
Inulin
1000 mg
Lactic Acid Bacteria 1
49 million CFU
1 Consisting of a combination of Enterococcus faecium , Lactobacillus acidophilus , Lactobacillus plantarum and Lactobacillus casei .
[0060] VI. A typical formulation for pigs is: Glycine 20 mg Glutamine 100 mg MCT Fatty acids 11.4% Sodium (min) 5.0% Sodium (max) 5.75% Potassium 2.0% Magnesium 1.8% Vitamin A 20,000 IU Vitamin E 200 IU Thiamine HCl 500 mg Pyridoxine HCl 400 mg Glucose 8000 mg Zinc 90 mg Lactic Acid Bacteria 1 300 million CFU 1 Consisting of a combination of Enterococcus faecium , Lactobacillus acidophilus , Lactobacillus plantarum and Lactobacillus casei .
Delivery System
[0061] The delivery system for calves and adult cattle are in the form of “Boluses”. Electrolytes and energy will be packaged in one bolus and the Direct fed microbials will be provided in the second bolus. To differentiate the products, the boluses will be color-coded. “Electrolytes and energy bolus” will be “Pink” in color and the “direct fed microbial” bolus will be “white” in color. One pink and one white bolus make “One dose” or “One feeding”.
[0062] The delivery system for dogs and cats will be in the form of “Chewable tablets”.
[0063] Electrolytes and energy will be packaged in one tablet and the Direct fed microbials will be provided in the second tablet. In order to differentiate the products the tablets will be of different “shapes”. “Electrolytes and energy tablet” will be “Square” in shape and the “direct fed microbial” bolus will be “round” in shape. One round and one square tablet will make “One dose” or “One feeding”. In order to make the tablet palatable the product will be made with liver and fish flavor.
[0064] The delivery system for horse will be in the form of a “Non-aqueous gel”.
[0065] Electrolytes, energy and Direct fed microbials will be delivered in an oil based gel along with preservatives and stabilizers. The product will be packaged in multi-dose or single dose plastic syringes.
[0066] While this invention may be embodied in many forms, what is described in detail herein is a specific preferred embodiment of the invention. The present disclosure is an exemplification of the principles of the invention is not intended to limit the invention to the particular embodiments illustrated.
[0067] It is to be understood that this invention is not limited to the particular examples, process steps, and materials disclosed herein as such process steps and materials may vary somewhat. It is also understood that the terminology used herein is used for the purpose of describing particular embodiments only and is not intended to be limiting since the scope of the present invention will be limited to only the appended claims and equivalents thereof.
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BACKGROUND OF THE INVENTION
This invention relates to quick coupler devices for fluid systems, and more particularly, to a rigid mount, breakaway, quick coupler having a flow-check feature therein.
Similar devices of this type are well known in the art, however, there are disadvantages with most of these because of the mode of operation and the varied applications which the coupler encounters. Some of the prior art devices are directed to the agricultural environment wherein the coupler is mounted on a tractor for receiving fluid from the control valve of the tractor and for coupling with the hose nipple of a hydraulic implement to be actuated by the fluid power source. Often this implement is a closed fluid system so that the nipple is presented to the coupler under fluid pressure. In this event, the accommodation must be made for the different mechanical interconnection which occurs and the subsequent opening of the closed fluid valve of the nipple to a full open flow condition.
Most of the couplers of this type which rely on a spring to hold the nipple valve open are subject to an undesirable characteristic called flow-checking. Flow-checking occurs when a surge of oil moves from nipple to coupler with sufficient force to overcome the coupler valve spring and allow the nipple valve to close and check the flow of oil. Mechanically actuated stops have been provided in the past to prevent flow-checking and the instant invention is an improvement in this type of device.
One example of prior art valve is shown in U.S. Pat. No. 4,200,121 wherein a mechanical stop is provided to produce the flow-checking feature. The stop is in the form of a pin which is spring loaded in the direction of its locking position and which cooperates with the stem of the coupler valve support member to control the flow-check movement of the coupler valve. A sleeve is provided on the stem and is axially movable relative thereto for resetting the stop pin by means of a ramp surface on one edge of the sleeve. Resetting of the coupler occurs upon disengagement of the nipple and leaves it in a position of preparedness for the next engagement cycle. A second embodiment of coupler is described in this patent wherein a flow responsive vane provides rotary movement, against the action of a torsion spring, to actuate a detent cam for locking cooperation with the detent contour of the valve support stem.
Another prior art device is manufactured by the assignee of the above-noted patent, also employing a mechanical stop to prevent flow-checking. This stop is in the form of a hairpin spring in a right angle bend, where the legs of the pin straddle the valve stem under control of a shiftable sleeve and are spread by a ramp surface for resetting purposes.
A problem with the latter design is that the stop device is not actuated if the connecting nipple is not under pressure. In this instance the valve stem moves back only a short distance and does not cause shifting of the sleeve relative to the valve stem. Consequently, the nipple can flow-check. However, when flow-checking does occur, the coupler valve stem will move the full required distance wherein the sleeve separates from a shoulder on the stem and allows the stop to engage to prevent further flow-checking.
A still further form of prior art structure is shown in U.S. Pat. No. 4,398,561 wherein a mechanical stop cooperates with the coupler valve support stem to provide flow-checking. In this arrangement, however, the stop is activated by the flow of fluid through the coupler whereby a sleeve is moved to force locking balls into engagement with the stem. This type of design is subject to flow conditions and is dependent to some extent upon fluid viscosity and the like.
SUMMARY OF THE INVENTION
The instant invention relates to an agricultural quick coupler which allows connection of a nipple under hydraulic pressure and which includes a flow-check stop therein. The coupler is a rigid mount type which means that it can be mounted directly on the tractor control valve or connected to it with rigid piping. An arrangement of seals and chambers inside the coupler allows the transfer of oil which permits the internal movement of a body member therein relative to the outer housing, which is necessary to connect and disconnect the nipple. The coupler allows for breakaway without damage in the event of an accidental disconnect of the implement from the tractor.
This invention is provided by a coupling which includes a generally cylindrical housing having a threaded bore at one end for connection to a tractor control valve or the like and a relatively movable inner body member, carrying locking balls which cooperate with the housing to secure or release the nipple. The coupler valve is supported by a conventional support member, movable relative to the inner body member and biased to the valve closed position. The support member is a pin supported for axial movement and having an inner end adjacent the inner end of the body member for cooperation with the flow-check stop mechanism.
The stop mechanism comprises a stop member supported on a radially disposed pin, in turn supported in radial cross bores in the inner body member and movable therein in a diametral direction by the camming action of a ramp surface in the adjacent housing bore. A spring is used to bias the stop member against one end of the support pin and thus the support pin against the housing bore so that the stop member is moved by camming engagement with the housing into or out of the path of movement of the support pin for the coupler valve. The relative movement between the body member and housing is controlled by a detent which provides a releasable grip on the inner body member in two positions. This detent is overcome by outward axial force to move the body member to an outer position to automatically disengage the locking balls for release of the nipple.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a view in cross section of the coupler valve of the invention with a nipple partially inserted therein and the coupler valve in an open position.
FIG. 2 is a cross sectional view of the coupler valve of the invention with nipple inserted therein and with body member shifted to the full inward position.
FIG. 3 is a cross sectional view of the coupler valve of the invention with nipple inserted therein with the coupler and nipple valves returned to the full open positions.
FIG. 4 is a cross sectional view of the coupler valve of the invention showing the coupler valve in the closed position.
FIG. 5 is an enlarged cross sectional view of the stop member in the coupler valve of the invention.
FIG. 6 is an enlarged bottom view of the stop member of the invention.
DETAILED DESCRIPTION OF THE INVENTION
Referring now to the drawings, there is shown in several views the different stages of the coupling action of the coupler valve 10 of the invention. Coupler valve 10 comprises outer cylindrical housing 11 and inner cylindrical body member 12, axially slidable relative to housing 11 and having a bore adapted for receipt of nipple 14. Nipple 14 is typically connected to some form of agricultural implement or the like by means of a flexible hydraulic fluid line and is the termination for coupling to the coupler valve 10. In turn, the housing 11 of coupler valve 10 comprises a two part housing with the inner housing having a threaded bore 15 at one end which is adapted for connection directly to a control valve or to rigid conduit on a tractor. Bore 15 leads into a larger recessed bore 16, an intermediate taper section 18 and a smaller bore 19. The axially outer part of housing 11 includes a multi stepped bore 20 for receipt of body member 12.
Body member 12 in turn is a two part member threaded together for common movement by threads 21 and is adapted for axial sliding movement relative to housing 11 in housing bore 20. Various chambers are created between housing 11 and body member 12 by means of the multi-stepped configurations of the outer surface of body member 12 and the inner surface of bore 20 of housing 11 and which are sealed by o-ring seals 22. These provide equal volume chambers such that upon axial movement of body member 20, no differential in fluid displacement occurs and no differential fluid forces are developed. For a further description of the particulars of this type of coupler valve 10, reference is made to U.S. patent application Serial No. 450,890 issued to the same assignee and describing a similar breakaway fluid coupler valve having relatively movable inner and outer housing and body members.
Body member 12, while supported for axial sliding movement in housing 11, is retained in an inner or outer position with respect thereto by means of a detent device consisting of snap ring 24 secured in a groove in body member 12 and cooperating with inner and outer grooves 25, 26 in housing 11. Grooves 25, 26 are axially adjacent one another, but are spaced a distance to provide sufficient movement of body member 12 with respect to housing 11 to achieve locking engagement with nipple 14, and operation of the valves therein. Body member 12 is shown in its outer position with snap ring 24 in outer groove 26 and is readily movable to groove 25 by means of sufficient force axially applied to the outer end of body member 12 to cause compression of snap ring 24 and its shifting from groove to groove. Likewise, a similar operation obtains upon outwardly directed axial force upon body member 12 which as will be described in greater detail hereinafter provides the breakaway feature of the coupling valve 10.
Nipple 14 is a conventional quick connect type nipple comprising a cylindrical nose portion 28 having a bore therein with a spring loaded nipple valve 30 biased to a closed position against a nipple valve seat therein. Nipple 14 further includes groove 32 on the outer periphery thereof adjacent nose portion 28 for locking purposes.
Locking means comprising a plurality of circularly disposed balls 34 are received in a plurality of radial slots in the outer portion of body member 12 and are cammed radially inwardly of the slots by engagement with the outer portion of housing 11 as body member 12 is moved inwardly of housing 11. As best seen in FIG. 2, balls 34 are then cammed inwardly into groove 32 of nipple valve 14 and secured by housing 11 in a manner well understood in the art. Collar 35 is provided outwardly of housing 11 and fixed to body member 12, providing a means for manually grasping body member 12 for movement between inner and outer positions thereof.
Coupler valve seat 40 is formed on the inner periphery of body member 12 and cooperates with coupler valve 41 which in this embodiment of the invention is a ball valve member for closing and opening the inner bore 44 of body member 12. A circular strut 45, open to fluid flow therethrough, is clamped in body member 12 between the inner and outer parts thereof adjacent threads 21 and includes an axial bore therein in which valve support pin 48 is received for axial sliding movement relative to body member 12. Support pin 48 includes cup 49 at its outer end for partially receiving ball valve 41 and is biased to an outward position by means of spring 50 acting between strut 45 and a flange on cup 49. Thus, valve 41 is typically urged against coupler valve seat 40 to a closed position as best seen in FIG. 4 in the absence of other influences and serves to close the inner bore of body member 12 against fluid flow therethrough. Valve spring 50 has a spring rate about twice as strong as the spring rate of nipple valve 30 such that in the absence of other influences, coupler valve 41 will urge nipple valve 30 to an open position, the latter being limited to a maximum open position by a mechanical stop therein (not shown). This full flow position of the coupler valve 10 is best depicted in FIG. 3, wherein it is noted that the outermost edge of coupler valve 41 is approximately adjacent the inner periphery of coupler valve seat 40, providing a relatively large open space thereabout for full flow through the valve seat 40.
The stop means for preventing flow-checking of coupler valve 41 consists of cylindrical stop pin 52, stop member 54 and spring 55, which cooperate with the inner end of valve support pin 48. Stop pin 52 includes an enlarged cylindrical head 56 at one end thereof and is received in opposed cross bores in body member 12 at the innermost end thereof, placing stop pin 52 in a radial disposition and in alignment with valve support pin 48. Stop member 54 is a disc better seen in enlarged detail in FIGS. 5 and 6, having central bore 58 extending through elongated hub 59 and slidably receiving stop pin 52. The hub 59 of stop member 54 is urged against enlarged head 56 of the stop pin by means of spring 55 surrounding pin 52 and located between the inner periphery of body member 12 and a recessed surface in the lower face of stop member 54. The upper face 60 of stop member 54 is flat and serves to engage the side of the innermost end of valve support pin 48 as best seen in FIG. 2, for retaining stop member 54 against the bias of spring 55 in a position out of the path of movement of valve support pin 48. Thus, it will be seen that stop member 54 is urged by spring 55 in an upward direction as viewed in the figures, together with stop pin 52 so that the enlarged head 56 of stop pin 52 engages larger bore 16, taper section 18 or smaller bore 19 of housing 11, unless restrained as indicated in FIG. 2 by the inner end of valve support pin 48. The head 56 of pin 52 is domed to facilitate movement from surface to surface and the camming action of pin 52.
When body member 12 is in its outermost position as depicted in FIG. 1, stop pin 52 is in engagement with smaller bore 19, placing stop member 54 out of the axial path of movement of valve support pin 48. In FIG. 3 body member 12 is in its innermost position with stop pin 52 in engagement with the larger bore 16 of housing 11 placing stop member 54 in the path of movement of valve support pin 48, thereby preventing further inward movement, or movement to the right, of the valve support pin 48 or coupler valve 41. As body member 12 is moved outwardly from its innermost position, the enlarged head 56 of stop pin 52 moves along taper surface 18 thereby compressing spring 55 and allowing stop pin 52 to be received in smaller bore 19 in the position depicted in FIG. 1.
DESCRIPTION OF OPERATION
Referring now to FIG. 1, the initial stage of the coupling of nipple 14 to coupler valve 10 is depicted with the nose 28 of nipple 14 in engagement with a fluid seal 62 located in a groove in the outer portion of body member 12. Nipple valve 30 is pressurized and held in its outermost position as depicted in the usual condition of operation, thereby forcing coupler valve 41 from its valve seat 40 to the position shown, moving also therewith valve support pin 48 against the bias of spring 50. In this condition of the coupler valve 10, body member 12 is in its outermost position with snap ring 24 disposed in outer groove 26 thereby also placing stop pin 52 in engagement with the smaller bore 19 of housing 11, with stop member 54 thus in a lower position and out of the path of movement of valve support pin 48.
Continued inward insertion of nipple 14 is depicted in FIG. 2, wherein locking balls 34 begin to engage groove 32 thereby initiating inward movement of body member 12 against the resistance of snap ring 24. With such inner movement to the position depicted in FIG. 2, the inner end of valve support pin 48 passes over the upper surface 60 of stop member 54 thereby preventing further radial movement of stop member 54 or stop pin 52. At the end position depicted, locking balls 34 are fully received in grooves 32 and secured by housing 11, with body member 12 moved to the position wherein snap ring 24 is engaged in inner groove 25. As noted, since body member 12 is in its innermost position, stop pin 52 has been moved to the location of the larger bore 16 in housing 11 but is prevented from engagement therewith by the engagement of stop member 54 with the inner end of valve support pin 48. As pressure is equalized in coupler valve 10, when the flow control valve (not shown) on the tractor, for example, coupled to inlet bore 15 is opened, nipple valve 30 is mechanically urged only by coupler valve 41 and since coupler valve spring 50 is of a greater spring rate, it moves nipple valve 30 and coupler valve 41 to the full open position depicted in FIG. 3. Upon such movement of coupler valve 41 to the left as viewed in FIG. 3, valve support pin 48 is moved therewith under urging of spring 50 so that the inner end thereof is disengaged from the upper surface 60 of stop pin 52 allowing stop member 54 to be moved upwardly under the urging of spring 55 to a position adjacent the end of valve support pin 48, or in the path of return movement thereof. During such movement stop pin 52 is moved to a position where the enlarged head 56 thereof is in engagement with the larger bore 16 of housing 11. By this arrangement stop member 54 is positioned to block any movement of valve pin 48 back into the coupler to provide a positive means to prevent flow-checking.
In the event a nipple 14 is presented to coupler valve 10, which nipple is not under pressure when connected, the internal arrangement of coupler valve 10 will be as depicted in FIG. 3 wherein both coupler valve 41 and nipple valve 30 are open and stop member 54 is in a position to prevent flow-checking. Stop member 54 has moved to the position of the larger bore 16 of housing 11 by inward movement together with body member 12, but since coupler valve 41 has not been retracted inwardly together with valve support pin 48, stop member 54 and stop pin 52 are free to move radially under the urging of spring 55 to the position depicted in FIG. 3.
FIG. 4 is a depiction of the disconnected position of coupler valve 10 wherein nipple 14 has moved body member 12 through the interengagement between the locking balls 34 and against the bias of detent snap ring 24 to the position where the snap ring 24 is engaged in the outermost groove 26. Stop pin 52 is carried with body member 12 against the taper section 18 into the smaller bore 19 of housing 11, forcing stop member 54 downwardly against spring 55 so that the upper surface 60 of stop member 54 is out of the path of movement of valve support pin 48, in preparation for receipt of nipple 14 as described with respect to FIG. 1. There is no need to provide alignment means between stop member 54 and stop pin 52 as the stop member is symmetrical and may be oriented in any position on stop pin 52.
Stop member 54 is shown in the form of a disc which requires no specific orientation on pin 52, but other devices could be used as well which, for example, might have a bore to receive the inner end of valve support pin 48. A device such as this, however, would have to be appropriately keyed so that the bore thereof is always presented to support pin 48. | A rigid mount, breakaway, quick coupler for fluid interconnection includes a spring-activated mechanical stop therein to prevent flow-checking. The flow check stop is supported in a cross bore in a movable inner body member of the coupler and cooperates with a ramp surface for positioning thereof in aligned or laterally displaced positions from the axially movable, flow-checking valve pin, thereby respectively to prevent or allow valve pin movement. | 8 |
FIELD OF THE INVENTION
[0001] The present claimed invention relates generally to the field of computer operating systems. More particularly, embodiments of the present claimed invention relate to a system for subscribing and publishing kernel level events to user level applications.
BACKGROUND ART
[0002] A computer system can be generally divided into four components: the hardware, the operating system, the application programs and the users. The hardware (e.g., central processing unit (CPU), memory and input/output (I/O) devices) provides the basic computing resources. The application programs (e.g.,database systems, games business programs (database systems, etc.) define the ways in which these resources are used to solve computing problems. The operating system controls and coordinates the use of the hardware resources among the various application programs for the various users. In doing so, one goal of the operating system is to make the computer system convenient to use. A secondary goal is to use the hardware in an efficient manner.
[0003] The Unix operating system is one example of an operating system that is currently used by many enterprise computer systems. Unix was designed to be a time-sharing system, with a hierarchical file system, which supported multiple processes. A process is the execution of a program and consists of a pattern of bytes that the CPU interprets as machine instructions (text), data and stack. A stack defines a set of hardware registers or a reserved amount of main memory that is used for arithmetic calculations.
[0004] The Unix operating system consists of two separable parts: the “kernel” and the “system programs.” Systems programs consist of system libraries, compilers, interpreters, shells and other such programs that provide useful functions to the user. The kernel is the central controlling program that provides basic system facilities. The Unix kernel creates and manages processes, provides functions to access file-systems, and supplies communications facilities.
[0005] The Unix kernel is the only part of Unix that a user cannot replace. The kernel also provides the file system, CPU scheduling, memory management and other operating-system functions by responding to “system-calls.” Conceptually, the kernel is situated between the hardware and the users. System calls are the used by the programmer to communicate with the kernel to extract computer resource information. The robustness of the Unix kernel allows system hardware and software to be dynamically configured to the operating system while applications programs are actively functional without having to shut-down the underlying computer system.
[0006] Thus, when system hardware or software resource changes are implemented in a computer system having the Unix operating system, the kernel is typically configured or reconfigured to recognize the changes. These changes are then made available to user applications in the computer system. Furthermore, as system errors and faults occur in the underlying operating system, the kernel is able to identify these errors and faults and make them available to applications that these error and faults may affect. Applications typically make system calls by way of “system traps” to specific locations in the computer hardware (sometimes called an “interrupt” location or vector) to collect information on these system errors. Specific parameters are passed to the kernel on the stack and the kernel returns with a code in specific registers indicating whether the action required by the system call was successfully completed or not.
[0007] [0007]FIG. 1 is a block diagram illustration of an exemplary prior art computer system 100 . The computer system 100 is connected to an external storage device 180 and to an external drive device 120 through which computer programs can be loaded into computer system 100 . The external storage device 180 and external drive 120 are connected to the computer system 100 through respective bus lines. The computer system 100 further includes main memory 130 and processor 110 . The drive 120 can be a computer program product reader such a floppy disk drive, an optical scanner, a CD-ROM device, etc.
[0008] [0008]FIG. 1 additionally shows memory 130 including a kernel level memory 140 . Memory 130 can be virtual memory which is mapped onto physical memory including RAM or a hard drive, for example. During process execution, a programmer programs data structures in the memory at the kernel level memory 140 . User applications 160 A and 160 B are coupled to the computer system 100 to utilize the kernel memory 140 and other system resources in the computer system 100 . In the computer system 100 shown in FIG. 1, when kernel events occur, each of the applications 160 A and 160 B have to independently perform poll or query operations to become aware of these events. Furthermore, each application has to initiate system calls to the kernel 140 to extract information on a particular event.
[0009] This typically results in the applications blocking or waiting for the kernel 140 to extract event information. Having the applications 160 A and 160 B independently issue system calls to the kernel to extract kernel event information further requires the applications to always preempt the kernel to extract event information. This can be inefficient, time consuming and costly. It may also require the applications to terminate or suspend other processes while preempting the kernel to extract kernel event information.
SUMMARY OF INVENTION
[0010] Accordingly, to take advantage of the many legacy application programs available and the increasing number of new applications being developed, a system is needed that allows a programmer to add extensions to a kernel to publish the occurrence of kernel level events to user level applications data without disrupting the functionality of the kernel for other operations. Further, a need exists to use existing legacy programs without having to recompile the underlying kernel in the operating system each time a new event is published from the kernel. A need further exists for an improved and less costly program independent operating system, which improves efficiency, reliability and provides a means to compile programs without losing the embedded features designed in these programs. A need further exists to reliably publish kernel level events to application programs and transparently filter events for other programs that have no need for these events.
[0011] What is described herein is a computer system having a kernel structure that provides a technique for monitoring and publishing kernel level events to user level applications by an asynchronous notification mechanism without having to recompile the kernel modules that publish the events. Embodiments of the present invention allow programmers to add system level loadable modules to existing kernel modules and provide a mechanism to extract and publish events to the user level applications without having user applications clogging the kernel with event query or poll requests. Embodiments of the present invention allow a system event framework in the kernel to publish the occurrences of hardware and software changes to specific user applications in a computer system. These kernel events may also include kernel errors and faults. Events detected by the kernel system event framework are asynchronously published to the user applications as they occur to avoid interruption of other operations of these applications.
[0012] The system event framework further provides users with a number of semantics that allow user level applications to subscribe to specific events in the kernel. The system event framework of the present invention further allows the non-interfering additions to a single entity without the need for pre-existing code to change.
[0013] Embodiments of the present invention further include kernel event publication logic that identifies kernel level events based on categories submitted by kernel subsystems and publishes these events as they occur to the specific applications. In one embodiment of the present invention, the kernel event publisher allows users to dynamically add to existing event characteristics based on unique identifiers to each event that an application wishes to subscribe.
[0014] Embodiments of the present invention also include event data system queues that dynamically queue the kernel events being monitored as they occur. The system event queues enable the kernel to buffer the system event data prior to dispatching the data to user level applications. The event data comprises a class and sub-class definition of the event. The event data also includes identification information that uniquely identifies each event for a particular application.
[0015] Embodiments of the present invention further include event data loadable modules that are implemented as intermediaries between the user applications subscribing to the kernel events and the kernel. The system event loadable modules receive all events published by the kernel and asynchronously distribute the events to the applications based on the class and unique identifier information. The system event loadable modules may be dynamically added to the system event framework dispatching daemon of the present invention without the need to recompile the underlying framework or event consumers or producers. The system event loadable modules also include acknowledgement logic that is triggered by each application when an event is received by the application to indicate receipt of the event. This allows the kernel to flush the system event queue of pending events after the events have been delivered. Further, system event loadable modules allow new features to be added to the base framework without recompilation of framework entities, a reboot of the operating system or restarting the system event daemon.
[0016] Embodiments of the present invention further include a system event daemon that accepts delivery of the kernel events and dispatches the events to the appropriate system event loadable module. The system event daemon monitors the system event loadable modules to ensure that events queued by the kernel are delivered to the appropriate applications. The system daemon further ensures that when event delivery is completed to the applications, the kernel is notified to flush the kernel event queues.
[0017] Embodiments of the present invention further include event subscription logic that allows user applications to subscribe to certain kernel events. The kernel event subscription logic is based on the event class and sub-class types. The event subscription logic establishes a connection between the system event daemon and the user application to create a connection path to deliver kernel event data to the applications. The event subscription logic also manages subscribers on behalf of the system event daemon and filters the kernel event buffers for each event subscriber in order to free kernel entries.
[0018] Embodiments of the present invention further include a system event configuration file registration feature that provides event information that is used by the present invention to determine when an application or script should be launched or invoked in response to a specific event. The system event configuration file feature is implemented as a loadable module to the system event framework daemon. As such, changes to the configuration file features may be made independent of the daemon and the base system event framework.
[0019] Embodiments of the present invention further include a device driver interface module that enables the addition of device drivers to enable individual user applications to independently publish a kernel level events. The device driver interface module further minimizes the number of interfaces a driver must use to log a system event.
[0020] These and other objects and advantages of the present invention will no doubt become obvious to those of ordinary skill in the art after having read the following detailed description of the preferred embodiments which are illustrated in the various drawing figures.
BRIEF DESCRIPTION OF THE DRAWINGS
[0021] The accompanying drawings, which are incorporated in and form a part of this specification, illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention:
[0022] [0022]FIG. 1 is a block diagram of a prior art computer system;
[0023] [0023]FIG. 2 is a block diagram of a computer system in accordance with an embodiment of the present invention;
[0024] [0024]FIG. 3 is a block diagram of an embodiment of the kernel event monitoring framework system of the present invention;
[0025] [0025]FIG. 4 is a block diagram of one embodiment of an internal architecture of a system event daemon of one embodiment of the kernel event monitoring framework of the present invention;
[0026] [0026]FIG. 5 is a block diagram of one embodiment of a system event flow of the kernel event monitoring framework of the present invention;
[0027] [0027]FIG. 6 is a block diagram of another embodiment of the system event flow of the kernel event monitoring framework of the present invention;
[0028] [0028]FIG. 7 is a block diagram of one embodiment a public registration interface for user applications to the kernel event monitoring framework of the present invention; and
[0029] [0029]FIG. 8 is a flow diagram illustration of one embodiment of an event subscription and publication of the kernel event monitoring framework of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0030] Reference will now be made in detail to the preferred embodiments of the invention, examples of which are illustrated in the accompanying drawings. While the invention will be described in conjunction with the preferred embodiments, it will be understood that they are not intended to limit the invention to these embodiments.
[0031] On the contrary, the invention is intended to cover alternatives, modifications and equivalents, which may be included within the spirit and scope of the invention as defined by the appended claims. Furthermore, in the following detailed description of the present invention, numerous specific details are set forth in order to provide a thorough understanding of the present invention. However, it will be obvious to one of ordinary skill in the art that the present invention may be practiced without these specific details. In other instances, well-known methods, procedures, components, and circuits have not been described in detail as not to unnecessarily obscure aspects of the present invention.
[0032] The embodiments of the invention are directed to a system, an architecture, subsystem and method to monitor kernel level events and to publish the occurrence of those events to subscribing user level applications. In accordance with an aspect of the invention, a kernel level event data monitoring system provides user applications the ability to dynamically receive notification of kernel events as they occur for particular applications transparently to the underlying operating system and the other applications running in the computer system.
[0033] [0033]FIG. 2 is a block diagram illustration of one embodiment of a computer system 200 of the present invention. The computer system 200 according to the present invention is connected to an external storage device 280 and to an external drive device 220 through which computer programs according to the present invention can be loaded into computer system 200 . External storage device 280 and external drive 220 are connected to the computer system 200 through respective bus lines. Computer system 200 further includes main memory 230 and processor 210 . Drive 220 can be a computer program product reader such a floppy disk drive, an optical scanner, a CD-ROM device, etc.
[0034] [0034]FIG. 2 shows memory 230 including a kernel level memory 240 . Memory 230 can be virtual memory which is mapped onto physical memory including RAM or a hard drive, for example, without limitation. During process execution, a programmer programs data structures in the memory at the kernel level memory 240 . According an embodiment of the present invention, the kernel memory level includes a kernel level system event framework system (KLFS) 250 . The KLFS 250 enables a programmer to subscribe to and monitor kernel level events for particular user level applications 260 that the programmer is implementing and the KLFS 250 dynamically notifies the intended applications 260 of the occurrence of such events. The notification of the subscribed events as they occur are non-interfering to other applications that may be running on the user's computer system.
[0035] The KLSF 250 comprises application interfaces for kernel level publication and applications interfaces for user level notification of events occurring in the kernel 240 . The KLFS 250 provides a standardized event buffer and payload (e.g., data) that is delivered to the subscribing user applications. The KLFS 250 further comprises libraries to extract event data from the event buffers and a daemon that dispatches the events to the user level applications.
[0036] [0036]FIG. 3 is a block diagram illustration of one embodiment of the kernel level system event monitoring framework system (KLFS) 250 of the present invention. The KLFS 250 comprises standardized event data module 300 , application interface (API) library module 310 , kernel publication module 320 , system event loadable (SLM) module 330 and system daemon module 340 .
[0037] The standardized event data module 300 provides event handles to particular system event objects. The system event types may include a class of related event conditions or a subclass of particular conditions with a class. The event data module also provides a set of unique event identifiers that provides high resolution timestamp and sequencing numbers to uniquely identify events as they occur in the kernel 240 .
[0038] The event data module 300 further provides a set of publisher identifiers that uniquely identifies each kernel event subscriber. The publisher identifiers differentiate the same event type generated from different sources or publishers. In one embodiment of the present invention, the event data module 300 further generates a set of unique data attributes that comprise a set of name-value pairs that further describe the event conditions as they occur in the kernel 240 .
[0039] The kernel event publication module 320 publishes the events as they occur in the kernel 240 . In one embodiment of the present invention, each event contains a number of buffers with a set of header information. The header information is typically filled in by the KLFM 250 , except the class and sub-class information. The event buffer also contains a publisher identifier which allows the KLFS 250 to differentiate the same event from different sources. The kernel event publisher 320 also provides the data payload containing specific data that a specific publisher requires.
[0040] The kernel event publication module 320 is preferably a set of routines that serve as the building blocks to the kernel's subsystem specific modules, such as the device driver interface (DDI). The kernel event publication module 320 also allocates memory for each event handle provided along with each subscription request to the KLFS 250 . The kernel event publication module 320 further frees memory associated with each event handle, e.g., freeing of header and any attribute data.
[0041] In one embodiment of the present invention, the event publication module 320 also adds new attributes (name-value pair) to any system event attribute list that is created by the KLFS 250 by creating the list if the data will be the first attribute element on the list. The event publication module 320 also attaches attribute data to a previously allocated event object and similarly detaches attribute data from event objects.
[0042] Still referring to FIG. 3, the system event loadable module (SLM) 330 acts as an intermediary between the user applications programs 260 making event subscriptions and the kernel 240 . The SLM 330 receives all events as they occur in the kernel 240 and passes the events on to the requesting applications 260 . In one embodiment of the present invention, the kernel level events are buffered and queued for presentation to the SLM 330 .
[0043] The SLM 330 further provides a mechanism to allow the programmer (user) to add special features to the system event daemon on the user's computer. The SLM 330 primarily acts based on the event type being monitored in the kernel and subscribed by the applications program. Event buffers generated by the kernel 240 are filtered and passed by the SLM 300 to other applications in the computer system 200 as needed.
[0044] The SLM 330 also provides the KLFS 250 a level of reliability to deliver kernel events to the subscribing applications. In one embodiment of the present invention, the SLM 330 communicates with the overlying applications 260 in a one-to-one relationship to ensure that events generated for a particular application are not mistakenly delivered to another application. The SLM 330 includes acknowledgement logic that acknowledges receipt of buffered event designated to the SLM 330 . The acknowledgement logic enables the KLFS 250 to release buffered events or retry delivery.
[0045] The system daemon module 340 typically resides on the user's computer system and communicates to the KLFS 250 via an interface. The system daemon module 340 primarily communicates with the kernel 240 with the SLM 330 acting as clients of the system daemon 340 . The system daemon module 340 accepts delivery of system event objects from the kernel 240 and through a dispatching thread temporarily places the buffered events data on each SLM 330 client queue.
[0046] Once an event delivery is made to the SLM 330 , the buffer is removed based on the acknowledgement receipt sent by the SLM 330 to the system event daemon 340 . There are several reasons for the SLM 330 to acknowledge receipt of an event delivery. One is to ensure that the event data buffers are not freed from the kernel 240 until the SLM 330 confirms it has received the event. Another is to allow the SLM 330 to request that delivery be retried if it is not able to process the event data immediately. In one embodiment of the present invention, the system event daemon dispatches the event data in a multi-threaded process to each respective SLM 330 .
[0047] Reference is now made to FIG. 4 which is a block diagram illustration of one embodiment of the system event daemon 340 of the present invention. As depicted in FIG. 4, the system event daemon 340 comprises signal handling thread module 400 , dispatch buffers 410 , kernel door server thread 420 , dispatch thread 430 , delivery thread 440 and event completion thread 450 .
[0048] The signal handling thread 400 receives signal handles from the applications 260 and coordinates draining of the SLM 330 queue as the data in the queues of the dispatch buffers 410 are delivered to the SLM 330 . Upon delivery of the queued buffered data, the signal handling thread 400 sends a completion signal to the kernel 240 to indicate completion of all event data delivery. This causes all outstanding event data deliveries to be flushed from the system event daemon 340 . The signal handling thread 400 then revokes the kernel door 420 . The signal thread 400 also waits for signals, e.g., HUP, INT, STOP and TERM to gracefully shut down the system event daemon. In one embodiment of the present invention, if the HUP signal is presented to the signal thread 400 , the SLMs 330 are unloaded and then reloaded.
[0049] The kernel door server thread 420 handles door up-calls from the kernel and copies event objects into a waiting buffer in the dispatch buffers 410 . If the buffer 410 is unavailable, the kernel door server thread 420 returns a “not-available” signal. The kernel doors 420 typically are a mechanism by which the kernel 240 communicates with user level processes such as the system event daemon 340 .
[0050] The dispatch thread 430 provides a mechanism through which the event buffers 410 are dispatched to each client (e.g., SLMs 330 ). These dispatches are accomplished by placing the buffers on a per-client event queue. Once an event buffer has been dispatched to all clients, a completion package is placed on the completion queue 450 . The completion package contains the event identifier and the client reference count.
[0051] The event delivery thread 440 delivers the event data to each client subscribing to the event. Each client delivery thread extracts the next event buffer on its queue and calls the appropriate SLM 330 delivery routine to implement delivery of the event data. After a successful return from the SLM 330 , the buffer is removed from the buffer queue 410 and an event completion is signaled to the event completion thread 450 for the particular client.
[0052] Once all clients have signaled completion of processing a particular event buffer 410 , the event is released from the kernel by the event completion thread 450 .
[0053] [0053]FIG. 5 is a data flow diagram of one embodiment 500 of the flow of data in the kernel system event framework 250 of the present invention. As shown in FIG. 5, events generated by the kernel 240 are published by the event publisher 320 to the subscribing applications 530 . Each event is stored in an event buffer with associated payload (data). The event buffer is first allocated and initialized with event specific data provided by the kernel event publisher 320 and system specific identification (e.g., timestamp and sequencer). The event buffer is subsequently queued in the system event queue 520 for delivery to the system daemon 340 . Each event buffer includes a set of header information. The header information is typically filled in by the system event framework 250 , except the class and sub-class information.
[0054] Each system event buffer includes an event type, which comprises a class and a sub-class. An event class typically defines a set of related event conditions and the sub-class defines a particular condition within the class. The event buffers also include a unique event identifier that is unique to each event buffer in the system queue 520 . In one embodiment of the present invention, the event identifier comprises a high resolution time stamp and a sequence number for each event. An exemplary event may be defined as follows:
[0055] event header
[0056] class
[0057] subclass
[0058] timestamp
[0059] sequencer
[0060] vendor
[0061] publisher
[0062] self-describing event* class-specific data (e.g., name-value pairs).
[0063] where:
[0064] class is the class of the event;
[0065] sub-class is the sub-class of the event;
[0066] vendor is the name of the vendor defining the event, for example the stock symbol of the vendor;
[0067] publisher is the name of the application, driver or system module producing the event;
[0068] timestamp is a high resolution time assigned at event buffer initialization time;
[0069] sequencer is a monotonically increasing value assigned at initialization time.
[0070] Events from the system event queue 520 are extracted by the system daemon 340 . The daemon 340 retrieves from the system event queue 520 the event buffers and through a dispatching thread places the buffers in each respective client's (applications 530 ) queue for delivery. Each of the applications 530 has an event buffer queue that stores events generated by the kernel 240 .
[0071] Once delivery is made to each of the modules 1 - 3 , the buffer is removed from the daemon's event completion thread. In one embodiment of the present invention, the event buffers are not removed from the daemon's event completion thread until each of modules 1 - 3 confirms receipt of the event. Confirmation of the receipt of events ensures the reliable delivery of events to the SLMs 330 .
[0072] [0072]FIG. 6 is a data flow diagram of another embodiment 600 of event data flow in the present invention. In the embodiment disclosed in FIG. 6, a configuration file 610 , a configuration file daemon 620 and a sys event post file 630 are added to the kernel system event framework 250 . Based on the contents of the configuration file 610 , an application is launched or invoked in response to a particular event.
[0073] The configuration file 610 provides class, sub-class, publisher and arbitrary attribute data that is used to indicate when an application should be launched. For example, if a user wishes to subscribe to event information for when a printer is either configured or de-configured to the system, the configuration file 610 is configured with the printer name, etc. The printer detect logic in the kernel 240 is invoked to configure the printer information in the kernel sub-systems and generate an event ( e.g., addition of a new printer) to all applications subscribing to be notified of the addition or deletion of printers from the kernel 240 .
[0074] An exemplary configuration file of one embodiment of the present invention is as follows:
“class; sub-class; vendor; publisher; reserved1; reserved2; path[arg1 arg2 . . . ]” For example: with an event described by: class event vendor pub user flag service [arg1 arg2 . . . ] ec_conf esc_dc QQQ qd - - /opt/QQQ/qd/bin/qdconfig -c ${device_name}
[0075] where:
[0076] class is the class of the event;
[0077] sub-class is the sub-class of the event;
[0078] vendor is the name of the vendor defining the event, for example the stock symbol of the vendor;
[0079] publisher is the name of the application, driver or system module producing the event;
[0080] timestamp is a high resolution time assigned at event buffer initialization time;
[0081] sequencer is a monotonically increasing value assigned at initialization time.
[0082] The sys event post API 630 allows user level applications to generate events similar to events generated by the kernel 240 . In the embodiment shown in FIG. 6, the system event framework 250 further includes a device driver system event interface 605 . A wrapper function logic in the system event post event file 630 enables the addition of a device driver interface (DDI) that allows device drivers to call the SLMs 330 to place events. The DDI interface calls specific driver interface conventions and returns DDI specific errors in case of a failure. In one embodiment of the present invention, the DDI interface minimizes the number of interfaces a driver must use to publish system events.
[0083] [0083]FIG. 7 is a block diagram illustration of one embodiment of system event subscription logic 700 of the present invention. The system event subscription logic 700 provides a mechanism for the system event framework to establish connections between the system event daemon and a subscribing application. A handle is created to hold the connection path and the subscribing application. The system event subscription logic 700 further provides the kernel system event framework 250 with a mechanism to free previously allocated system event handles generated by the system event daemon 340 after events have been delivered to the subscribing applications. The system event subscription logic 700 further includes a system event unsubscribe logic that allows the system event framework 250 to disable delivery of system event notifications to subsequent system events that occur in the kernel according to a system event type list. In one embodiment of the present invention, the system event type list may be used to subscribe to events of interest to the subscribing application.
[0084] The event subscription feature is implemented as a special purpose SLM 330 . User applications may engage in event subscription in the present invention through library interface 310 that establishes and maintains event subscription connection paths between the event subscription SLM and the subscribing application. The system event daemon 340 opens the libraries and delivers event buffers to the SLMs 330 and the SLM 330 in turn delivers the event buffers to the user application. The event buffers are asynchronously delivered to the user application via, for example, call back routines in which system programs deliver the event buffers to the user applications.
[0085] In the example shown in FIG. 7, events from the system event daemon 340 are passed to the event dispatcher 711 and queued for delivery in the system event queue module 712 . The queued events are then provided to the event delivery module 713 which delivers the events to the event subscriber SLM. The event subscriber SLM in-turn makes door calls to the door server 718 , 725 and 735 for each respective subscriber application 720 , 730 and 740 to make delivery of each respective system event buffer (A-C) to each respective application. Each of the event handles 719 , 727 and 738 establishes a connection between the system event daemon 340 and the subscribing application. The handle holds the connection path (e.g., file system name) and the calling applications' event delivery routine. After an event is delivered, the handles respectively close the connection between the system event daemon and the calling application and frees the system event daemon handles previously allocated.
[0086] [0086]FIG. 8 is an exemplary computer controlled flow diagram of one embodiment of event subscription and delivery of the present invention. As shown in FIG. 8, implementation of an event subscription and delivery is initiated by a computer system user application subscribing to the kernel system framework 250 event notification logic for particular events. At step 810 , the kernel system framework 250 allocates and initializes event buffers for the events being subscribed. At step 820 , the framework 250 queues the event buffers for delivery. After the event buffers have been queued, the framework 250 notifies the system event daemon 340 of the queued events.
[0087] At step 825 , the queued event buffers are extracted and dispatched at step 830 to the corresponding SLMs 330 . At step 835 , the event subscription SLM 330 checks for subscribing users or applications to the queued events. At step 840 , the subscribing SLM 330 determines whether the identified subscribers have subscribed to a particular event type.
[0088] If the identified subscribers have subscribed to the specific event type determined by the subscribing SLM 330 , the framework 250 opens connection to the particular application for event delivery at step 845 .
[0089] At step 850 , the framework 250 checks to determine whether a queued event buffer has been successfully delivered to the subscribing application. If the event has been successfully delivered, the framework 250 returns success at step 855 to the dispatching SLM 330 and continues delivery of other events in the queue buffer. If an event is unsuccessfully delivered, a return retry is signaled to the dispatching SLM 300 at step 860 .
[0090] At step 865 , the framework 250 performs a second check to determine whether an event buffer has been delivered. If during this check the event buffer has been delivered, the event buffer is freed at step 870 and processing ends at step 880 . If, on the other hand, the event buffer has not been delivered, the framework 250 performs a delivery retry at step 875 , to re-deliver the event buffer.
[0091] In a typical operation of one embodiment of the KLFS 250 , the event publisher 310 calls the system event allocation and initialization module 510 . The system event allocation and initialization module 510 has the event data which includes the class, sub-class, publisher identifier and attribute data. The KLFS 250 then places the event data into a single buffer for each event. The system daemon 340 in communicating with the kernel 240 extracts the event buffers stored in the system event log 320 and dispatches the event data to the SLMs 330 which subsequently place the event buffers in each subscribing applications individual event buffers. For example, if there is a fault condition in the kernel 240 as a result of a device driver receiving many time-outs at its ports. The kernel 240 will call the system event log 320 to log the particular condition. The KLFS 250 will then compose the fault event class as, for example, “an ec_fault”; a sub-class will be defined as “time-outs” and the KLFS 250 will fill the unique identifier for the event and the event publisher will further publish the event in terms of the attribute data.
[0092] In this example, the attribute data will be defined as a set of name-pair value (e.g., time-out with an intrinsic value specifying the time-out limit). Applications subscribing to this event will extract the event data and notice the time-out limit (e.g., 3 ) and will be able to dynamically adjust processing to the specific device driver when the time-out is over.
[0093] The foregoing descriptions of specific embodiments of the present invention have been presented for purposes of illustration and description. They are not intended to be exhaustive or to limit the invention to the precise forms disclosed, and obviously many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and its practical application, to thereby enable others skilled in the art to best utilize the invention and various embodiments with various modifications are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims appended hereto and their equivalents. | An event subscription and publication system for dynamically notifying user level applications of kernel level events. The kernel level events may include hardware and software events as well as system level errors that occur in the kernel. User level applications that need information on these kernel level events subscribe to the event monitoring and publication framework of the present invention and are notified of these kernel level events when they occur. Upon notification of an event, the user application also is provided with specific information classifying the nature and details of the event. The kernel event monitoring and publication system of the present invention allows user level applications to be dynamically notified of kernel level events without requiring the user level application to interrupt the normal processing states to identify these events when the events occur. | 6 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims the benefit under 35 U.S.C. §371 of published PCT Patent Application Number PCT/EP 2011/061218, filed Jul. 4, 2011, claiming priority to French Patent Application Number FR1055779 filed on Jul. 16, 2010, and published as WO2012/007305 on Jan. 19, 2012, the entire contents of which is hereby incorporated by reference herein.
TECHNICAL FIELD OF INVENTION
[0002] The present invention relates to a head-up display device, in particular for motor vehicles, lorries, buses, trains, aircraft, etc. In particular, the invention relates to a head-up display device with a retractable combiner.
BACKGROUND OF INVENTION
[0003] A head-up display device typically includes a projection unit that produces a light beam intended to be directed towards a combiner in order to project images, in particular operating and driving information of a vehicle, in the form of a virtual image, in the field of view of a user, in particular a pilot or motor vehicle driver.
[0004] Designed originally for the display of information to pilots of combat aircraft, head-up display devices are increasingly used today in particular in the motor vehicle sector, more particularly in cars of medium and high range. Head-up display devices are reputed to contribute to road safety as they allow drivers to read the information without their eyes leaving the road in front of them. The virtual image containing the displayed information is moreover projected at a distance of a few meters in front of the driver, which allows him to read the information without modification of the accommodation of his eyes.
[0005] Head-up display devices exist which use a part of the windscreen as combiner, i.e. as the optical element which combines the light beam containing the information having to be presented to the user with the light coming from the environment. Other head-up display devices include a combiner independent of the windscreen. Such a combiner comprises a strip having the necessary optical properties to deviate at least a substantial part of the beam coming from the projection unit towards the user, while being sufficiently transparent to allow passage at the same time of a substantial part of the ambient light coming from the environment.
[0006] It has proved desirable to be able to protect the optical elements of the head-up display device, for example against dust and other detrimental influences, risking deterioration of the projection quality.
[0007] Another problem is the adjustment of the head-up display device to the needs of the driver. In particular, because the angle of view (the angle relative to the nominal direction up to which the image can be viewed with sufficient contrast) of a head-up display device is typically fairly small and the position of the eyes of the user can vary greatly from one user to the other, the head-up display device should be provided with means allowing the user to adjust the direction in which the beam carrying the information to be displayed at the height of his eyes is returned.
[0008] U.S. Pat. No. 5,394,203 describes a head-up display device comprising a combiner in the form of a reflective strip mounted tilting and acting as a lid that is closed when the device is not in use. However, given that the strip acts as a lid, one of its sides remains exposed to the detrimental influences.
[0009] Application WO 2007/057608 presents a head-up display device with a retractable combiner. The combiner is mounted on a movable support so as to be able to be displaced between a display position, in which the combiner is upright facing the driver, and a storage position, in which the combiner is returned back into the case which protects all of the optical and mechanical components of the head-up display device. The limit of travel of the movable support carrying the combiner can be adjusted to obtain adjustment of the angle of slope of the combiner and thus the angle of slope of the axis going from the eyes of the driver to the virtual image.
[0010] However, the head-up display device of application WO 2007/057608 does not allow adjustment of the distance at which the virtual image is displayed. Now the adjustment of the projection distance is very advantageous from the ergonomic point of view, as it allows the position of the virtual image to be suited relative to the mechanical architecture of the vehicle (in particular relative to the dimensions of the bonnet). Moreover, this type of adjustment allows the user to suit the display to his viewing conditions.
[0011] Document JP 10 333080 discloses a head-up display device with two deflection mirrors in the optical path between the projector and the combiner. The first of the two mirrors from the projector is mounted rotatable or displaceable in translation to be able to change the vertical position of the virtual image in the field of view of the user.
[0012] Document US 2005/0024490 describes a head-up display device, in which the last mirror, i.e. the one that is in the field of view of the user is retractable. In its storage position, the mirror forms the lid of the head-up display device. The rear face of this mirror (i.e. the upper face in the storage position) is provided with a foldable cover. This cover is deployed when the mirror is closed to give an appearance of quality to the device. The mirror can be formed as combiner; in this case, the cover is completely retracted when the mirror is in the display position.
[0013] Document U.S. Pat. No. 5,237,455 describes a head-up display device with a retractable combiner. The opening through which the combiner can be manually removed from and returned to the case is closable by a curtain. The opening and closing of this curtain is also performed manually.
SUMMARY OF THE INVENTION
[0014] A head-up display device comprises a projector to generate a light beam loaded with information to be displayed, a combiner having a display position to display the information in the field of view of a user and an optical system defining an optical path between the projector and the combiner when the latter is in its display position, to direct the light beam at the combiner. In accordance with the invention, the optical system comprises at least a first and a second deviation mirror in the optical path. The first mirror is arranged to receive the light beam from the projector and return it towards the second mirror, the latter being arranged to return the light beam on the optical path towards the combiner. The device also comprises an actuation system configured to adjust the length of the optical path between the projector and the combiner by positioning of the first and second deviation mirrors one relative to the other. By means of the arrangements of the invention, it is possible to adjust the distance at which the virtual image is situated from the combiner (projection distance).
[0015] The actuation system preferably comprises a mechanism coupled both to the first and to the second mirror. The mechanism could be manually driven by the user (e.g. by means of an adjustment lever connected to the mechanism). However, for more user comfort, the mechanism is preferably driven by an electric motor (e.g. a servomotor) which the user can control by means of a control button (e.g. on the dashboard).
[0016] In accordance with an advantageous embodiment of the invention, the second mirror is coupled to the mechanism so as to be displaceable in translation (preferably perpendicularly to its surface), and the first mirror is coupled to the mechanism to pivot by an angle determined as a function of the displacement of the second mirror. The angle of slope of the first mirror is in particular preferably given by a linear function of the displacement of the second mirror relative to a reference position. By this coupling of the first and second mirrors, it is ensured that the light beam arrives at the combiner whatever the position of the intermediate mirrors. In a way, by means of the first mirror, automatic aiming of the light beam at the second mirror and at the combiner is performed. On adjustment of the projection distance, the virtual image therefore remains substantially on the same axis passing through the eyes of the driver and the combiner.
[0017] The projector preferably comprises a spatial light modulator (in English: “spatial light modulator”), e.g. a holographic memory, in which the information to be displayed is stored in the form of holograms, or a backlit liquid crystal display. In this case, the projector advantageously comprises a backlighting light source (e.g. a laser source or one or more luminescent diodes) arranged to send through the liquid crystal display a light beam not yet loaded with the information to be displayed, and in which the liquid crystal display is mounted displaceable transversally to the direction of the light beam. In accordance with a first modification, the light beam can remain immobile when the spatial light modulator is displaced. In accordance with another modification, the projector is configured displaceable in translation in its entirety. It will be noted that the translation of the spatial light modulator transversally to the direction of the beam permits adjustment of the transversal position of the virtual image relative to the axis: eyes of the driver—combiner. The device preferably comprises a control lever mechanically coupled to the spatial light modulator, by means of which the user can adjust the transversal position of the virtual image. Alternatively, the spatial light modulator is displaceable by means of an electric motor (e.g. a servomotor) which the user can control by means of a button or a control knob. The button or the knob in this case transmit the adjustment instructions to the head-up display (e.g. via the communication network of the vehicle), which translates them into a mechanical movement. A modification of the invention in accordance with which the user can control the projection distance and the transversal position by a same button or control knob is considered as particularly ergonomic.
[0018] The combiner can be formed as a semi-reflective mirror (flat or curved) or diffractive combiner (i.e. a combiner that deviates the light towards the user by means of an optical diffraction grating, optionally integrating an enlargement of the virtual image and/or a luminance level control.) The combiner is advantageously made of a plastics material.
[0019] In accordance with a very advantageous embodiment of the invention, the combiner is formed as a retractable combiner having a storage position in addition to its display position. The combiner is then preferably connected to an articulated mechanism configured to displace the combiner between the display position and the storage position.
[0020] In accordance with this embodiment of the invention, the head-up display device preferably comprises a case in which are arranged the projector, the optical system and the combiner, the case being provided with a first opening, through which the combiner can pass on its displacement between the storage and display positions, and a second opening, through which the light beam can pass from the optical system towards the combiner.
[0021] Preferably, the case also comprises a closure curtain to close the first opening when the combiner is in its storage position.
[0022] It will be appreciated that the movement which the combiner performs on its passage from the storage position to the display position can be so designed that the combiner and/or the mechanism to which the combiner is connected forces (e.g. by pushing) the curtain out of the path of the combiner to open the passage through the first opening.
[0023] The case preferably comprises a trapdoor closing the second opening when the combiner is in its storage position. Still more advantageously, the trapdoor is provided with a housing space to receive the curtain when this is forced out of the path of the combiner.
[0024] The opening and closing mechanism of the trapdoor is advantageously coupled to the mechanism intended to displace the combiner between the display position and the storage position.
[0025] The head-up display device preferably comprises a return means, e.g. a return spring, arranged to accumulate mechanical energy when the curtain is forced out of the path of the combiner and to use this energy to return the curtain into a closure position of the first opening when the combiner passes from its display position to its storage position.
[0026] The man skilled in the art will note that the system for retraction of the combiner and/or closure of the trapdoor can be formed independently of the system for adjustment of the projection distance described above. However, these two aspects of the invention are combined in particularly advantageous manner in the embodiment described by way of illustration below.
BRIEF DESCRIPTION OF DRAWINGS
[0027] Other features and characteristics of the invention will become apparent from the detailed description of an advantageous embodiment presented below, by way of illustration, with reference to the attached drawings. These show:
[0028] FIG. 1 : a partial three-dimensional view of a head-up display device in accordance with a preferred embodiment of the invention;
[0029] FIG. 2 : a longitudinal section of the system for retraction of the combiner of the device of FIG. 1 , with the combiner in its storage position;
[0030] FIG. 3 : a longitudinal section of the system of FIG. 2 , the combiner being between its storage position and its display position;
[0031] FIG. 4 : a partial view of the system for opening and closing the curtain protecting the combiner in its storage position;
[0032] FIG. 5 : a partial view of the system of FIG. 4 , with the combiner in its display position;
[0033] FIG. 6 : a basic diagram of the system for adjustment of the position of the virtual image; and
[0034] FIG. 7 : a partial view of the mechanism of FIG. 6 .
DETAILED DESCRIPTION
[0035] FIG. 1 shows a perspective view of a head-up display device 10 for a motor vehicle, in accordance with a preferred embodiment of the invention. The device 10 comprises a system for retraction of the combiner, described in more detail with reference to FIGS. 2 to 5 , as well as a system for adjustment of the position of the virtual image, described in more detail below with reference to FIGS. 6 and 7 .
[0036] The device 10 firstly comprises a projector 12 to generate the light beam loaded with the image representing the information to be displayed to the driver of the vehicle. The projector 12 includes a liquid crystal display 14 , a light source 16 (coherent or non-coherent, depending on the type of the combiner, which can be diffractive or reflective producing a backlighting light beam and a mirror 18 returning the backlighting beam coming from the source 16 through the liquid crystal display 14 . The liquid crystal display functions as a spatial light modulator and produces the image that will be displayed to the driver. The optical path between the projector 12 and the display position of the combiner 20 is defined by an optical system. This comprises a first deviation mirror 22 and a second deviation mirror 24 . The first mirror 22 is arranged to receive the light beam from the projector 12 and return it towards the second mirror 24 , which is arranged to return the light beam to the combiner 20 , when this is in its display position (shown in FIG. 1 ).
[0037] The combiner 20 is retractable by means of a retraction system shown in more detail in FIGS. 2 to 5 . In addition to its display position, the combiner 20 has a storage position essentially flattened inside the case 25 of the head-up display device 10 . The combiner 20 is fixed to an articulated mechanism which displaces it between the display and storage positions. More precisely, the articulated mechanism comprises, on either side of the combiner 20 , a first connecting rod 26 and a second connecting rod 28 which are joined by an articulation 30 at one of their ends. The other end of the first connecting rod 26 is housed movable in rotation on a first bearing 32 displaceable in translation by an electric motor 34 , while the other end of the second connecting rod 28 is housed movable in rotation on a second bearing 36 fixed relative to the case 25 . The combiner 20 is attached to the first connecting rod 26 . To bring the combiner from its storage position (shown in FIG. 2 ) to its display position, the motor 34 turns a pinion 38 , which drives the displacement of the first bearing 32 on a rack 40 and therefore the shortening of the base of the triangle the vertices of which are formed by the bearings 32 and 36 and by the articulation 30 . As a result the combiner 20 rises progressively as the first and second bearings 32 , 36 approach each other. When the combiner 20 is completely upright, the motor 34 stops and locks the articulated mechanism in the bent position. Preferably, the limit of travel of the pinion 38 on the rack 40 is adjustable by the driver, who can thus adjust the slope of the combiner 20 in the display position.
[0038] The case 25 of the device 10 comprises a first opening, through which the combiner 20 passes on its displacement between the storage and display positions, and of a second opening, through which the light beam passes from the optical system towards the display position of the combiner 20 . A closure curtain 42 is provided to close the first opening and protect the combiner 20 against dust when the combiner 20 is in its storage position.
[0039] As shown in FIGS. 4 and 5 , the movement performed by the combiner 20 on its passage from the storage position to the display position is so designed that the combiner pushes the curtain 42 out of its path to open the passage through the first opening. When the combiner 20 pushes back the curtain 42 , this is displaced in slideways 44 provided on the side walls of the case 25 (see FIG. 1 ) and on the trapdoor 46 provided to close the second opening when the combiner is in its storage position. On the lower side of the trapdoor 46 , the grooves 48 define a housing receiving the curtain 42 when this is displaced out of the path of the combiner 20 . When the curtain 42 is displaced by the combiner 20 , it pushes against a fixing piece 50 , fixed to a return spring 52 that stretches and accumulates mechanical energy. In the display position of the combiner, the curtain 42 remains in abutment against the combiner 20 . The mechanical energy accumulated in the return spring 52 is used to return the curtain 42 into the closure position of the first opening when the motor 34 operates in the opposite direction and the combiner 20 passes from its display position to its storage position
[0040] To open and close the trapdoor 46 , the head-up display device comprises a trapdoor opening and closing mechanism coupled to the mechanism intended to displace the combiner 20 between the display position and the storage position. The mechanism for opening and closing the trapdoor comprises a spring 54 , a driving element 56 , slideways 58 and a pivoting element 60 attached to the trapdoor 46 . When the combiner 20 is in its storage position, the motor 34 and the bearing 32 abut against the driving element which is at its limit of travel and holds the trapdoor 46 closed by means of the pivoting element 60 . In this position, the spring 54 is compressed. When the motor 34 and the bearing 32 are displaced in the direction of the second bearing 36 following a command for turning on the head-up display device 10 , the spring 54 is decompressed and displaces the driving element 56 in the slideways 58 . This displacement turns the pivoting element 60 about its axis 62 and the trapdoor passes into the open position, thus permitting the passage of the light beam coming from the projector 12 .
[0041] The head-up display device 10 also includes a system for adjustment of the position of the virtual image ( FIGS. 6 and 7 ). The projection distance of the virtual image is adjustable by means of a system for actuation of the deviation mirrors 22 and 24 . The vertical position of the virtual image can moreover be adjusted by a system for translation of the liquid crystal display 14 .
[0042] The principal of the adjustment of the projection distance around a nominal distance is explained with reference to FIG. 6 . The image comprising the information to be displayed is generated by the projector 12 . The length p of the optical path between the projector and the combiner (in the display position) is given by
[0000] p=L 0 +L 1 +L 2 Eq. 1,
[0000] in which L 0 designates the distance between the projector and the mirror 22 (also M 1 in FIG. 6 ), L 1 the distance between the mirror 22 and the mirror 24 (also M 2 ), and L 2 the distance between the mirror 24 and the combiner 20 .
[0043] The distance of the virtual image from the combiner D iv can be approximated with sufficient accuracy by the product of the length of the optical path between the projector and the combiner p and the enlargement factor g of the combiner (Eq. 2).
[0044] To adjust the projection distance, the length of the optical path between the projector 12 and the combiner 20 can therefore be adjusted. In the device 10 , the length of the optical path p is adjusted by positioning of the first and second deviation mirrors 22 and 24 one relative to the other.
[0045] Two cases can be distinguished. When it is required to reduce the projection distance (relative to the nominal projection distance), the mirror 24 is displaced upwardly in FIG. 6 (perpendicularly to its surface) and the mirror 22 is simultaneously turned anticlockwise. When it is required to increase the projection distance (relative to the nominal projection distance) the mirror 24 is displaced downwardly in FIG. 6 (perpendicularly to its surface) and the mirror 22 is simultaneously turned clockwise.
[0046] In this way, the projection distance can be varied between a minimum value D iv — min and a maximum value D iv — max , defined respectively by Eq. 3 and Eq. 4
[0000] D iv — min =g ·( L 0 +L 1 min +L 2 min ) and Eq. 3
[0000] D iv — min =g ·( L 0 +L 1 max +L 2 max ) Eq. 4.
[0047] The extreme positions of the mirrors 22 and 24 are shown by broken lines in FIG. 6 .
[0048] The mirrors 22 and 24 are positioned by means of a mechanism coupled both to the first and to the second mirror (see FIG. 7 ). The mechanism is driven by an electric motor 64 which the user can control by means of a control button (e.g. on the dashboard).
[0049] The second mirror 24 is coupled to the mechanism so as to be displaceable in translation perpendicularly to its reflective surface. The first mirror 22 is coupled to the mechanism to pivot by an angle θ determined as a function of the displacement of the second mirror 24 . As shown in FIG. 7 , the mirror 24 is fixed on a movable support which can slide perpendicularly to the reflective surface of the mirror 24 . The mirror 24 is positioned by means of an electric motor 64 that drives a pinion 66 meshing in a rack 68 fixed on the movable support carrying the mirror 24 . When the motor 64 turns, it causes the simultaneous turning of the first mirror 22 , by means of a gear and belt mechanism 70 . The transmission ratios between the motor 64 and the second mirror 22 , on the one hand, and between the motor 64 and the mirror 22 , on the other, are so selected that automatic aiming is effected of the light beam at the second mirror 24 and at the combiner 20 and it is therefore ensured that the light beam arrives substantially at the same place on the combiner 20 whatever the position of the intermediate mirrors 22 and 24 . On adjustment of the projection distance, the driver does not therefore see the virtual image to be displaced vertically or laterally.
[0050] To position the virtual image vertically, the liquid crystal display 14 can be displaced transversally relative to the direction of the backlighting light beam coming from the light source 16 . ( FIG. 7 does not show the deviation mirror 18 between the light source 16 and the liquid crystal display 14 .) The displacement of the liquid crystal display 14 is effected by means of an electric motor 72 , which drives a pinion 74 , and rack 76 system. As the displacement of the liquid crystal display 14 is in a plane perpendicular to the light beam, there is no notable resulting variation in the projection distance of the virtual image.
[0051] The driver can therefore adjust the projection distance and the vertical position of the virtual image independently.
[0052] To control the different electric motors (which can be servomotors), the head-up display device 10 comprises a control unit (not shown in the figures) having one or more interfaces for interaction with the user (e.g. control buttons). In the example shown in the figures, the user can in particular adjust the slope of the combiner (determined by the limit of travel of the pinion 38 on the rack 40 ), which allows him to adjust the display to his height (or, more precisely, the height of his eyes); The projection distance (determined by the position of the mirrors 22 and 24 ); and the vertical position of the virtual image (determined by the position of the liquid crystal display 14 ).
[0053] It will be appreciated that the head-up display device 10 is in a compact, easily integrated form, while offering the facility of adjustment to the individual needs of the user.
[0054] While this invention has been described in terms of the preferred embodiments thereof, it is not intended to be so limited, but rather only to the extent set forth in the claims that follow.
KEY
[0000]
10 head-up display device
12 projector
14 liquid-crystal display
16 light source
18 mirror
20 combiner
22 first deviation mirror
24 second deviation mirror
25 case
26 first connecting rod
28 second connecting rod
30 articulation
32 first bearing
34 electric motor
36 second bearing
38 pinion
40 rack
42 closure curtain
44 slideway
46 trapdoor
48 groove
50 fixing piece
52 return spring
54 spring
56 driving element
58 slideway
60 pivoting element
62 pivoting axis
64 electric motor
66 pinion
68 rack | The invention relates to a head-up display device, including a projector for generating a light beam carrying information to be displayed, a combiner having a display position for displaying the information in the field of vision of a user, and an optical system defining an optical path between the projector and the combiner when the latter is in the display position thereof, for directing the light beam onto the combiner. The optical system includes a first and a second deflecting mirror. The first mirror is arranged for receiving the light beam from the projector and for sending said light beam to the second mirror, the latter being arranged for sending the light beam over the optical path toward the combiner. An actuation system is provided for adjusting the length of the optical path between the projector and the combiner by positioning the first and second deflecting mirrors. | 6 |
CROSS-REFERENCES TO RELATED APPLICATIONS
[0001] The present application claims priority to Japanese Patent Application No. 2003-368302, filed on Oct. 29, 2003.
BACKGROUND OF THE INVENTION
[0002] The present invention relates to placing restriction on the photographic function of a portable electronic device.
[0003] JP Unexamined Patent Pub. No. 1999-261674 discloses a photography-restricting system to automatically prohibit the photographic function of a portable device in prohibited modes in facilities where such a use of portable electric devices in specific modes is restricted. The photography-restricting system comprises a controller installed on a ceiling or the like in public facilities and a portable electric device comprising a portable telephone. The portable electric device has a plurality of operating modes. The controller comprises a signal-generating circuit, a transmission circuit, an antenna, etc., and transmits control signals periodically in the public facilities. The portable electric device comprises an antenna, a receiving unit, a transmitting unit, a transmitter/receiver unit, etc. The transmitter/receiver unit has an operating-mode-setting means for shifting from a standby-for-receiving mode to a receiving-prohibiting mode.
[0004] JP Unexamined Patent Pub. No. 2002-135838 discloses an automatic control system to restrict the operation of portable electric devices in places where restriction is required and does not restrict the operation of portable electric devices in other places where restriction is not required. The automatic control system of portable electric devices is capable of automatic changeovers, rendering it unnecessary to ask people not to take photos or not to use flashlights. More specifically, a radio wave carrying a control signal is transmitted into a zone, which people pass through, for restricted place or space. On the other hand, a radio wave carrying a restriction-lifting signal is transmitted into a zone, which people pass through, for places where restriction is not required. The portable electric devices which have received the restriction-lifting signal return to the normal-operation mode.
[0005] JP Unexamined Patent Pub. No. 2002-27554 discloses a control technique for (i) improving the convenience of users and controlling the function of telephoning as well as other functions of a portable terminal 101 by controlling the functions of the terminal from the viewpoints of users in addition to the unilateral control of functions of the terminal from a station. A device 102 for transmitting and receiving radio waves in local areas generates and transmits function-regulating information, which corresponds to the regulations in a specific area, to restrict the operation of cameras 113 and recording means 114 of portable terminals 101 in the specific area. The local transmitting/receiving means 111 of portable terminals 101 receive the function-regulating information from the device 102 . When the function-control means 118 of portable terminals 101 find that the function-regulating information is of the prohibition of a function or functions, the outputting means 117 of portable terminals 101 notify the users of the prohibition by means of display, sound, or vibration.
BRIEF SUMMARY OF THE INVENTION
[0006] Portable electronic devices with camera functions have become very popular recently. With such portable electronic devices, people can take photographs easily at any place. It is sometimes, however, desirable to prevent people from taking pictures using such devices for various reasons, e.g., to protect a person's privacy.
[0007] The above JP patent applications are directed to address such a concern. The techniques disclosed thereto, however, restrict the photography function of all portable electronic devices in a given area; therefore, if an unforeseen event occurs for which photography is needed, these devices cannot be used to take pictures. Also, it is not possible to allow one group of portable electronic devices to take pictures while restricting another group of portable electronic devices from taking pictures, or restrict the use of portable electronic devices in different ways at different times.
[0008] Accordingly, one feature of the present invention provides an information processor capable of solving the above problems and improving the convenience of users.
[0009] In one embodiment, a portable electronic device comprises a photograph-taking component configured to capture an image of an object; a receiver configured to receive information on photography restriction from a first external communication source, wherein the first external communication source transmits first information if the portable electronic device is considered to be within a photography restriction area; and a controller configured to place the portable electronic device in a restricted photography mode if the first information is received by the receiver, the restricted photography mode allowing the photograph-taking component to capture an image of a given object, the captured given object being represented by image data. The portable electronic device is configured to operate the photograph-taking component in the restricted photography mode and a non-restricted photography mode.
[0010] In one embodiment, a method for controlling an image capturing feature of a portable electronic device configured to capture images includes receiving a photography restriction signal by the portable electronic device from a communication source provided external to the portable electronic device; converting a photography mode of the portable electronic device from a first photography-capturing mode to a second photography-capturing mode in response to the photography restriction signal received from the external communication source; and thereafter, capturing an image of an object using the second photography-capturing mode of the portable electronic.
[0011] In another embodiment, a portable electronic device including an image capturing feature includes means for receiving a photography restriction signal by the portable electronic device from a communication source provided external to the portable electronic device; means for setting the portable electronic device from a first photography-capturing mode to a second photography-capturing mode in response to the photography restriction signal received from the external communication source; and means for capturing an image of an object using the second photography-capturing mode of the portable electronic.
[0012] Yet another embodiment is directed to a handheld electronic device including a computer program for controlling an image capturing feature of the handheld electronic device. The program comprises code for receiving a photography restriction signal by the handheld electronic device from a communication source provided external to the handheld electronic device; code for converting a photography mode of the handheld electronic device from a first photography-capturing mode to a second photography-capturing mode in response to the photography restriction signal received from the external communication source; and code for capturing an image of an object using the second photography-capturing mode of the handheld electronic.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] FIG. 1 is an illustration of a system for restricting the photograph-taking functions of portable electronic devices in accordance with embodiments of the present invention.
[0014] FIG. 2 is a block diagram of a portable electronic device of FIG. 1 .
[0015] FIG. 3 is a block diagram of the portable electronic device in the system for restricting the photo-taking functions of portable electronic devices according to the first embodiment of the present invention.
[0016] FIG. 4 is an exemplary flowchart restricting the photograph-taking function performed by the portable electronic device of FIG. 3 .
[0017] FIG. 5 is an example of the notice of restriction of photography to be displayed on the displaying unit of the portable electronic device of FIG. 3 .
[0018] FIG. 6 is an exemplary flowchart for displaying a photograph taken according to the flowchart of FIG. 4 on the displaying unit of the portable electronic device.
[0019] FIG. 7 is a block diagram of the portable electronic device in the system for restricting the photograph-taking functions of portable electronic devices according to the second embodiment of the present invention.
[0020] FIG. 8 is an exemplary flowchart restricting the photograph-taking function of the portable electronic device of FIG. 7 .
[0021] FIG. 9 is a block diagram of the portable electronic device in the system for restricting the photograph-taking functions of portable electronic devices according to the third embodiment of the present invention.
[0022] FIG. 10 is an exemplary flowchart restricting the photograph-taking function of the portable electronic device of FIG. 9 .
[0023] FIG. 11 is a block diagram of the portable electronic device in the system for restricting the photograph-taking functions of portable electronic devices according to the fourth embodiment of the present invention.
[0024] FIG. 12 illustrates a process for restricting the photograph-taking function of the portable electronic device of FIG. 1 , according to one embodiment of the present invention.
[0025] FIG. 13 is a block diagram of the portable electronic device in the system for restricting the photograph-taking functions of portable electronic devices according to the fifth embodiment of the present invention.
[0026] FIG. 14 illustrates a process for restricting the photograph-taking function of the portable electronic device of FIG. 13 , according to one embodiment of the present invention.
[0027] FIG. 15 illustrates a process for lifting the restriction of photography in accordance with the sixth embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0028] With reference to drawings, preferred embodiments for a system to restrict the functions of photography of cameras that are integrated to portable electronic devices in accordance with the present invention are described below in detail. FIG. 1 is an exemplary illustration of the system.
[0029] A specific area 101 is a designated area, such as the inside of a movie theater or concert hall. The camera features of portable electronic devices 102 are restricted when they are brought into the specific area 101 . This restriction is lifted by performing a predefined procedure or adding another restriction.
[0030] FIG. 2 is an exemplary block diagram of a portable electronic device 102 . The portable electronic device 102 comprises a photograph-taking means 201 (or camera or camera component), a controller 202 to control the portable electronic device 102 , a storage 203 to store image data, a displaying unit 204 such as a display or speaker, an input means 205 such as buttons for a user to input data and instructions, a receiving means 206 to receive signals including information about the restriction of photography from a fixed station 210 , and a means 207 for switching to different operations. The operation-changeover means 207 may be included in the controller 202 .
[0031] With the above construction, the changeover means 207 restricts the function of photography of the portable electronic device 102 and lifts the restriction in accordance with the information about the restriction of photography received by the receiving means 206 . Information about the restriction of photography is included in prescribed control signals to be transmitted from a transmitter installed in the specific area 101 or at a gateway of the specific area 101 .
[0032] With reference to drawings, the restriction of photography by the operation-changeover means 207 will be described below.
[0000] First Embodiment
[0033] The restriction of the function of displaying a photographed image by encoding its image data before storage are described below.
[0034] FIG. 3 is a block diagram of the portable electronic device 102 according to the first embodiment. The portable electronic device 102 a of FIG. 3 corresponds to the portable electronic device 102 of FIG. 2 plus a transmitting means 301 , an encoding means 302 , and a decoding means 303 . The portable electronic device may be a handheld device that is configured to be operated while being held on a user's hand. Examples of such handheld devices include mobile phones and personal digital assistants.
[0035] FIG. 4 is a flowchart of the process 400 of the control of functions performed by the portable electronic device 102 a . In Step 401 , the user of the portable electronic device 102 a operates the input means 205 to take pictures using the photograph-taking means 201 . In Step 402 , it is determined whether or not photography is restricted based on information received by the receiving means 206 . If photography is not restricted, a picture is taken in Step 405 and its image data are stored in the storage 203 in Step 407 . Then, the process ends in Step 408 . If it is determined in Step 402 that photography is restricted, the message shown in FIG. 5 is displayed on the displaying unit 204 to notify the restriction to the user of the portable electronic device 102 a . Then, a photograph is taken in Step 404 and its image data are encoded by the encoding means 302 in Step 406 . The encoded image data are stored in the storage 203 in Step 407 and the process ends in Step 408 .
[0036] FIG. 6 illustrates a process 660 for displaying the picture taken according to the process 400 on the displaying unit 204 , according to one embodiment.
[0037] In Step 601 , the user of the portable electronic device 102 operates the input means 205 to request the display of the picture taken according to the process 400 on the displaying unit 204 . In Step 602 , the controller 202 determines whether or not the image data of the picture are encoded. If the image data are not encoded, the picture is displayed in Step 605 . Then, the process ends in Step 606 . If the controller 202 determines in Step 602 that the image data are encoded, a decoding key is inputted in Step 603 . In Step 604 , it is determined whether or not the decoding key is correct. If the decoding key is correct, the encoded image data are decoded by the decoding means 303 and the image or picture is displayed (Step 605 ). Then, the process ends in Step 606 . If the decoding key is wrong or no decoding key is inputted, the process ends without displaying the image/picture in Step 606 .
[0038] A decoding key may be obtained by sending the image data of a taken photograph to a certain database of a police station, firehouse, or the like through the transmitting means 301 or by making a payment to a charging system.
[0000] Second Embodiment
[0039] According to the second embodiment, the image data of the portable electronic device 102 are sent to a fixed station. FIG. 7 is a block diagram of the portable electronic device 102 b according to the second embodiment, which corresponds to the portable electronic device 102 of FIG. 2 plus a transmitting means 301 . FIG. 8 illustrates a process 800 performed by the portable electronic device 102 b . In Step 801 , the user of the portable electronic device 102 b operates the input means 205 to take pictures using the photo-taking means 201 . A picture is taken in Step 802 . In Step 803 , it is determined whether or not camera features are restricted based on the information received by the receiving means 206 . If photography or camera feature is not restricted, the image data of the picture taken at step 802 are stored in the storage 203 in Step 805 , and the process ends in Step 806 . If photography is restricted, the image data of the photograph are sent to the fixed station 210 in Step 804 and the process ends in Step 806 . The station 210 may be a server or storage system that is wirelessly coupled to the portable electronic device via the transmitting means 301 .
[0040] When the user of the portable electronic device 102 b requests the display of the photograph, the image data of the photograph are received from the fixed station 210 and the photograph is displayed on the displaying unit 204 . The image data may be received either via a wireless or wired communication link. The restriction of photography is accomplished by storing image data not locally (in the portable electronic device 102 b ), but in a remotely located device (in the fixed station 210 ).
[0000] Third Embodiment
[0041] According to the third embodiment of the present invention, the photograph-taking modes of the portable electronic device 102 are restricted if it has two or more photograph-taking modes regarding the quality and resolution of images, the function of revising images by signal processing, etc.
[0042] FIG. 9 is a block diagram of the portable electronic device 102 of the third embodiment, which corresponds to the portable electronic device 102 of FIG. 2 plus an image-signal processing means 901 .
[0043] FIG. 10 illustrates a process 1000 relating to the control of functions of the portable electronic device 102 c . In Step 1001 , the user of the portable electronic device 102 c operates the input means 205 to take a picture using the photo-taking means 201 . In Step 1002 , it is determined from the information received by the receiving means 206 whether or not photography is restricted. If photography is not restricted, a picture is taken in Step 1004 , and the process ends in Step 1006 . If photography is restricted, at least one or more functions of the image-signal processing means 901 are suspended in Step 1003 and a photograph is taken in Step 1005 . Then, the process ends in Step 1006 .
[0000] Fourth Embodiment
[0044] According to the fourth embodiment, the user of the portable electronic device 102 is notified of the restriction of photography by a siren or light emission.
[0045] FIG. 11 is a block diagram of the portable electronic device 102 according to the fourth embodiment, which corresponds to the portable electronic device 102 of FIG. 2 plus a means of outputting sound or light 1101 .
[0046] FIG. 12 illustrates a process 1200 relating to the control of functions of the portable electronic device 102 d . In Step 1201 , the portable electronic device 102 d is placed in a photograph-taking mode. In Step 1202 , it is determined from the information received by the receiving means 206 whether or not photography is restricted. If photography is not restricted, a photograph is taken in Step 1205 , and the portable electronic device 102 is switched to non-photograph-taking mode in Step 1207 . Then, the processing is ended in Step 1209 . If photography is restricted, the means of outputting sound or light 1101 (or an outputting device) starts to output sound or light in Step 1203 . A photograph is taken in Step 1204 . The portable electronic device 102 is switched to a photograph-taking mode in Step 1206 . The means of outputting sound or light 1101 stops outputting sound or light in Step 1208 . Then, the process ends in Step 1209 . According to this embodiment, sound or light is always outputted while the portable electronic device 102 is a photograph-taking mode. Thus, the intention of the user of the portable electronic device 102 to take photographs can be notified to people around him.
[0000] Fifth Embodiment
[0047] According to the fifth embodiment, the photograph-taking function of the photograph-taking means 201 is restricted and the restriction is lifted based on positional information obtained through a GPS function while the portable electronic device 102 is in the specific area 101 .
[0048] FIG. 13 is a block diagram of a system to restrict the photography of portable electronic devices 102 e according to the fifth embodiment. The portable electronic device 102 comprises a photograph-taking means 201 , a controller 202 to control the portable electronic device 102 , a storage 203 to store image data, a displaying unit 204 such as a display, a means 206 of receiving signals from a fixed station 210 , a means 207 of changeover among operations, a means 1301 of finding the position of the portable electronic device 102 based on the positional information, and a means 1302 of finding whether the position is within a restricted area or not. The reference numeral 1303 is a map information database, which comprises a storage 1304 to store information about restricted areas and restrictions in the restricted areas, a processing unit 1305 , and a communicating unit 1306 .
[0049] FIG. 14 illustrates a process 1400 for restricting photography feature of the above system. In Step 1401 , the position-finding means 1301 determines the position of the portable electronic device 102 . In Step 1402 , the portable electronic device 102 gets the information about the restriction of photography stored in the storage 1304 of the map information database 1002 through the fixed station 210 . In Step 1403 , the means 1302 determines from the information on the restriction of photography whether or not the position of the portable electronic device 102 is within a restricted area. If the portable electronic device 102 is not within a restricted area and the photography feature of the portable electronic device 102 is restricted, the restriction on photography is lifted in Step 1405 . Then, the process ends in Step 1408 . If the portable electronic device 102 is within a restricted area, it is determined based on the information about the restriction on photography in Step 1404 whether or not photography is allowed. If photography is not allowed, the photograph-taking function of the portable electronic device 102 is suspended in Step 1407 , and the process ends in Step 1408 . If photography is allowed conditionally, the image data is encoded as described in the first embodiment, or the image data is transmitted to the fixed station 210 , as described in the second embodiment, or part of signal processing is suspended as described in the third embodiment, or sound or light is outputted as described in the fourth embodiment in Step 1406 . Then, the process ends in Step 1408 .
[0000] Sixth Embodiment
[0050] According to the sixth embodiment, the restriction is lifted with or without other conditions if the portable electronic device 102 is within the specific area 101 and photography is restricted.
[0051] FIG. 15 illustrates a process 1500 for lifting the restriction of photography. In Step 1501 , the user of the portable electronic device 102 operates the input means 205 to request lifting of the restriction of photography. In Step 1502 , information on the restriction of photography is obtained through the receiving means 206 . The information may also be obtained beforehand. In Step 1503 , the controller 202 determines from the information in the restriction of photography whether or not the restriction of photography can be lifted. If the restriction cannot be lifted, the process ends. If the restriction can be lifted, the controller 202 determines in Step 1504 whether or not there are conditions for lifting the restriction. If there are no conditions for lifting the restriction, the restriction is lifted in Step 1506 , and the process ends. If there are conditions for lifting the restriction, the functions corresponding to the conditions for lifting the restriction are added in Step 1505 , and the restriction is lifted in Step 1506 . Then, the process ends.
[0052] The user may choose one from a plurality of restrictions included in the information on the restriction of photography.
[0053] With the above configuration of the system, photographs can be taken even in restricted areas if conditions for photography are satisfied.
[0054] As described above, according to the present invention, portable electronic devices, e.g., cell phones, may be used to take pictures in restricted areas under certain situations while preventing unauthorized photography in a restricted place by suspending one or more functions of the above photograph-taking means. Besides, by adding a system to lift the suspension of functions, either unconditionally or conditionally, under certain specific circumstances, portable electronic devices are allowed in emergency or such suspension of functions can be imposed on only certain selected portable electronic devices or persons. Moreover, a system for billing users of portable electronic devices for photography in specific areas can be constructed by combining the above system for restricting photography and a charging payment system.
[0055] According to the present embodiments, the photograph-taking functions of portable electronic devices with the function of a video camera can be appropriately restricted in public facilities such as movie theaters, art museums, and concert halls.
[0056] The present invention has been described using specific embodiments. These embodiments may be modified or changed without departing from the scope of the present invention. The scope of the present invention, accordingly, should be determined using the appended claims. | A portable electronic device comprises a photograph-taking component configured to capture an image of an object; a receiver configured to receive information on photography restriction from a first external communication source, wherein the first external communication source transmits first information if the portable electronic device is considered to be within a photography restriction area; and a controller configured to place the portable electronic device in a restricted photography mode if the first information is received by the receiver, the restricted photography mode allowing the photograph-taking component to capture an image of a given object, the captured given object being represented by image data. The portable electronic device is configured to operate the photograph-taking component in the restricted photography mode and a non-restricted photography mode. | 7 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims the benefit of the filing date of U.S. Provisional Patent Application No. 61/619,719 filed Apr. 3, 2012, the disclosure of which is hereby incorporated herein by reference.
FIELD OF THE INVENTION
[0002] This invention relates to switchable or active technology glazing devices, and in particular, relates to the obscuration of such devices.
BACKGROUND OF THE INVENTION
[0003] Insulated glass units (IGUs) include opposing glass lite panels separated by a spacer along the edge in which the spacer and the glass sheets create a seal around a dead air space (or other gas, e.g., argon, nitrogen, krypton). A series of thin films, known as electrochromic glazings, are applied or deposited to one of the glass lite panels. Electrochromic glazings or coatings include electrochromic materials that are known to change their optical properties in response to the application of an electric potential which can create coloration or tinting within the electrochromic glazings. Common uses for these glazings include architectural windows, as well as windshields and mirrors of automobiles. Further details regarding the formation of IGUs can be found in, for example, U.S. Pat. No. 7,372,610; U.S. Pat. No. 7,593,154; and U.S. Pat. Appl. Publ. No. 2011/0261429 A1, the entire disclosures of which are hereby incorporated by reference herein.
[0004] Current IGUs often have printed busbars and have non-active or non-coloring areas near edges of visible viewing regions within such IGUs that are generally perceived to be aesthetically undesirable features. Obscuration has been used to mask these undesirable features. Current edge obscuration however utilizes a straight solid line, i.e., “hard edge,” that cannot sufficiently disguise conspicuous or recognized misalignment. Precise alignment of the IGUs by a contractor, such as a glazing contractor, working on the installation or repair of IGUs may be difficult and expensive.
[0005] Thus, there exists a need for obscuration that disguises recognized misalignment without incurring such labor-intensive costs.
SUMMARY OF THE INVENTION
[0006] As used herein, the terms “width” and “length” refer to directions parallel to surfaces of a substrate. The term “thickness” is used to refer to a dimension measured in a direction perpendicular to the surfaces of such a substrate.
[0007] To lessen the visual or actual impact of these often undesirable features, at least one side of an electrochromic device, such as an edge thereof, may include one or more obscuration patterns. An obscuration pattern desirably may be designed to disguise undesirable features along the visible edges of an electrochromic device and have a minimum width necessary to perform this function in order to maximize the unobstructed viewing area through an electrochromic device and to add the least amount of cost to the production of such devices.
[0008] In some arrangements, an obscuration pattern may be printed. In some arrangements, the pattern may be formed using screen-printing of inorganic or organic inks, such as but not limited to an ink based on reactive acrylates, that bond to a substrate, such as but not limited to glass, after a heat treatment, such as but not limited to curing by ultraviolet light or other known curing methods. In some arrangements, the reactive acrylates preferably may be dark or pigmented, which may act to obscure a view of undesirable features. In some arrangements, an obscuration pattern is prepared by digital printing of organic inks, inorganic inks, or mixtures thereof. Such digital printing may be used to automatically and accurately print patterns, which may have any color, onto the substrate. In some arrangements, a pattern in accordance with the present invention may be formed onto glass, for example tempered glass used for vehicle windshields. In some arrangements, a screen-printed pattern may be printed on any of a series of attachable substrates such as but not limited to float glass, electrochromic glass, or a thin film material. In such arrangements, the pattern on each of these individual substrates may have approximately the same dimensions, each having approximately the same pattern.
[0009] In some arrangements, a pattern may be applied using adhesive tape, which may be used to apply an obscuration band, an obscuration band being an opaque area in the glass, as used herein. In some such arrangements, straight lines or for shapes, such as but not limited to circular, rectangular, or triangular dots that may be formed on the adhesive tape, which may then be applied directly to a substrate.
[0010] In some arrangements, the obscuration pattern may be applied to two sides, which may be two edges, of an electrochromic device. In some arrangements, the obscuration pattern may be applied to three sides, which may be three edges, of an electrochromic device. In some arrangements, the obscuration pattern may be applied to four sides, which may be four edges, of an electrochromic device. In some arrangements, the obscuration pattern may be predetermined over at least a portion of the electrochromic device. In some arrangements, the pattern may be repeating in a direction parallel to a given side of an electrochromic device. In some arrangements, the pattern may be repeating in a direction perpendicular to a given side of an electrochromic device.
[0011] In some arrangements, an obscuration pattern may be formed from a single layer or coating of repeating shapes. In other arrangements, a final pattern may be the result of forming multiple overlapping shapes or patterns, which may be formed from single or multiple coatings. In other arrangements, single layers of single layer or multiple layer patterns or even separate layers of a multiple layer pattern may include the same or different colors. In some arrangements, the pattern may include a sequence of dots of the same size. In other embodiments, the pattern may include dots of varying sizes. In other embodiments, the dots may have different sizes in which radii of a sequence of the dots decrease in a direction away from an initial solid pattern. In some arrangements, the pattern may include a series of lines having either or both of various thicknesses and opacities. In some such arrangements, the series of lines may be parallel while in other such arrangements, the series of lines may be skewed or even perpendicular to other lines of the series of lines.
[0012] In some arrangements, the obscuration pattern may be placed onto other fixtures or coatings or other layers already on a substrate such as but not limited to a reflective coating, a solar control coating, or a photocatalytic layer coating that may make cleaning of a substrate easier.
[0013] In accordance with an embodiment of the invention, an electrochromic device may be provided that includes a substrate, an electrochromic coating, and at least one patterned layer. The electrochromic coating may overlie a portion of the substrate within a visible region of the substrate. The electrochromic coating may have an outer edge spaced from an outer boundary of the visible region of the substrate. The outer edge of the electrochromic coating and the outer boundary of the visible region may define a working region. The patterned layer may be deposited within the working region. The patterned layer may include a plurality of spaced apart shapes.
[0014] In some arrangements, the electrochromic device may be inserted within a frame. The shapes may run parallel to at least one of (i) the outer edge of the electrochromic coating, an inner edge of a seal between the device and the frame, and (iii) and an inner rim of the frame. In some arrangements, the shapes may be lines. In some such arrangements, the shapes may be parallel. In some arrangements, the shapes may be dots.
[0015] In some arrangements, the dots may include at least a first plurality of dots arranged along a first line and a second plurality of dots arranged along a second line. In some such arrangements, the first plurality of dots may be parallel to the second plurality of dots. In some arrangements, each dot of the first plurality of dots may have a first size and each dot of the second plurality of dots may have a second size in which the first size is different than the second size. In some arrangements, the dots may include at least a third plurality of dots arranged along a third line. In some such arrangements, the third plurality of dots may be parallel to the first and second pluralities of dots. In some such arrangements, each dot of the first, second, and third pluralities of dots may have first, second, and third radii, respectively. In some such arrangements, the second pluralities of dots may be between the first and third pluralities of dots. In some such arrangements, the first radii of the first plurality of dots may be greater than the second radii of the second plurality of dots. In some such arrangements, the second radii of the second plurality of dots may be greater than the third radii of the third plurality of dots.
[0016] In some arrangements, at least some of the shapes may have at least one of different widths and different thicknesses. In some arrangements, the device may be inserted within a frame. In some arrangements, the visible region may be defined by one of an inner edge of a seal between the device and the frame and an inner rim of the frame. In some arrangements, some of the spaced apart shapes may have a different shape than other ones of the spaced apart shapes. In some such arrangements, the shapes may include any of circles, triangles, and rectangles. In some arrangements, the patterned layer may have a thickness in the range between about 1 micrometers and 50 micrometers.
[0017] In some arrangements, the substrate may include at least one of a reflective coating, a solar control coating, and a photocatalytic coating. In some such arrangements, the patterned layer may be deposited onto any one or more of these coatings. In some arrangements, the substrate may have four sides. In some such arrangements, the patterned layer may be applied to one of (i) only one side, (ii) only two sides, (iii) only three sides, and (iv) all four sides of the substrate. In some arrangements, at least a portion of the patterned layer may be formed of a plurality of overlapping layers. In some arrangements, at least one layer of the plurality of overlapping layers may have a different color than another of the plurality of overlapping layers. In some arrangements, at least one of the spaced apart shapes may have a different color than another one of the spaced apart shapes. In some arrangements, the patterned layer may be deposited onto the outer edge of the electrochromic coating. In some arrangements, the patterned layer may be deposited onto the substrate such that it overlaps a projection on the substrate of the outer edge of the electrochromic coating within said visible region.
[0018] In accordance with another embodiment, an electrochromic device including a substrate, an electrochromic coating, and at least one patterned layer. The electrochromic device may be inserted within a frame. The electrochromic coating may cover a portion of the substrate within a visible region of the substrate. The visible region may be defined by one of an inner edge of a seal and an inner rim of the frame. The electrochromic coating may have an outer edge spaced from an outer boundary of the visible region of the substrate. The outer edge of the electrochromic coating and the outer boundary of the visible region may define a working region. The patterned layer may be deposited within the working region. The patterned layer may include at least one of (i) a plurality of lines spaced apart from each other and (ii) a plurality of dots spaced from one another.
[0019] In accordance with another embodiment, a substrate may include a stack of thin films having at least one edge. The substrate may further include at least one patterned layer deposited on top of the thin film edge. The patterned layer may run approximately the length of the edge. The patterned layer may include at least one of (i) a series of lines and (ii) a series of dots.
[0020] In some arrangements, the stack of thin films may include at least one electrochromic material. In some arrangements, the electrochromic material may comprise a mixed tungsten-nickel oxide. In some arrangements, the electrochromic material may be a tungsten oxide.
BRIEF DESCRIPTION OF THE DRAWINGS
[0021] FIG. 1 is a cross-sectional elevation view of a portion of an electrochromic device installed within a frame in accordance with an embodiment of the invention.
[0022] FIGS. 2 (A)-(C) are plan views of examples of different obscuration patterns in accordance with various arrangements of the invention.
[0023] FIGS. 3 (A)-(B) are plan views of examples showing the edge of the glass, an unprinted band, the printed band, and the visible region.
[0024] FIG. 4 is a process flow diagram of an arrangement for fabricating an electrochromic device with an obscuration pattern in accordance with an embodiment of the invention.
DETAILED DESCRIPTION
[0025] Referring to FIG. 1 , in accordance with an embodiment, an electrochromic device may be an insulated glass unit (IGU) 5 having an inboard glass lite 9 and an outboard glass lite 10 . As shown, the inboard glass lite 9 may be made clear float glass. As further shown, the outboard glass lite 10 may include an outer ply layer 16 between and defined by an exterior surface 11 and an interior surface 12 , which may be made of clear float glass. The outboard glass lite 10 may include an inner ply layer 18 between and defined by an inner surface 13 and an inside surface 14 . In some arrangements, the inner ply layer 18 may include a clear float glass. As shown in FIG. 1 , the inside surface 14 of the inner ply layer 18 may be coated with an electrochromic coating 15 , which may be various oxide thin films known to those of ordinary skill. The outboard glass lite 10 may include an interlayer 17 between the outer ply layer 16 and the inner ply layer 18 , which may be a clear layer. Electrochromic coatings are composed of stacks of thin-films and are, for example, disclosed in U.S. Pat. Nos. 7,372,610 and 7,593,154, the disclosures of which are hereby incorporated by reference herein. Of course, the electrochromic coatings are not limited to those disclosed above and may include other types of coatings, such as but not limited to thermochromic coatings.
[0026] As further illustrated in FIG. 1 , in some arrangements, the IGU 5 may include a spacer 30 which may be inserted between outer and inner spacer seals 38 , 39 , respectively. The outer and inner spacer seals 38 , 39 in turn may be inserted between, and may be sealingly engaged with, the spacer 30 and the inside surface 14 and the spacer 30 and an interiorly facing surface of the inboard glass lite 9 , respectively. In some arrangements, the spacer 30 and the outer and inner spacer seals 38 , 39 may circumscribe a perimeter (not shown) of the IGU 5 between the inboard glass lite 9 and the outboard glass lite 10 . In this manner, the spacer 30 and the outer and inner spacer seals 38 , 39 may surround a visible region 90 as discussed further herein.
[0027] Exterior to the IGU 5 may be an architectural building frame 1 . Inner frame seal 19 may be inserted between, and may be sealingly engaged with, the frame 1 and the exterior surface 11 and outer frame seal 20 may be inserted between, and may be sealingly engaged with, the frame 1 and an exteriorly facing surface of the inboard glass lite 9 . In some arrangements, the frame 1 and the inner and outer frame seals 19 , 20 may circumscribe inner and outer perimeters (not shown) of the IGU 5 interior to and exterior to the IGU 5 , respectively. In this manner, either or both of the frame 1 and the inner and outer frame seals 19 , 20 may surround, and further may define, at least a portion of the visible region 90 , as discussed further herein.
[0028] Still referring to FIG. 1 , in some arrangements, an outer edge 25 of the electrochromic coating 15 may be formed along the inside surface 14 at a distance D+x from an edge 21 of the outboard glass lite 10 . In such arrangements, as shown, the distance D may be a distance from the edge 21 to a line through an inner tip 22 of the outer frame seal 20 perpendicular to the inside surface 14 . In the example shown, the distance x may be a distance from the line through the inner tip 22 of the outer frame seal 20 perpendicular to the inside surface 14 to the outer edge 25 of the electrochromic coating 15 . Such a distance is representative of what is typically considered to be the visible region of the IGU 5 through which a person 45 will view the environment 50 which is not coated with electrochromic coating. Accordingly, this region is not subject to a change in optical properties and, as such, may not be able to be tinted in contrast to the region having a layer coated with the electrochromic coating.
[0029] As further illustrated in FIG. 1 , an obscuration pattern 99 , as described further herein, preferably may be formed on and along the interior surface 12 of the glass lite 10 , although in alternative arrangements, it may be formed on and along other surfaces of the glass lite 10 , such as but not limited to the inside surface 14 . The obscuration pattern 99 , as in the example of FIG. 1 , preferably may be formed over a minimum distance to cover the portion of the region designated as having a distance x along at least a portion of the outer perimeter of the IGU 5 . In some arrangements, the obscuration pattern 99 may extend a distance x+y, as further shown in FIG. 1 , in which the distance y may correspond to a distance from the outer spacer seal 38 to the tip 22 of the outer frame seal 20 , as in this example, or to an analogous obstruction at the exterior surface 11 . Such a distance y represents a region that may also be visible to a person looking through an IGU, which is typically called the “clear edge” of the glass lites of an IGU. In other arrangements, the obscuration pattern 99 may extend a distance D+x in which no spacer is used. As shown, the obscuration pattern 99 may be formed around all or only a portion of the outer perimeter of the interior surface 12 so as to provide obscuration at all sides. In other arrangements, the obscuration pattern may be formed around only some of the sides or only a portion of some of the sides of the IGU.
[0030] In some such arrangements, the distance D+x preferably may be in the range between about 1 mm to about 30 mm, and more preferably in the range between about 5 mm to about 15 mm. In some such arrangements, the distance x preferably may overlap a projection of the electrochromic coating in a range between about 1 mm and about 10 mm, more preferably in a range between about 2 mm and about 5 mm, and most preferably in a range between about 2 mm and about 3 mm. In some such arrangements, the distance x+y preferably may be in the range between about 1 mm and about 20 mm and more preferably in the range between about 2 mm to 10 mm.
[0031] In some alternative arrangements, an obscuration pattern may be located along any of the exterior surface 11 , the interior surface 12 , and the inner surface 13 . In some such arrangements, the obscuration pattern preferably may have a width that covers at least the distance x, as described previously herein with respect to the obscuration pattern 99 . Moreover, in some such arrangements, the obscuration pattern preferably may have a width that covers a maximum of the distance x+y in instances in which a spacer is used, as further described previously herein with respect to the obscuration pattern 99 , and a maximum of the distance D+x in instances in which a spacer is not used.
[0032] In some alternative arrangements, the obscuration pattern may be combined with other fixtures or coatings, such as but not limited to a reflective coating, which may be placed along the exterior surface 11 , the interior surface 12 , and optionally the inner surface 13 , a solar control coating which may be placed along interior surface 12 , or a photocatalytic coating, which may be deposited onto the exterior surface 11 or the inner surface 13 . (See FIG. 1 ).
[0033] Referring now to FIGS. 2 (A)-(C), an obscuration pattern in accordance with an embodiment may come in a variety of forms. As shown in FIG. 2(A) , an obscuration pattern 100 may include a solid line 101 . The solid line 101 may have a width that fully covers the portion of a visible region of an IGU over a distance x as described previously with respect to FIG. 1 . As shown, the obscuration pattern 100 may include a series of lines 111 - 113 parallel to one another and to the solid line 101 , although in some arrangements, the lines may be parallel in a direction perpendicular to the solid line 101 , skew to one another or even cross-hatched, or may be in other repeating, aesthetically pleasing, patterns. As shown, the line 111 may be wider than the line 112 which may be wider than the line 113 . However, in alternative arrangements, each of these lines may have the same width as at least one other of the lines. In some alternative arrangements, there may be a fewer or a greater number of lines in addition to the solid line 101 .
[0034] As shown in FIG. 2(B) , an obscuration pattern 200 may include a solid line 101 . The line 101 may have a width that fully covers the portion of a visible region of an IGU over a distance x as described previously with respect to FIG. 1 . As shown, the obscuration pattern 200 may include a series of dots along lines 211 - 213 parallel to one another, although in some arrangements, the dots may be parallel to one another in a direction perpendicular to the solid line 101 or may be in other repeating, aesthetically pleasing, patterns. As shown, the dots within the line of dots 211 may be wider than the dots within the line of dots 212 which may be wider than the dots within the line of dots 213 . However, in alternative arrangements, the dots of any of these lines may have the same width as the dots of any other line of dots. In some alternative arrangements, there may be a fewer or a greater number of lines of dots in addition to the solid line 101 .
[0035] As shown in FIG. 2(C) , an obscuration pattern 300 may have a solid line 101 and parallel lines of dots 311 - 313 in a similar configuration to the lines of dots 211 - 213 of FIG. 2(B) . However, in this example, the lines of dots 211 - 213 in FIG. 2(B) may all have a greater width than the counterpart lines of dots 311 - 313 shown in FIG. 2(C) . As further shown in the examples of FIGS. 2(B) and 2(C) , the lines of dots 211 may intersect with the solid line 101 whereas the lines of dots 311 may not intersect with the solid line 101 . Such options may be design choices in which greater obscuration may be accomplished through the intersection of shapes of an obscuration pattern with the solid line but at a loss of some of the visible region through which a person may view the environment.
[0036] In some alternative arrangements, at least a portion of the obscuration pattern may formed of a variety of shapes, such as but not limited to lines of triangles, circles, or rectangles. In some alternative arrangements, such shapes may have holes in the middles thereof. In some alternative arrangements, such shapes may be evenly spaced apart within at least a portion of the obscuration pattern.
[0037] As illustrated in the examples of FIGS. 3(A) and (B), an obscuration pattern may be formed on different types of reflective coatings. As shown in FIG. 3(A) , a solid line 401 may be formed on a glass lite 410 to define a clear edge 402 around an outer perimeter of the glass lite 410 . As shown in FIG. 3(B) , the solid line 401 may be formed on a glass lite 450 to define the clear edge 402 . As shown, a series of lines of dots 411 - 414 may also be formed on the glass lite 450 . Such lines of dots 411 - 414 may have a shape and configuration that are a combination of the lines of dots 211 - 213 and 311 - 313 , as discussed with respect to FIGS. 2(A) and (B). As shown the example of FIG. 3(B) , each of the solid line 401 and the lines of dots 411 - 414 may be formed with any reflective coating (e.g., Si 3 N 4 , low E coatings, and pyrolytic coatings).
[0038] Referring now to the process flow diagram illustrated in FIG. 4 , an obscuration pattern, such as those described previously herein, may be formed by a digital printing process 500 . In this manner, it is believed that such a process provides a flexible way to automatically and accurately print patterns onto a substrate, such as a glass lite of an IGU. It is believed that such patterns may be of any color as well as of any shape when viewed in a plan view substantially perpendicular to the substrate and that the substrate may include any of convex and concave surfaces.
[0039] Such digital printing technology may be called a “drop on demand technology.” As shown in a step 510 of FIG. 4A , a pattern model may be created using production software, such as but not limited to MES from LISEC. In a step 520 , the pattern model created may be sent to an ink printer, such as but not limited to a RS35 Polytype. In other arrangements, the printer may be a GlassJet printer from DIPTECH. In a step 530 , a glass sheet, which may be a glass lite such as those described previously herein, or other substrate having any variety of known shapes and dimensions, may be conveyed to an inlet of the ink printer. In alternative arrangements, the glass sheet may be moved to the inlet of the printer through other processes known to those of ordinary skill in the art, such as by a manual movement of the sheet or through the use of a fork lift. In a step 540 , a first layer of ink, which may be made of materials such as but not limited to reactive and unreactive acrylates (even those that may be UV cured) may be dispensed, which may be by a jetting, onto a surface of the glass sheet through printhead of the printer. The reactive acrylates preferably may be dark or pigmented to act as obscuration. Also, the inks may be silicon based inks. Using a piezoelectric membrane in the printhead to dispense the ink, the amount of ink jetted may be controlled to accurately dispense consistent amounts of ink. Moreover, using such printers, the print heads may be translated over the glass sheet and dispense ink drops in predetermined positions on the glass sheet only when needed. In this manner, the obscuration pattern may be deposited and formed onto the glass sheet. For example, the obscuration patterns 99 , 100 , 200 , and 300 , described previously herein, may all be formed in this manner.
[0040] In some arrangements, as shown in a step 535 , to increase the adhesion of the ink to the glass sheet, a primer optionally may be applied onto a surface of the glass sheet. Such a primer may be applied by any number of processes such as vapor deposition, spray, pad printing, screen printing, or other methods known to those of ordinary skill in the art. In some arrangements, the primer optionally may be applied prior to step 540 in which the obscuration pattern may be printed. As further shown in step 535 , the primer may be applied by a printer at the same time as the ink printing. In some instances, the primer may be dispensed by the same printer dispensing the ink.
[0041] In a step 550 , ultraviolet (UV) lamps may be turned on and used to cure the first layer of ink after the ink has been deposited. The lamps preferably may be turned on in a range of approximately 15 seconds at the normal operating temperature of such lamps before the printing process starts. In some arrangements, such lamps may be located on both sides of the printheads of the printer such that the ink may be cured during the ink printing step 540 (as well as during the ink printing step 570 described further herein). In such a curing process, the ink may be cured at a rate of approximately 200 W/cm. In alternative arrangements, the ink may fired in an IR oven after some or preferably all ink printing steps, such as the steps 540 and 570 . It should be noted that this curing step is, in some embodiments, not used to replace thermal heat treatment steps used to enhance thin film layers or a stack of thin film layers (as disclosed in U.S. Pat. No. 7,372,610, the disclosure of which is hereby incorporated by reference herein) or heat treatment steps used in the production of electrochromic device laminates (as disclosed in copending U.S. patent application Ser. Nos. 13/040,787 and 13/178,065, the disclosures of which are hereby incorporated by reference).
[0042] In a step 560 , the printheads may be translated one step forward such that the one or more nozzles on the printheads partially overlies the first layer of ink on the glass sheet. The step that the printheads are translated may depend on one or both of the spacing to be applied between different layers of ink and a thickness desired for portions of the obscuration pattern.
[0043] In a step 570 , a subsequent layer of ink may be dispensed, which may be by jetting such as described with respect to step 540 . During such a step, the subsequent layer may be dispensed partially over the first layer and partially over an area of the glass in which no ink has been deposited, i.e., a clear area of the glass. In a step 580 , the UV lamps may be reactivated to cure the subsequent layer of ink. In alternative arrangements, such subsequent layer of ink may be fired in an IR oven as described previously herein with respect to the first layer of ink.
[0044] In a step 585 , each of steps 560 to 580 may be repeated to dispense and cure another subsequent layer of ink. During any of the ink printing steps 540 , 570 , and 585 , the thickness of each layer of ink preferably may be in the range between 10 and 200 microns, and more preferably may be in the range between 40 and 100 microns.
[0045] In a step 590 , following the deposition of all intended layers of ink, the glass sheet may be moved to an outlet conveyer which may move the glass sheet to a new location for further processing, such as to form an IGU. In alternative arrangements, the glass sheet may be moved by other well-known processes. As shown in a step 595 , the glass sheet may be conveyed or otherwise moved to be laminated. When laminating the glass sheet, the thickness of the obscuration pattern may be monitored to avoid potential undesirable lamination issues. Accordingly, the thickness of the obscuration pattern preferably may have a thickness in the range of less than about 100 micrometers, and more preferably between about 1 to about 50 μm, to obtain the desired optical density to avoid stress and optical distortion of the laminate when printed on either of surfaces of a glass lite such as the interior surface 12 and the inner surface 13 of the glass lite 10 . | An electrochromic device is provided. The device may be inserted within a frame. The device may include a substrate, an electrochromic coating, and a patterned layer. The electrochromic coating may overlie a portion of the substrate within a visible region of the substrate. The electrochromic coating may have an outer edge that is spaced from an outer boundary of the visible region of the substrate. The outer edge of the electrochromic coating and the outer boundary of the visible region may define a working region. The patterned layer may be deposited within the working region. The patterned layer may include a plurality of spaced apart shapes. | 2 |
This application is a continuation-in-part application of our copending application Ser. No. 560,931 filed Nov. 25, 1983, filed Mar. 25, 1983, published as WO83/03363 on Oct. 13, 1983, now abandoned.
The invention concerns a chromatographic process for separating natural and synthetic nucleic acids from low to very high molecular weight (molecular weight up to 50×10 6 ) by using surface modified carrier materials that contain cavities, and in particular to the chromatographic separation of nucleic acids having a chain length from about 5 to about 5000 nucleotides, natural and synthetic ribonucleic acids having one or two strands (RNA), like transfer RNA, ribosomal RNA, messenger RNA and viral RNA, natural desoxyribonucleic acid (DNA) and DNA fragments, particularly plasmid DNA and phagene DNA by using such carrier materials.
The progress in biochemistry, molecular biology and genetic engineering, and the application thereof to medicine, pharmacology and agriculture requires the quick separation and purification of discrete nucleic acids species. Thus, for instance, there often arises in genetic engineering the problem that from a naturally occurring mixture of 100 and more different nucleic acids of high molecular weight, a single molecular species must be purified homogeneity. The individual nucleic acids are known to be characterized by nucleotide sequence, molecular weight, size and shape.
Of special interest are long-chain ribo- and deoxyribo-oligonucleotides, natural ribonucleic acids (RNA), like transfer RNA and 7S RNA, viral RNA and messenger RNA, deoxyribonucleic acids (DNA), DNA fragments and plasmid DNA.
Traditional techniques force scientists to choose between resolution and recovery and are time consuming often hours or days to complete. Separation of high molecular weight nucleic acids is often done by gel electrophoresis or ultracentrifugation in CsCl density gradients. The high resolution of gel electrophoresis is very favorable but the recovery of the purified samples is low and the quality is often diminished because of contaminations with the gel matrix (soluble oligomeric agarose or acrylamide) yielding an inefficient biological activity in cell transformation and enzymatic reactions, e.g. digestion with restriction endonucleases, ligation, and reverse transcription. In addition electrophoresis is time consuming requiring hours or days to complete. Although for the special case of plasmid preparation banding in CsCl density gradients may be performed, it requires prolonged ultracentrifugation at high speed and consumes large amounts of CsCl and has the disadvantage of being expensive in respect to CsCl and service cost for the ultracentrifuge.
Chromatographic processes have proved advantageous for many separation problems in organic chemistry. High-performance liquid chromatography (HPLC) offers the most advantages in relation to resolution, short consumption of time and reproducibility. Said process has hithereto been used in the form of gel permeation chromatography (GPC), ion-exchange chromatography and reversed-phase chromatography (RP chromatography). However, for the separation of nucleic acids, these processes had the following disadvantages:
GPC is able only to separate small from very large molecules and resolution decreases above molecular weights of about 250,000, i.e. about 350 basepairs DNA.
The prior art ion exchangers and reversed-phase chromatography resins could only be used with high resolution for small molecules such as oligonucleotides, e.g. chain length up to 15 nucleotides (Fritz et al.; Biochemistry (1978) 17, 1257-1267). In the separation of nucleic acids of high molecular weight such as long-chain ribo- and deoxyribo-oligonucleotides, natural RNA's, like transfer RNA and 7S RNA, viral RNA and messenger RNA, DNA, DNA fragments and plasmid DNA, the required resolution into individual nucleic acid species could not be obtained.
Although hydrophobic-ionic RPC-5 chromatography material such as described by Larson, J. E. et al (The Journal of Biological Chemistry (1979) 254, 5535-5541) had been successfully used in the separation of DNA fragments, the flow rates that is, very long durations of chromatography, and the low chromatographic stability of the RPC-5 material are of great disadvantage. Due to the chemical properties of the RPC-5 material, bleeding of the liquid ion-exchanger Adogen 464 occurs, contaminating the purified samples.
With prior art chromatography, it was not possible to separate or isolate into the individual molecular species complex nucleic acid mixtures, with high resolution and high velocity, or to analyze said mixtures. It is thus an object of the present invention to provide a chromatographic process, wherewith the above-mentioned disadvantages are eliminated. Yet another object of the present invention is to provide in a single run the separation into their components, with very high resolution and high velocities, of macromolecular mixtures of the most varied kinds, which contain components of very different dimensions, for example, in the range of 30 Angstroms to 1,000 Angstroms. Still another object of the invention is to provide separation materials suitable for employment at high flow rates, wide temperature ranges and with extended durability. A high loading capacity is desirable with the nucleic acid mixtures to be separated. Contrary to the contraindications of the prior art, the present invention provides a chromatographic resin, with which it is possible to separate in a chromatographic process complex nucleic acid mixtures having a very broad spectrum of molecular size at very high resolution.
Because of its simplicity and the stable resin, this process is suitable for routine use in industry and research.
More particularly, the present invention provides the surface modification of a carrier material of a chromatographic resin, for the chromatographic separation of nucleic acids, using an inert particle, preferably silica gel. This silica gel is a high performance liquid chromatography silica gel, and preferably has a particle size of about 2 to 100 microns. A suitable, commercially available silica gel for this purpose is 10 micron LiChrosphere SI 4000 sold by E. Merck, Germany. However, the silica gel may be any chromatographic grade silica gel.
In the initial step, the silica is reacted with a bifunctional silane, e.g. γ-glycido-oxypropyl-trimethoxysilane in toluene. The reaction is conducted for a time and at a temperature to produce a product comprising γ-glycido-oxypropyl-trimethoxysilane covalently bound to the silica. An excess of γ-glycido-oxypropyl-trimethoxysilane to reactive silanol sites on the silica is used, a 5-fold excess being preferred. After reaction, the product epoxy-silica is filtered through a glass filter funnel yielding a filter cake. The filter cake is washed with hexane, dioxane and methanol to remove the silane and soluble impurities. Then the epoxy-silica is dried in vacuo. In the next step, if for example, the surface is modified into an anion-exchanger, the epoxy-silica is reacted with a N,N-dialkylalcohol, e.g. N,N-diethylethanol in toluene. After reaction, the resulting anion-exchanger diethylaminosilica gel (DEAE-silica) is removed by suction through a glass filter funnel and washed with methanol, acetone and ether and dried in vacuo.
For chromatography of nucleic acids the resulting chromatographic resin is dispersed in methanol and fed under pressure into a stainless steel column (diameter 6 mm, length 125 mm) at a flow-rate of 5 ml/min with a high-pressure pump with methanol as an eluent. The packed column is washed with water and connected to a liquid chromatograph (DuPont LC 850) equipped with an UV-detector. The separation is carried out with a gradient elution of increasing ionic strength in aqueous buffers at pH between 4 to 8. With this chromatographic resin water soluble nucleic acids can be separated conveniently and rapidly with high resolution.
The process described according to the invention is the first chromatographic process that has the following properties:
1. General applicability to the separation of nucleic acids.
2. Short chromatographic periods and high reproducibility of the elution profiles by the use of pressure-stable resins in HPLC equipments.
3. High loading capacity.
4. Chromatographic materials having long-term stability (no "bleeding" of the chromatography columns).
Unlike prior art chromatographic resins, which were exclusively based on the chemical properties of the carrier materials, the point of departure of the instant invention is the finding that the size and/or the shape of the cavities of the resin is of quite essential importance for the separation and must be in a specific relationship to the size of the nucleic acid species to be isolated. It has been found that the size of the cavities must amount to 1 to 40 times that of the components to be isolated. If the dimensions of the individual components to be separated differ from each other by more than a factor 40, it is possible to carry out the separation in several steps using carrier materials having suitably sized cavities. According to a preferred embodiment of the invention, there is provided a suitable modification of the surface. It has proved very advantageous here that the groups responsible for the interaction with the substances to be separated have been anchored to the surface by flexible chain molecules. This effect is obtained, for instance, by using γ-glycido-oxypropyl-trimethoxysilane. As interaction-producing groups there are contemplated strongly and weakly basic anion exhangers, strongly and weakly acidic cation exchangers, groups having hydrophobic interactions, groups having polarization interactions, and groups that combine several of the aforementioned properties. Since it has been found that in many applications bivalent metal ions can give rise for considerable hindrances, it has further been proposed according to the invention that all parts that come in contact with the solvents consist of noble metal, glass or plastic, or have adequate coatings of noble metal, glass or plastic.
More particularly, in accordance with a preferred embodiment of the invention, there is provided a process for the chromatographic separation of nucleic acids using a chromatographic carrier prepared by reacting a carrier material that contains cavities and has a grain size of from 2 to 100 μm, a cavity size of from 10 to 4000 nm and a specific surface of from 5 to 800 m 2 /g with a silanization reagent of the general formula
R.sub.1 R.sub.2 R.sub.3 SiR.sub.4 I.
wherein R 1 corresponds to one alkoxy radical having from 1 to 10 C atoms, preferably --OCH 3 , --OC 2 H 5 or --OC 3 H 7 , or one halogen atom, preferably --Cl, or one dialkyl amino group with identical or different alkyl radicals having from 1 to 6 C atoms, R 2 and R 3 correspond to a hydrocarbon radical having from 1 to 10 C atoms, preferably --CH 3 , --C 2 H 5 or C 3 H 7 , or an alkoxy radical having from 1 to 10 C atoms, preferably --OCH 3 , --OC 2 H 5 or --OC 3 H 7 , or one halogen atom or one alkyl radical having from 4 to 20 C atoms interrupted by at least one oxy or amino group, wherein said radical can also be replaced once or more by halogen, cyano, nitro, amino, monoalkylamino, dialkylamino, hydroxy or aryl, and R 4 corresponds to a hydrocarbon chain having from 1 to 20 C atoms or an alkyl radical interrupted by at least one oxy or amino group, wherein said radical can also be replaced once or more by halogen, cyano, nitro, amino, monoalkylamino, dialkylamino, alkoxy, hydroxy, aryl and/or epoxy, preferably ##STR1## and then, to form the final carrier, reacting the carrier containing said cavities with a reagent of the general formula
X-R-Y II
wherein X is an amino, hydroxy, epoxy group or one halogen atom, R is a hydrocarbon chain having from 2 to 20 C atoms, or an alkyl radical interrupted by at least one oxy or amino group, wherein said radical can also be replaced once or more by halogen, cyano, nitro, amino, monoalkylamino, dialkylamino, alkoxy, hydroxy, aryl and/or epoxy and Y is a hydrocarbon radical having from 1 to 10 C atoms and functional groups that form anion or cation exchangers, wherein said radical can be replaced once or more by amino, monoalkylamino, dialkylamino, quaternary alkylamino, carboxyl, boric acid, alkyl and aryl sulfonic acid groups, wherein the diameter of the cavities amounts to from 1 to 40 times, more preferably 1 to 20 times the maximum dimension of the respective nucleic acid to be isolated or the maximum dimension of the largest of all nucleic acids contained in the mixture.
In a particularly preferred embodiment of the invention, the carrier material used has a cavity size of from 50 to 1000 nm and a specific surface of at most 200 m 2 /g. Preferably silicon dioxide is used as carrier material. In one preferred embodiment of the invention, the cavities are formed by semispherical recesses; in another preferred embodiment the cavities are tubular. Preferably the solution containing nucleic acids to be separated and the elution substance are kept free from bivalent metal ions by using noble metal, glass and/or plastic for columns, pipes, valves and pumps of the chromatographic equipment.
BRIEF DESCRIPTION OF THE DRAWING
The invention is explained in more detail with reference to the figures, which show:
FIGS. 1A, 1B, and 1C show segments and cross sections through carrier materials of different cavity sizes; and
FIGS. 2, 3, 4, 5 and 6 are graphic illustrations of separations profiles obtained in accordance with the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The invention is explained in more detail in the following examples:
EXAMPLE 1
A weak anion exchanger according to the present invention was synthesized by the following process:
Commercial 50 g LiChrosphere SI 4000 silica gel particles (E. Merck, Darmstadt, Germany) with a partical size of 10 μm and a poresize of 4000 Angstroms is activated in a 1000 ml three-necked flask at a pressure of <1 mbar for 24 hours at the temperature of 200° C. After cooling, it was aerated with dry nitrogen and suspended in 100 ml dry γ-glycidooxypropyl-trimethoxysilane in 500 ml dry toluene and 1 ml tributylamine. The reaction took place for 10 hours reflux under a nitrogen atmosphere and with continuous stirring at 400 rpm. After the reaction, the excess γ-glycidooxypropyl-trimethoxysilane and toluene were removed by suction and the product epoxy-silica was washed four times with 400 ml dry hexane and two times 400 ml dry ether and dried in vacuo. With a four-necked flask including an inner thermometer, return-flow cooler, stirrer and nitrogen inlet pipe, the epoxy-silica gel was reacted with 100 ml dry N,N-diethyl-aminoethanol in 400 ml toluene. The reaction was catalyzed by addition of 1 ml BF 3 /ether and boiled for 12 hours under reflux. After reaction, the final chromatographic resin dimethylamino-silica gel (DEAE-Silica) was removed by suction and washed two times with 400 ml dioxane, 400 ml methanol and 200 ml ether, and dried at 50° C. in vacuo. The yield amounted to 51.5 g.
For column packing 3 g of the resulting chromatographic resin was dispersed in 50 ml methanol and was fed under pressure into a stainless steel column (diameter 6 mm, length 125 mm) connected to a 50 ml packing reservoir at a flow-rate of 5 ml/min with a high-pressure pump with methanol as an eluent. The packed column was disconnected from the packing reservoir, washed with methanol and water and connected to a liquid chromatograph (DuPont LC 850) equipped with a UV-detector. The separation is carried out with a gradient elution of increasing KCl concentration in 5 M urea, 30 mM potassium-phosphate buffer, pH 6.5
EXAMPLE 2--EFFECT OF PORE SIZE
The effect of the cavity size of the chromatographic resin on the interaction with the macromolecule is explained with reference to FIG. 1. A macromolecule (1) cannot sufficiently penetrate in the too small cavity (2) of the carrier material (3) in order to enter into an optimal interaction. On the other hand, the cavity (4) of more favorable dimensions permits very intensive interactions. To increase the interactions, the interaction producing groups are anchored on the cavity surface by flexible chain molecules (5). If on the contrary the cavity (6) is too large, then a reduction in interaction is again to be expected.
In FIG. 2 are illustrated separation examples of long-chain nucleic acids. The cavity diameters are - as indicated in the drawing--100 Angstroms, 300 Angstroms, 500 Angstroms and 4000 Angstroms. As example for a separation of long-chain nucleic acids, there was selected a natural mixture of transfer RNA (80 Angstroms size), ribosomal 5S RNA (110 Angstromes size), 7S RNA (300 Angstroms size) and viroid RNA (450 Angstroms size, a plant pathogene infectious RNA). It can be clearly seen in FIG. 2 that the largest pore size selected gave the best separation, and it is not to be ruled out that with a cavity size between 1000 Angstroms and 4000 Angstroms a still better separation would be obtained. In FIG. 4 the example from FIG. 2 has been further optimized by a shallower gradient elution. A complete separation of all four components is obtained. The diethylamino silica gels used in the examples had the loading capacity of 4.8 mg nucleic acid mixture/g (100 Angstroms), 17 mg nucleic acid mixture/g (500 Angstroms) and 5.6 mg nucleic acid mixture/g (4000 Angstroms).
EXAMPLE 3--SEPARATION OF OLIGORIBONUCLEIC ACIDS
Oligo-ribo-adenylic acids with chain lengths from 3 to 40 nucleotides were chromatographically purified using the anion-exchange resin obtained in Example 1 (FIG. 3). Synthetic oligonucleotides of defined length and sequence are required for modern genetic engineering and molecular biology.
Column: 6 mm×125 mm stainless steel, elution with a linear gradient from 0 to 1 M KCl in 200 min, in 5 M urea, 30 mM potassium-phosphate buffer, pH 5.5, at a flow rate of 1 ml/min, 35 bar, 22° C.
EXAMPLE 4--VIROID RNA
Viroid RNA (PSTV) from total RNa from infected plants was chromatographically purified using the anion-exchange resin obtained in Example 1 (FIG. 4). The purified nucleic acid was pure to spectroscopic, hydrodynamic and thermodynamic properties and was fully active in enzymatic experiments.
Column: 6 mm×125 mm stainless steel, elution with a linear gradient from 250 mM to 1000 mM KCl in 200 min, in 5 M urea, 30 mM potassium-phosphate buffer, pH 6.5, flow rate 1.5 ml/min, 45 bar, 22° C.
EXAMPLE 5--DNA-RESTRICTION FRAGMENTS
Chromatography of high molecular weight DNA restriction fragments was carried out using the anion-exchange resin obtained in Example 1 (FIG. 5). The DNA fragments were obtained by digestion of pBR 322 plasmid DNA with Hinf 1 yielding following sizes: 75, 154, 220, 298, 344, 396, 506, 517 and 1631 basepairs, respectively. It is remarkable that even the 506 and 517 basepair fragments could be separated from each other.
Column: 6 mm×125 mm stainless steel, elution with a linear gradient from 700 mM to 1200 mM KCl in 100 min, in 5 M urea, 30 mM potassium-phosphate buffer, pH 6.5, flow rate 1 ml/min, 35 bar 22° C.
EXAMPLE 6--PLASMID DNA FROM CRUDE CELL LYSATE
Purification of 50 μg plasmid pBR 322 DNA from crude cell lysate prepared by the lysozyme/EDTA method (D. B. Clewell and D. R. Hellinsky, proceedings of the National Academy of Sciences, USA (1969), 62, 1159-1166) was carried out using the anion-exchange resin obtained in Example 1 (FIG. 6). Column: 6 mm×125 stainless steel, elution with a linear gradient from 300 mM to 1500 mM KCl in 50 min, in 5 M urea, 30 mM potassium-phosphate buffer, Ph 6.5, flow rate 1.5 ml/min, 45 bar, 22° C.
Various changes may be made in the foregoing process without departing from the spirit and scope of the present invention. | A process for the chromatographic separation of nucleic acid using a chromatographic carrier material is described in which the surface of the carrier material is specially modified. | 1 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of priority to U.S. Provisional Application Ser. No. 62/265,520, filed Dec. 10, 2015, the disclosure of which is herein incorporated by reference in its entirety.
FIELD
[0002] The present disclosure generally relates to the field of endoscopy and specifically, to systems and methods for visualizing lesions and/or tumors within the gastrointestinal (GI) tract. In particular, the present disclosure relates to an extendable and retractable endoscopic hood that provides enhanced visibility as compared to an endoscope alone without interfering with the ability to navigate the endoscope through the narrow strictures and tortuous anatomy of the GI tract.
BACKGROUND
[0003] Endoscopes are commonly used to detect colorectal cancers within the gastrointestinal (GI) tract during a colonoscopy procedure. Some lesions and/or tumors are relatively easy to visualize due to their raised profile and/or large size. However, many lesions and/or tumors include a flat or depressed profile that makes them difficult to identify. This is especially true when these lesions and/or tumors are small and/or hidden within folds of the lumen wall. Visibility may be improved by incorporating an opaque or transparent hood on the distal end of the endoscope, which allows the folds of the lumen wall to be exposed. Unfortunately, endoscopic hoods dramatically reduce the ability of the endoscope to navigate the tortuous anatomy of the GI tract. For example, retroflexion in the colon may be more difficult with an endoscopic hood. In some instances, the endoscopic hoods may also collect feces/debris that obstructs visibility. Once visibility is obstructed, the endoscope must be withdrawn from the patient to clear the feces/debris, thereby prolonging the procedure and increasing the risk of harm to the patient. If strict bowel preparation procedures are not followed, many colonoscopy procedures must be prematurely terminated or canceled altogether.
SUMMARY
[0004] The present disclosure provides an extendable/retractable endoscopic hood that allows physicians to more readily identify small, flat and/or depressed lesions and/or tumors.
[0005] In one embodiment, the present disclosure provides an endoscopic system comprising an endoscope comprising an elongate body having a proximal end and a distal end; an endoscopic hood coupled to the distal end of the endoscope, the endoscopic hood comprising a proximal end, a distal end, and a lumen extending therebetween, wherein the lumen is configured to receive the distal end of the endoscope; a flexible inflatable member coupled to the distal end of the endoscopic hood, wherein the inflatable member is moveable between a deflated retracted configuration and an inflated extended configuration; and a conduit disposed alongside the elongate body of the endoscope, the conduit comprising a proximal end, and a distal end, wherein the distal end of the conduit is fluidly connected to a lumen of the inflatable member. The inflatable member may comprise a non-compliant or semi-compliant (e.g., semi-rigid) material, including, by way of non-limiting example, PEBAX, PET, PEN, PBT, PEEK, Hytrel, polyurethane and nylon. The non-compliant or semi-compliant material may be transparent. The inflatable member may include a balloon. The distal end of the inflatable member may be substantially longitudinally coextensive with the distal end of the endoscope when the inflatable member is in the deflated retracted configuration. The inflatable member may comprise one or more folds when in the deflated retracted configuration. At least a portion of the inflatable member may extend distally beyond the distal end of the endoscope when the inflatable member is in the inflated extended configuration. The portion of the inflatable member that extends distally beyond the distal end of the endoscope may form a hollow cylinder. An inner or outer surface of the hollow cylinder may include a series of parallel and evenly spaced line segments. The proximal end of the conduit may be fluidly connected to a fluid source, including, by way of non-limiting example, a gas or a liquid. The conduit may include a hydraulic tube. Flowing a fluid into the lumen of the inflatable member may move the inflatable member into the extended configuration, and flowing a fluid out of the lumen of the inflatable member may move the inflatable member into the retracted configuration.
[0006] In another embodiment, the present disclosure provides an endoscopic system comprising an endoscope comprising an elongate body having a proximal end, and a distal end, wherein at least a portion of the distal end includes a threaded outer surface; an endoscopic hood coupled to the distal end of the endoscope, wherein endoscopic hood is moveable between a retracted configuration and an extended configuration, the endoscopic hood comprising a proximal end, a distal end, a threaded inner surface, and a lumen extending between the proximal and distal ends, wherein the lumen is configured to receive the distal end of the endoscope such that the threaded outer surface of the endoscope rotatably engages the threaded inner surface of the endoscopic hood, an actuator disposed alongside the elongate body of the endoscope, the actuator comprising a proximal end, and a distal end, wherein the distal end of the actuator is coupled to the proximal end of the endoscopic hood and where the proximal end of the actuator is rotatable by user.
[0007] The endoscopic hood may comprise a transparent material, including, by way of non-limiting example, polymers including polyethylene, polyethylene terephthalate (PET), high-density polyethylene (HDPE), low density polyethylene (LDPE), polyvinyl chloride (PVC), polypropylene, polystyrene, polyester, polycarbonate, polyethersulfone, polyacrylate (PC) and polyetherketone (PEEK).
[0008] Rotating the proximal end of the actuator in a first direction may move the endoscopic hood distally along the threaded outer surface of the endoscope. Rotating the proximal end of the actuator in a second direction may move the endoscopic hood proximally along the threaded outer surface of the endoscope. A portion of the endoscopic hood may extend distally beyond the distal end of the endoscope when in the extended configuration. The portion of the endoscopic hood that extends distally beyond the distal end of the endoscope may be in the form of a hollow cylinder. An inner or outer surface of the hollow cylinder may include a series of parallel and evenly spaced line segments. The portion of the endoscopic hood that extends distally beyond the distal end of the endoscope may be unthreaded. The distal end of the endoscopic hood may be substantially longitudinally coextensive with the distal end of the endoscope when in the retracted configuration. The actuator may include a sheath disposed about a length of the endoscope body. The actuator may include a plurality of wires extending longitudinally along the elongate body. The actuator may further comprise a plurality of rings extending around the elongate body, wherein the rings are longitudinally spaced along a length of the elongate body, and wherein the plurality of wires are attached to the rings.
[0009] In another embodiment, the present disclosure provides a method of examining a body passageway, comprising inserting, into a body lumen of a patient, an endoscopic system comprising an endoscope comprising an elongate body having a proximal end and a distal end; an endoscopic hood coupled to the distal end of the endoscope, the endoscopic hood comprising a proximal end, a distal end, and a lumen extending therebetween, wherein the lumen is configured to receive the distal end of the endoscope; a flexible inflatable member coupled to the distal end of the endoscopic hood, wherein the inflatable member is moveable between a deflated retracted configuration and an inflated extended configuration; and a conduit disposed alongside the elongate body of the endoscope, the conduit comprising a proximal end, and a distal end, wherein the distal end of the conduit is fluidly connected to a lumen of the inflatable member, positioning a distal end of the endoscopic system adjacent a target tissue; moving the inflatable member from the retracted configuration to the extended configuration such that the inflatable member exerts a force against a fold in the target tissue, thereby exposing an obscured portion of the target tissue; and visualizing the obscured portion of the target tissue through the inflatable member. The method may further comprise moving the inflatable member from the extended configuration to the retracted configuration and repositioning the endoscope adjacent a different target tissue.
[0010] In another embodiment, the present disclosure provides a method of examining a body passageway, comprising inserting, into a body lumen of a patient, an endoscopic system comprising an endoscope comprising an elongate body having a proximal end, and a distal end, wherein at least a portion of the distal end includes a threaded outer surface; an endoscopic hood coupled to the distal end of the endoscope, wherein endoscopic hood is moveable between a retracted configuration and an extended configuration, the endoscopic hood comprising a proximal end, a distal end, a threaded inner surface, and a lumen extending between the proximal and distal ends, wherein the lumen is configured to receive the distal end of the endoscope such that the threaded outer surface of the endoscope rotatably engages the threaded inner surface of the endoscopic hood, an actuator disposed alongside the elongate body of the endoscope, the actuator comprising a proximal end, and a distal end, wherein the distal end of the actuator is coupled to the proximal end of the endoscopic hood and where the proximal end of the actuator is rotatable by user; positioning the endoscopic system adjacent a target tissue; moving the endoscopic hood from the retracted configuration to the extended configuration such that the distal end of the endoscopic hood exerts a force against a fold in the target tissue, thereby exposing an obscured portion of the target tissue; and visualizing the obscured portion of the target tissue through the endoscopic hood. The method may further comprise moving the endoscopic hood from the extended configuration to a retracted configuration and repositioning the endoscope adjacent a different target tissue.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] Non-limiting embodiments of the present disclosure are described by way of example with reference to the accompanying figures, which are schematic and not intended to be drawn to scale. In the figures, each identical or nearly identical component illustrated is typically represented by a single numeral. For purposes of clarity, not every component is labeled in every figure, nor is every component of each embodiment of the disclosure shown where illustration is not necessary to allow those of ordinary skill in the art to understand the disclosure. In the figures:
[0012] FIG. 1 depicts an endoscopic hood that includes an inflatable member in a retracted configuration, according to one embodiment of the present disclosure.
[0013] FIG. 2 depicts the endoscopic hood of FIG. 1 on the distal end of an endoscope, according to another embodiment of the present disclosure.
[0014] FIG. 3 depicts the endoscopic hood of FIG. 1 on the distal end of an endoscope with the inflatable member in an extended configuration, according to another embodiment of the present disclosure.
[0015] FIG. 4 depicts an endoscopic hood that includes a threaded inner surface, according to another embodiment of the present disclosure.
[0016] FIG. 5 depicts the endoscopic hood of FIG. 4 in a retracted configuration on the distal end of an endoscope, according to another embodiment of the present disclosure.
[0017] FIG. 6 depicts the endoscopic hood of FIG. 4 in an extended configuration on the distal end of an endoscope, according to another embodiment of the present disclosure.
[0018] FIG. 7 depicts an alternative embodiment of an endoscopic hood that includes a threaded inner surface, according to another embodiment of the present disclosure.
[0019] FIGS. 8A-8B depict an endoscopic hood on the distal end of an endoscope positioned within the GI tract, with the inflatable member in a retracted configuration adjacent to a lesion hidden within a fold of the lumen wall ( FIG. 8A ), and the inflatable member in an extended configuration exposing the hidden lesion ( FIG. 8B ), according to one embodiment of the present disclosure.
[0020] FIGS. 9A-9B depict an endoscopic hood on the distal end of an endoscope positioned within the GI tract, with the endoscopic hood in a retracted configuration adjacent to a lesion hidden within a fold of the lumen wall ( FIG. 9A ), and the endoscopic hood in an extended configuration exposing the hidden lesion ( FIG. 9B ), according to another embodiment of the present disclosure.
[0021] It is noted that the drawings are intended to depict only typical or exemplary embodiments of the disclosure. It is further noted that the drawings may not be necessarily to scale. Accordingly, the drawings should not be considered as limiting the scope of the disclosure. The disclosure will now be described in greater detail with reference to the accompanying drawings.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0022] Before the present disclosure is described in further detail, it is to be understood that the disclosure is not limited to the particular embodiments described, as such may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting beyond the scope of the appended claims. Unless defined otherwise, all technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the disclosure belongs. Finally, although embodiments of the present disclosure are described with specific reference to an endoscope hood attached to the distal end of an endoscope, the endoscope hood disclosed herein may be attached to a variety of medical devices that are inserted into a variety of lumens of a patient, including for example, guide lumens, ports, optical wands and the like. As used herein, the term “distal” refers to the end farthest away from a medical professional when introducing a device into a patient, while the term “proximal” refers to the end closest to the medical professional when introducing a device into a patient.
[0023] In one embodiment, the present disclosure provides a transparent retractable extension (TRE) endoscopic system for visualizing small and/or hidden lesions or tumors within the lumen wall of the GI tract. As illustrated in FIG. 1 , in one embodiment the endoscopic system of the present disclosure may include an endoscopic hood 110 comprising a proximal end 114 , a distal end 116 and a lumen 118 extending therebetween. A flexible inflatable member 120 (e.g. a balloon) is coupled to the distal end 116 of the endoscopic hood 110 . A conduit 130 comprising a distal end 136 is disposed along an outer surface of the endoscopic hood 110 , such that the distal end 136 of the conduit 130 is fluidly connected to a lumen of the flexible inflatable member 120 . The proximal end (not shown) of the conduit 130 is fluidly connected to a fluid source (not shown) to deliver an inflation fluid into the lumen of the flexible inflatable member. The inflation fluid may include a variety of physiologically inert liquids (e.g., buffered solutions such as sterile saline) or gases (e.g., oxygen, nitrogen, hydrogen, carbon dioxide, helium etc.) as are known in the art. The flexible inflatable member 120 may be moveable from a deflated retracted configuration 120 a comprising one or more folds 122 , to an inflated extended configuration 120 b ( FIG. 3 ) by flowing the inflation fluid from the fluid source into the lumen of the flexible inflatable member 120 . Similarly, the flexible inflatable member 120 may be moveable from an inflated extend configuration 120 b to a deflated retracted configuration 120 a by flowing the inflation fluid from the lumen of the flexible inflatable member 120 back to the fluid source.
[0024] The flexible inflatable member 120 may include a combination of elastomeric and semi to non-compliant materials that lack elastic properties and can only assume one shape when in the expanded configuration. In one embodiment, the non-compliant or semi-compliant material of the flexible inflatable member 120 is transparent. For example, flexible inflatable member 120 may include one or more thermoplastics and/or thermosets. Examples of thermoplastics include polyolefins; polyamides (e.g., nylon, such as nylon 12, nylon 11, nylon 6/12, nylon 6, nylon 66); polyesters (e.g., polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polytrimethylene terephthalate (PTT)); polyethers; polyurethanes; polyvinyls; polyacrylics; fluoropolymers; copolymers and block copolymers thereof, such as block copolymers of polyether and polyamide (e.g., PEBAX®); and mixtures thereof. Examples of thermosets include elastomers (e.g., EPDM), epichlorohydrin, polyureas, nitrile butadiene elastomers and silicones. Other examples of thermosets include epoxies and isocyanates. Biocompatible thermosets may also be used. Biocompatible thermosets include, for example, biodegradable polycaprolactone, poly(dimethylsiloxane) containing polyurethanes and ureas and polysiloxanes. Ultraviolet curable polymers, such as polyimides and acrylic or methacrylic polymers and copolymers may also be used.
[0025] Referring to FIG. 2 , the lumen 118 of the endoscopic hood 110 may be configured to receive (e.g., via frictional or interference fit) the distal end 106 of an endoscope 100 . The conduit 130 and endoscopic hood 110 may be further secured longitudinally along the elongate body 102 of the endoscope 100 by one or more clips 124 . While the clip 124 of FIG. 2 engages a full circumference of the outer surface of the elongate body 102 , a variety of clip configuration are contemplated by the present disclosure, including, for example, clips that only engage a portion of the outer surface of the elongate body. To facilitate navigation within the tortuous anatomy of the GI tract, the flexible inflatable member 120 may be substantially longitudinally coextensive (e.g., flush) with the distal end 106 of the endoscope 100 when in the deflated retracted configuration 120 a. As illustrated in FIG. 3 , the flexible inflatable member 120 may move from a deflated retracted configuration 120 a ( FIG. 2 ) to an inflated extended configuration 120 b by flowing an inflation fluid from the fluid source (not shown) through conduit 130 into the lumen of the flexible inflatable member 120 such that at least a portion of the flexible inflatable member 120 forms a hollow cylinder that extends distally beyond the distal end 106 of the endoscope 100 . In one embodiment, the hollow cylinder may include a series of parallel and evenly spaced line segments (not shown) to allow the physician to monitor how far the distal end 126 of the inflatable member 120 extends beyond the distal end 106 of the endoscope 100 . As will be understood by one of skill in the art, the line segments (e.g., marked lines, hatch marks, hash marks, tick marks, etc.) may be formed, etched, scribed and/or drawn on an inner or outer surface of the hollow cylinder.
[0026] As illustrated in FIG. 4 , in another embodiment the endoscopic system of the present disclosure may include an endoscopic hood 210 comprising a proximal end 214 , a distal end 216 and a lumen 218 extending therebetween. The endoscopic hood 210 may be formed from a translucent or transparent material, such as a clear polymer-based material (e.g., clear plastics, etc.) as are known in the art. In one embodiment, a proximal portion of the endoscopic hood 210 defining the lumen 218 may include a threaded inner surface 215 while a distal portion of the endoscopic hood 210 defining the lumen 218 may be unthreaded 217 (e.g., smooth). An actuator 230 may extend proximally from the proximal end 214 of the endoscopic hood 210 . In one embodiment, the actuator 230 may include a plurality of wires/cables 240 connected to each other by one or more rings 242 .
[0027] Referring to FIG. 5 , the lumen 218 of the endoscopic hood 110 may be configured to receive the distal end 206 of an endoscope 200 . In one embodiment, a portion of the distal end 206 of the endoscope 200 may include a threaded outer surface 208 configured to rotatably engage the corresponding threaded inner surface 215 of the endoscopic hood 210 . The plurality of wires/cables 240 of the actuator 230 may extend longitudinally along the elongate body 202 of the endoscope 200 . One or more rings 242 may be longitudinally spaced along the length of the elongate body 202 of the endoscope 200 to connect the plurality of wire/cables 240 . The wire/cables 240 and rings 242 may be formed from may sufficiently flexible and torsionally compliant materials (e.g., shape-memory polymers and/or shape-memory metals as are known in the art) to bend and/or flex as the endoscope is advanced and/or retracted through a body lumen of the patient, while still being able to translate rotational force at the proximal end (not shown) of the actuator 230 to the endoscopic hood 210 . To facilitate navigation within the tortious anatomy of the GI tract, the endoscopic hood 210 may be substantially longitudinally coextensive (e.g., flush) with the distal end 206 of the endoscope 200 when in the retracted configuration 210 a. As illustrated in FIG. 6 , the endoscopic hood 210 may move from a retracted configuration 210 a ( FIG. 5 ) to an extended configuration 210 b by rotating the proximal end (not shown) of actuator 230 in a first (e.g., clockwise) direction along the threaded outer surface 208 of the endoscope 200 such that at least a portion of the endoscopic hood 210 forms a hollow cylinder that extends distally beyond the distal end 206 of the endoscope 200 . In one embodiment, as discussed above, an inner and/or outer surface of the hollow cylinder may include a series of parallel and evenly spaced line segments (not shown) to allow the physician to monitor how far the distal end 216 of the endoscopic hood 210 extends beyond the distal end 206 of the endoscope 200 . Still referring to FIG. 6 , in one embodiment, the portion of the endoscopic hood 210 extending distally beyond the distal end 206 of the endoscope 200 may include a smooth (e.g., unthreaded) inner surface 217 , thereby minimizing surface area for intestinal debris to collect within the lumen 218 of the endoscopic hood 210 . The endoscopic hood 210 may be moveable from the extended configuration ( FIG. 6 ) to the retracted configuration ( FIG. 5 ) by rotating the proximal end (not shown) of actuator 230 in a second (e.g., counter-clockwise) direction along the threaded outer surface 208 of the endoscope 200 .
[0028] Referring to FIG. 7 , in another embodiment the actuator may include an elongate sheath 238 disposed about and extending longitudinally along the length of the elongate body 202 of the endoscope 200 . As with actuator 230 , the endoscopic hood may be moved from the retracted configuration to the extended configuration by rotating the proximal end (not shown) of the elongate sheath 238 in a first (e.g., clockwise) direction along the threaded outer surface 208 of the endoscope 200 , and from the extended configuration to the retracted configuration by rotating the proximal end (not shown) of the elongate sheath 238 in a second (e.g., counter-clockwise) direction along the threaded outer surface 208 of the endoscope 200 .
[0029] As illustrated by FIGS. 8A-8B , in use and by way of example, the endoscopic system of FIG. 2 may be inserted into a body lumen (e.g., GI tract) of a patient such that the distal end 106 of the endoscope 100 is positioned adjacent a target tissue that includes one or more folds 10 that the physician believes to be hiding or otherwise obstructing visualization of a lesion 5 . The flexible inflatable member 120 may then be moved from the deflated retracted configuration ( FIG. 8A ) to an inflated extended configuration ( FIG. 8B ) as explained above such that the distal end 126 of the flexible inflatable member 120 extends distally beyond the distal end 106 of the endoscope 100 . When in the inflated extended configuration the distal end 126 of the flexible inflatable member 120 exerts a longitudinal force against one or more folds of the lumen wall, thereby stretching and exposing the target tissue hidden or obscured within the fold. The physician may then visualize the target tissue, which may include a lesion, through the transparent material of the flexible inflatable member 120 . If the exposed tissue does in fact include a lesion, the physician may then resect the tissue using methods known in the art, or alternatively, make note of the lesion for resection by a subsequent interventional procedure. The physician may then return the flexible inflatable member 120 to the deflated retracted configuration ( FIG. 8A ) as discussed above, and reposition the distal end 106 of the endoscope 100 adjacent to the fold of another target tissue and repeat the steps outlined above. In addition to exposing tissues within the folds of the lumen wall, moving the flexible inflatable member 120 from the inflated extended configuration to the deflated retracted configuration allows intestinal debris that may have become lodged within the hollow cylindrical opening of the flexible inflatable member to be cleared from the endoscope.
[0030] As illustrated by FIGS. 9A-9B , in use and by way of example, the endoscopic system of FIG. 5 may be inserted into a body lumen (e.g., GI tract) of a patient such that the distal end 206 of the endoscope 200 is positioned adjacent a target tissue that includes one or more folds 10 that the physician believes to be hiding or otherwise obstructing visualization of a lesion 5 . The endoscopic hood 210 may then be moved from the retracted configuration ( FIG. 9A ) to an extended configuration ( FIG. 9B ) as explained above such that the distal end 216 of the endoscopic hood 210 extends distally beyond the distal end 206 of the endoscope 200 . When in the extended configuration the distal end 216 of the endoscopic hood 210 exerts a longitudinal force against one or more folds of the lumen wall, thereby stretching and exposing the target tissue hidden or obscured within the fold. The physician may then visualize the target tissue, which may include a lesion, through the transparent material of the endoscopic hood. If the exposed tissue does in fact include a lesion, the physician may then resect the tissue using methods known in the art, or alternatively, make note of the lesion for resection by a subsequent interventional procedure. The physician may then return the endoscopic hood 210 to the retracted configuration ( FIG. 9A ) as discussed above, and reposition the distal end 206 of the endoscope 200 adjacent to the fold of another target tissue and repeat the steps outlined above. In addition to exposing tissues within the folds of the lumen wall, moving the endoscopic hood 210 from the extended configuration to the retracted configuration allows intestinal debris that may have become lodged within the hollow cylindrical opening of the flexible inflatable member to be cleared from the endoscope. Accumulation of intestinal debris within the endoscopic hood may be further minimized by the smooth (e.g., unthreaded) inner surface 217 of the endoscopic hood which extends distally beyond the distal end 206 of the endoscope 200 .
[0031] All of the devices and/or methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the devices and methods of this disclosure have been described in terms of preferred embodiments, it may be apparent to those of skill in the art that variations can be applied to the devices and/or methods and in the steps or in the sequence of steps of the method described herein without departing from the concept, spirit and scope of the disclosure. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the disclosure as defined by the appended claims. | The present disclosure relates to the field of endoscopy. In particular, the present disclosure relates to systems and methods for navigating the tortious anatomy of the gastrointestinal (GI) tract and visualizing lesions and/or tumors obscured within folds of the lumen wall. | 0 |
FIELD OF THE INVENTION
This invention relates to the field of dry creamer powders for use in the food industry.
BACKGROUND OF THE INVENTION
Dry creamer powders are useful in the food industry as an economical and convenient replacement for liquid dairy products. As compared with liquid milk or cream, dry creamer powders have increased stability and ease of handling. A common use for creamer powders is their addition to hot beverages such as coffee or tea, where they provide a visual whitening effect and a palatable improvement. Creamer powders are further utilized as a milk substitute in the preparation of diverse food products such as sauces, beverages, shakes, foaming beverages, soups, salad dressings, food coatings, baked goods, puddings, confections, ice cream, frozen confections, and non-baked food products.
Compositions for dry creamer powders generally are known. A creamer powder composition usually comprises a dried emulsion of carbohydrate, fat or oil, and protein with added emulsifiers, stabilizers, and/or buffers. Most creamer powders are designed to be soluble in hot beverages. For example, U.S. Pat. No. 4,046,926 describes a typical hot-water soluble, non-dairy creamer composition that includes (by weight) 35-65% carbohydrate, 20-40% fat, 3-15% protein, emulsifiers and stabilizers. An example of a creamer powder that is soluble in cold water is described in publication WO 98/07329. This publication discloses a creamer powder composition that includes (by weight). 30-70% carbohydrate, 25-45% fat and 0.5-6% protein, emulsifiers and stabilizers. A creamer powder, whether soluble in hot or cold water, typically has carbohydrate and fat as major components by weight, and protein is a relatively minor component.
The edible fat in a creamer powder composition may be a fat or oil derived from animals or plants. Most typically, the edible fat is a vegetable fat or oil that is bland and neutral in taste. Coconut oil, for example, has been widely used. The WO 98/07329 publication discloses a cold water soluble creamer powder that uses sunflower oil, canola oil, or rapeseed oil.
Currently, an emphasis exists on the restriction of carbohydrate in the human diet as an aid to weight reduction. Restriction of carbohydrates in foods also may be recommended for people with medical conditions such as diabetes, epilepsy, and inherited disorders of carbohydrate metabolism. It is generally accepted in the food industry, however, that creamer powders contain a range of 30%-70% by weight carbohydrate for flavor, bulking or stability of the powdered emulsion. Few creamer powders have a carbohydrate content lower than 35% by weight. U.S. Pat. No. 6,020,017 discloses a range of 5-35% carbohydrate, and U.S. Pat. No. 4,446,164 discloses a range of 5%-40% carbohydrate.
Therefore, a need exists in the food industry for a creamer powder that is low in carbohydrate content for the preparation of nutritious, carbohydrate-restricted foods.
It is the principal object of the present invention to provide a composition for a creamer powder that has a low carbohydrate content.
The source of water-soluble protein in powdered creamers is usually a milk product, such as sodium caseinate (U.S. Pat. No. 4,046,926), whey protein (U.S. Pat. No. 4,446,164), or dry milk solids (U.S. Pat. No. 5,284,674). Although alternative sources of water-soluble proteins are known, these patents each disclose unsuccessful attempts to replace sodium caseinate with other water-soluble proteins in creamer powder compositions. Further, the '674 patent discloses that calcium caseinate is insoluble and is not preferred for use in a creamer powder.
U.S. Pat. No. 4,415,600 teaches that improved whitening can be obtained by replacing an amount of the sodium caseinate, up to 60%, with a soy protein derivative such as soy protein isolate, soy protein concentrate, or modified soy flour. However, the total protein in this creamer powder composition is only 5.25% by weight.
It is a further object of the present invention to provide a composition for a creamer powder that is low in carbohydrate and high in protein content.
It is a further object of the present invention to provide a composition that allows for variation in the source of soluble protein.
It is a further object of the present invention to provide a composition for a creamer powder that is low in carbohydrate and high in protein content by weight, and disperses easily in either hot or cold water-based liquids.
SUMMARY OF THE INVENTION
According to the present invention, the carbohydrate component of a dry creamer powder composition can be decreased significantly relative to the protein and fat components. Combinations of water-soluble protein, carbohydrate, and edible fat, appropriately emulsified and stabilized, can be processed to form a creamer powder that has less than approximately 5% carbohydrate by weight. Preferably, the creamer powder is stable in powder form, and also may be easily dispersed in hot or cold water-based liquids.
The creamer powder in one embodiment comprises high oleic vegetable oil as the preferred edible fat and calcium caseinate as the preferred water-soluble protein. In another embodiment, the creamer powder composition utilizes sources of water-soluble proteins other than milk-derived casein proteins. In yet another embodiment, the creamer powder composition contains mixtures of animal and plant water-soluble proteins.
The creamer powder may be utilized as an ingredient in foods where reduction of carbohydrate content and a nutritious food product are desired. Three embodiments disclose the use of the present invention as an ingredient in dry mix soup compositions. A further embodiment discloses the utilization of the creamer powder in a beverage.
The present invention may be useful in the preparation of foods, not only for people desiring weight reduction, but also for people with medical conditions requiring restriction of carbohydrate intake.
DETAILED DESCRIPTION OF THE INVENTION
According to the present invention, the carbohydrate component is decreased significantly relative to the protein and fat components of a dry creamer powder. Combinations of edible fat, water-soluble protein, carbohydrate and optional additives, appropriately emulsified and stabilized, are disclosed to form a creamer powder that has less than approximately 5% carbohydrate by weight.
The creamer powder of the present invention may contain from about 30% to 70% by weight of an edible fat component. The content of edible fat preferably ranges from about 40% to about 55%. Very preferably, the edible fat content is approximately 50%.
Edible fats suitable for use may include fats or oils from animal and/or vegetable sources. These edible fats may include saturated fats, monounsaturated fats, and/or polyunsaturated fats. A vegetable oil, preferably a monounsaturated vegetable oil, is favored.
The mono-unsaturated vegetable oil is very preferably non-hydrogenated to limit the content of trans fatty acids. Partially hydrogenated vegetable fats or oils may produce trans fatty acids. Since trans fatty acids are associated with an increase in low-density lipoproteins (LDL) in vivo, they should be restricted in nutrition for good health.
The term “long length fatty acids” as used herein refers to fatty acids with hydrocarbon chains ranging from fourteen to twenty-two carbons in length.
It is further preferred that the vegetable oil contains a high content by weight of oleic fatty acids. Oleic acid is an unsaturated fatty acid with a hydrocarbon chain that is eighteen carbons in length. The oleic acid fatty acid content of the vegetable oil preferably is at least 70% by weight. It is most preferred that the oleic acid content of the vegetable oil is approximately 85% by weight.
Monounsaturated, non-hydrogenated vegetable oils that are very preferred comprise sunflower oil, soybean oil, and canola oil. For example, a particularly preferred non-hydrogenated, mono-unsaturated sunflower oil is “TRI-SUN Extra AS100” from Ingredients International (AC Humko, 1115 Tiffany St., Boyceville, Wis. 54725). As described by the manufacturer, this oil is a high oleic sunflower oil extracted from traditionally crossbred sunflower crops and exhibits much greater stability than regular sunflower oil. The oleic fatty acid content is about 85%. It is low in saturated fat, contains no trans fatty acids, and has a neutral odor and taste. Tocopherol has been added to TRI-SUN Extra AS100 for oxygen stability without hydrogenation.
Alternatively, an oleic safflower oil that is known to be very stable also is very preferable for use in the present invention. For example, “Oleic safflower oil RBD” (Ingredients International, AC Humko) is a naturally stable liquid oil that has at least 75% by weight oleic acid. “Oleic safflower oil RBD” is a non-hydrogenated oil that is low in saturated fatty acids, has no trans fatty acids, and is high in mono-unsaturated fatty acids. It has a bland flavor, is growth hormone free, and is low in sodium.
The term “water-soluble protein” as used herein is defined as protein that is soluble in water-based liquids. The creamer powder of the present invention contains from about 40% to about 60% by weight of a water-soluble protein. The protein content preferably is about 40% to 50%. Very preferably, the protein content is approximately 45%.
The water-soluble protein component may be derived from animal protein and/or plant protein. The protein may be processed to improve its solubility in water; for example, hydrolyzed protein may be used in the present invention.
Animal proteins usable in the composition preferably comprise egg proteins, albumin, collagen, gelatin, and/or milk-derived proteins comprising casein, caseinate soluble protein, whey protein and/or demineralized whey protein.
For example, any of the caseinate soluble proteins comprising calcium caseinate, potassium caseinate, magnesium caseinate, and/or sodium caseinate may be used in the present invention. Calcium caseinate preferably is used. A source of calcium caseinate very preferred is “Alanate 385,” specification #13C385, from New Zealand Milk Products, Inc. (3637 Westwind Blvd., Santa Rosa, Calif. 95403). As described by the manufacturer, “Alanate 385” is a spray dried milk protein manufactured from fresh skim milk and surface treated with food grade glycerol mono-oleate. It is readily dispersible in water to form a stable colloidal suspension. “Alanate 385” has less than 0.01% sodium and exhibits excellent flavor stability. It is kosher, lactose-free, and recombinant growth hormone (rbGH) free, which is advantageous to meet consumer concerns.
Plant protein may be used in the present invention as the total protein component. Plant protein also may be used in various combinations as a mixture with animal protein in the present invention. Water-soluble proteins suitable for use in the present invention may be derived from plants. Nuts and seeds, as well as marine plants, can be used. Water-soluble proteins are preferably derived from the plants comprising bean, peanut, soybean, sunflower, flax, canola, oat, pea, wheat, and/or rice. The plant sources for water-soluble proteins most preferred comprise soybean, canola, sunflower and/or rice.
Carbohydrate may be included in the present invention only as needed and/or desired for quality, flavor characteristics and/or ease of production. Preferably, the carbohydrate content comprises less than 5% by weight of the creamer powder composition. The content of carbohydrate preferably ranges less than 3%. Very preferably, the carbohydrate content is less than 1% by weight of the creamer powder composition. Carbohydrate sources typically used in creamer powder compositions comprising corn syrup solids, fructose, maltose, and/or sucrose may be used in the present invention.
Any of the food approved emulsifiers typically used in creamer powders comprising mono-and diglycerides of fatty acids, lecithin, and soy lecithin may be used in the present invention. The content of mono- and diglycerides preferably ranges from about 2% to about 10% by weight of the creamer powder composition. The content of lecithin preferably is between 0% and 2%. Very preferably, mono- and diglycerides and lecithin are used in equal proportions.
Emulsion stabilizers are used in creamer powders to increase the stability of the emulsion and/or to aid in the maintenance of pH. Non-chemical and/or chemical stabilizers may be used in the present invention. The chemical stabilizers may comprise mineral citrates, mineral carbonates, mineral bicarbonates and/or mineral phosphates. The term “mineral” may comprise sodium, potassium, magnesium, aluminum, and/or calcium, and combinations thereof. Dipotassium phosphate and sodium citrate are preferred emulsion stabilizers in the present invention. The composition should include up to approximately 2% by weight emulsion stabilizers.
The creamer powder composition of the present invention may include additives to enhance the production, nutritional value, quality, and/or flavor of the creamer powder. The present invention also may contain additives that typically are used in the formulation of powdered creamer compositions, such as anti-caking agents and whitening agents. The optional additives may be chosen as appropriate for the food product to be prepared.
EXAMPLES
The following examples illustrate embodiments of the present invention, but are not meant in any way to restrict the effective scope of the invention. All parts and percentages are by weight unless otherwise noted.
Example 1
Composition of a Low-carbohydrate High-protein Creamer Powder
High oleic sunflower oil
50.7%
Calcium caseinate protein
44.6%
Lecithin (74% fat)
1.8%
Mono- and diglycerides
1.8%
Dipotassium phosphate
1.1%
100.0%
Example II
Composition of a Low-carbohydrate High-protein Creamer Powder: Soy Protein Isolate
High oleic sunflower oil
50.7%
Soy protein isolate
44.6%
Lecithin (74% fat)
1.8%
Mono- and diglycerides
1.8%
Dipotassium phosphate
1.1%
100.0%
Example III
Low-carbohydrate High-protein Creamer Powder: Protein Mixture
High oleic sunflower oil
50.7%
Calcium caseinate protein:soy
44.60%
protein isolate:whey protein isolate
(1:1:1)
Lecithin (74% fat)
1.80%
Mono- and diglycerides
1.80%
Dipotassium phosphate
1.10%
100.00%
Example IV
Dry Mix for Instant Soup (Beef Flavor) Using Low-carbohydrate High-protein Creamer Powder
Sunflower oil creamer powder
66.00%
(from EXAMPLE 1)
Beef flavor soup base
23.00%
(Superior Quality Foods,
2355 E. Francis, Ontario CA 91761)
Tomato powder
2.00%
Carrot powder
2.00%
Cabbage powder
2.00%
Broccoli powder
2.00%
Potato flakes
1.00%
Parsley flakes, dehydrated
1.00%
Corn starch (buffalo)
1.00%
100.00%
Example V
Dry Mix for Instant Soup (Vegetable Flavor) Using Low-carbohydrate High-protein Creamer Powder
Sunflower oil creamer powder (EXAMPLE 1)
62.00%
Vegetable base NMIDI (Superior Quality Foods)
31.00%
Carrot powder - 60
3.00%
Parsley flakes, dehydrated
2.00%
Corn starch (buffalo)
2.00%
100.00%
Example VI
Dry Mix for Instant Soup (Chicken Flavor) Using Low-carbohydrate High-protein Creamer Powder
Sunflower oil creamer powder (EXAMPLE 1)
67.00%
Chicken FIV soup base
29.00%
(Superior Quality Foods,
CFB LAS, SQF #909-923-733
Corn starch (buffalo)
3.00%
Parsley flakes, dehydrated
1.00%
100.00%
Example VII
Low-carbohydrate High-protein Creamer Powder Used in a Beverage
Calcium caseinate
48.50%
Low-carbohydrate creamer powder
30.00%
(EXAMPLE 1)
Whey protein isolate
12.70%
Natural flavors
3.50%
Vitamins and minerals
5.20%
Gums
0.10%
100.00%
While the invention is susceptible to various modifications and alternative forms, specific examples thereof have been shown by way of example and are herein described in detail. It should be understood, however, that the invention is not to be limited to the particular forms or methods disclosed; but to the contrary, the invention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the appended claims. | A composition for a creamer powder is disclosed that comprises approximately 40% to approximately 60% by weight water-soluble protein, edible fat, at least one emulsifier, at least one stabilizer and less than 5% by weight carbohydrate. The creamer powder composition is dispersible in either hot or cold water-based liquids. The low-carbohydrate high-protein creamer powder may be used in the preparation of nutritious, low-carbohydrate foods. | 0 |
This application is a continuation-in-part of U.S. Ser. No. 08/761,190, Dec. 6, 1996 which is a continuation-in-part of U.S. Ser. No. 08/345,820 filed Nov. 21, 1994 now U.S. Pat. No. 5,618,792.
The present invention relates to certain substituted oxadiazole, thiadiazole and triazole peptoids which are useful as inhibitors of serine proteases.
BACKGROUND OF THE INVENTION
The serine proteases are a class of enzymes which includes elastase, chymotrypsin, cathepsin G, trypsin and thrombin. These proteases have in common a catalytic triad consisting of Serine-195, Histidine-57 and Aspartic acid-102 (chymotrypsin numbering system). Human neutrophil elastase (HNE) is a proteolytic enzyme secreted by polymorphonuclear leukocytes (PMNs) in response to a variety of inflammatory stimuli. This release of HNE and its extracellular proteolytic activity are highly regulated and are normal, beneficial functions of PMNs. The degradative capacity of HNE, under normal circumstances, is modulated by relatively high plasma concentrations of α 1 -proteinase inhibitor (α 1 -PI). However, stimulated PMNs produce a burst of active oxygen metabolites, some of which (hypochlorous acid for example) are capable of oxidizing a critical methionine residue in α 1 -PI. Oxidized α 1 -PI has been shown to have limited potency as an HNE inhibitor and it has been proposed that alteration of this protease/antiprotease balance permits HNE to perform its degradative functions in localized and controlled environments.
Despite this balance of protease/antiprotease activity, there are several human disease states in which a breakdown of this control mechanism is implicated in the pathogenesis of the condition. Improper modulation of HNE activity has been suggested as a contributing factor in adult respiratory distress syndrome, septic shock and multiple organ failure. A series of studies also have indicated the involvement of PMNs and neutrophil elastase in myocardial ischemia-reperfusion injury. Humans with below-normal levels of α 1 -PI have an increased probability of developing emphysema. HNE-mediated processes are implicated in other conditions such as arthritis, periodontal disease, glomerulonephritis, dermatitis, psoriasis, cystic fibrosis, chronic bronchitis, atherosclerosis, Alzheimer's disease, organ transplantation, corneal ulcers, and invasion behavior of malignant tumors.
There is a need for effective inhibitors of HNE as therapeutic and as prophylactic agents for the treatment and/or prevention of elastase-mediated problems.
SUMMARY OF THE INVENTION
The present invention provides compounds which are useful as serine protease inhibitors, including human neutrophil elastase. These compounds are characterized by their relatively low molecular weight, high potency and selectivity with respect to HNE. Additionally, certain compounds of the invention have demonstrated oral bioavailability as exhibited by their higher blood levels after oral dosing. Oral bioavailability allows oral dosing for use in chronic disease, with the advantages of self-administration and decreased cost over other means of adminstration. The compounds described herein can be used effectively to prevent, alleviate or otherwise treat disease states characterized by the degradation of connective tissue by proteases in humans.
The present invention provides compounds comprising oxadiazole, thiadiazole or triazole ring structures, and can be generically described by the formula: ##STR1## wherein Z is a serine protease binding moiety, preferably an elastase binding moiety, and most preferably a human neutrophil elastase binding moiety. Specifically, Z is a carbonyl containing group, preferably an α-amino carbonyl containing group where the carbonyl carbon is covalently attached to the carbon of the heterocycle.
R 1 is alkyl, alkenyl or alkynyl optionally substituted with 1 or more, preferably 1-3, halo, hydroxyl, cyano, nitro, haloalkyl, alkylamino, dialkylamino, alkoxy, haloalkoxy, carboxyl, carboalkoxy, alkylcarboxamide, arylcarboxamide or --O--(C 5 -C 6 )aryl; hydroxyl, amino, alkylamino or dialkylamino; or cycloalkyl, alkylcycloalkyl, alkenylcycloalkyl, cycloalkenyl, alkylcycloalkenyl, alkenylcycloalkenyl, (C 5 -C 12 )aryl, (C 5 -C 12 )arylalkyl, (C 5 -C 12 )arylalkenyl, fused (C 5 -C 12 )aryl-cycloalkyl or alkyl fused (C 5 -C 12 )aryl-cycolalkyl optionally comprising 1-4 heteroatoms selected from N, O and S, and optionally substituted with halo, cyano, nitro, hydroxyl, haloalkyl, amino, aminoalkyl, dialkylamino, alkyl, alkenyl, alkylenedioxy, alkynyl, alkoxy, haloalkoxy, carboxyl, carboalkoxy, alkylcarboxamide, (C 5 -C 6 )aryl, --O--(C 5 -C 6 )aryl, arylcarboxamide, alkylthio or haloalkylthio.
X and Y are independently O, S or N, wherein N is optionally substituted with alkyl or alkenyl optionally substituted with 1-3 halo atoms; (C 5 -C 6 )aryl, arylalkyl or arylalkenyl optionally comprising 1-3 heteroatoms selected from N, O and S, and optionally subsituted with halo, cyano, nitro, hydroxyl, haloalkyl, amino, aminoalkyl, dialkylamino, alkyl, alkenyl, alkynyl, alkoxy, haloalkoxy, carboxyl, carboalkoxy, alkylcarboxamide, arylcarboxamide, alkylthio or haloalkylthio. Preferably, at least one of X or Y is N. It will be understood that where X or Y is a substituted N, both X and Y are N. Preferably, the compounds of the present invention comprise 1,2,4-oxadiazole (i.e., X is O; Y is N) or 1,3,4 oxadiazole rings (i.e., X is N; Y is O).
The compounds of the present invention may be conveniently categorized as Groups I through VI.
In one preferred embodiment, the invention provides compounds of the formula (Group I): ##STR2## wherein X, Y and R 1 are described above; R 2 and R 3 are independently or together H; alkyl or alkenyl optionally substituted with 1-3 halo, hydroxyl, thio, alkylthio, amino, alkylamino, dialkylamino, alkylguanidinyl, dialkylguanidinyl, guanidinyl, or amidylguanidine; --RCOR', --RCOOR', --RNR'R"R o or --RC(O)NR'R" where R is alkyl or alkenyl, and R', R" and R o are independently H, alkyl, alkenyl, cycloalkyl or (C 5 -C 6 )aryl; or cycloalkyl, alkylcycloalkyl, alkenylcycloalkyl, alkyl-oxyaryl, alkyl-thioaryl, alkyl-aminoaryl, (C 5 -C 12 )aryl, (C 5 -C 12 )arylalkyl or (C 5 -C 12 )arylalkenyl optionally comprising 1-4 heteroatoms selected from N, O and S, and optionally substituted with halo, cyano, keto, nitro, hydroxyl, haloalkyl, amino, aminoalkyl, dialkylamino, amidine, alkylamidine, dialkylamidine, alkyl, alkenyl, alkylenedioxy, alkynyl, alkoxy, haloalkoxy, carboxyl, carboalkoxy, alkylcarboxamide, (C 5 -C 6 )aryl, --O--(C 5 -C 6 )aryl, arylcarboxamide, alkylthio or haloalkylthio;
A is a direct bond, --C(O)--, --NH--C(O)--, --S(O) 2 --, --NH--S(O) 2 --, --OC(O)--, --C-- or an amino acid selected from, but not limited to, proline, isoleucine, cyclohexylalanine, cysteine optionally substituted at the sulfur with alkyl, alkenyl or phenyl optionally substituted with halo, cyano, nitro, haloalkyl, amino, aminoalkyl, dialkylamino, alkyl, alkoxy, haloalkoxy, carboxyl, carboalkoxy, alkylcarboxamide, arylcarboxamide, alkylthio or haloalkylthio; phenylalanine, homo-phenylalanine, dehydrophenylalanine, indoline-2-carboxylic acid; tetrahydrosioquinoline-2-carboxylic acid optionally substituted with alkyl, alkenyl or phenyl optionally substituted with halo, cyano, nitro, haloalkyl, amino, aminoalkyl, dialkylamino, alkyl, alkoxy, haloalkoxy, carboxyl, carboalkoxy, alkylcarboxamide, arylcarboxamide, alkylthio or haloalkylthio; tryptophan, tyrosine, serine or threonine optionally substituted with alkyl or aryl; histidine, methionine, valine, norvaline, norleucine, octahydroindole-2-carboxylic acid; asparagine, glutamine, ornithine and lysine optionally substituted at the side chain nitrogen with alkyl, alkenyl, alkynyl, alkoxyalkyl, alkylthioalkyl, alkylaminoalkyl, dialkylaminoalkyl, carboxyalkyl, alkoxycarbonyl alkyl or aryl, arylalkyl, cycloalkyl, alkylcycloalkyl, fused aryl-cycloalkyl or alkyl fused aryl-cycloalkyl optionally comprising 1 or more heteroatoms selected from N, O and S; and
R 4 is H, alkyl, alkenyl or alkynyl; or cycloalkyl, alkylcycloalkyl, (C 5 -C 12 )aryl, (C 5 -C 12 )arylalkyl, fused (C 5 -C 12 )aryl-cycloalkyl or fused alkyl (C 5 -C 12 )aryl-cycloalkyl optionally comprising one or more heteroatoms selected from N, O and S, and optionally substituted with alkyl, alkenyl, alkynyl, halo, cyano, nitro, hydroxyl, haloalkyl, alkoxy, amino, alkylamino, dialkylamino, carboxyl, haloalkoxy, carboalkoxy, alkylcarboxamide, aryl, arylalkyl, arylcarboxamido, alkylthio or haloalkylthio or is absent.
In a preferred embodiment, X is N and Y is O. In another preferred embodiment, X is O and Y is N. Preferably, R 4 --A is an arylalkyloxycarbonyl such as benzyloxycarbonyl; alkoxycarbonyl, arylsulfonyl, alkylsulfonyl or alkyl.
Preferably, R 2 and R 3 are alkyl such as methyl or isopropyl, or H. In one preferred embodiment, R 2 is isopropyl and R 3 is H.
In a preferred embodiment of the invention, R 1 is an optionally substituted aryl or arylalkyl group, such as an α,α-dimethylbenzyl, benzyl or phenyl group. According to several preferred embodiments, the benzene ring is substituted with an alkyl, such as methyl; with a haloalkyl, such as trifluoromethyl; or with a dialkylamino, preferably dimethylamino. In yet another embodiment, R 1 is a fused arylalkyl group such as methylenenaphthyl; or a fused aryl-cycloalkyl or alkyl fused aryl-cycloalkyl such as 3,4-methylenedioxybenzyl. In another embodiment, R 1 is an alkyl group, preferably (C 1 -C 8 )alkyl, either straight chain or branched, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, etc.
The present invention further provides compounds of the formula (Group II): ##STR3## wherein X, Y, R 1 , R 2 and R 3 are as described above;
B is --S(O) 2 --, --C(O)--, --OC(O)-- or --CH 2 C(O)--;
R 6 is ##STR4## wherein R' 2 and R' 3 are independently or together H; alkyl or alkenyl optionally substituted with 1-3 halo, hydroxyl, thio, alkylthio, amino, alkylamino, dialkylamino, alkylguanidinyl, dialkylguanidinyl, guanidinyl, or amidylguanidine; --RCOR', --RCOOR', --RNR'R"R o or --RC(O)NR'R" where R is alkyl or alkenyl, and R', R" and R o are independently H, alkyl, alkenyl, cycloalkyl or (C 5 -C 6 )aryl; or cycloalkyl, alkylcycloalkyl, alkenylcycloalkyl, alkyl-oxyaryl, alkyl-thioaryl, alkyl-aminoaryl, (C 5 -C 12 )aryl, (C 5 -C 12 )arylalkyl or (C 5 -C 12 )arylalkenyl optionally comprising 1-4 heteroatoms selected from N, O and S, and optionally substituted with halo, cyano, keto, nitro, hydroxyl, haloalkyl, amino, aminoalkyl, dialkylamino,amidine, alkylamidine, dialkylamidine, alkyl, alkenyl, alkylenedioxy, alkynyl, alkoxy, haloalkoxy, carboxyl, carboalkoxy, alkylcarboxamide, (C 5 -C 6 )aryl, --O--(C 5 -C 6 )aryl, arylcarboxamide, alkylthio or haloalkylthio;
R 13 is H, alkyl, halo, alkoxy, carboalkoxy, carboxyl, alkylthio, amino, alkylamino, dialkylamino, or aryl, arylalkyl, cycloalkyl, alkylcycloalkyl, fused aryl-cycloalkyl or alkyl fused aryl-cycloalkyl optionally comprising 1 or more heteroatoms selected from O, N and S, and optionally substituted with halo or alkyl;
R 14 is H, alkyl, alkenyl, amino, alkylamino, dialkylamino; or aryl, arylalkyl, cycloalkyl, alkylcycloalkyl, fused aryl-cycloalkyl, alkyl fused aryl-cycloalkyl or aryloxycarboxamide optionally comprising 1 or more heteroatoms selected from N, O and S, and optionally substituted with alkyl, halo, alkoxy, amino, alkylamino, dialkylamino, carboxyl, alkenyl, alkynyl, haloalkoxy, carboalkoxy, alkylcarboxamide, aryl, arylalkyl, arylcarboxamide, arylalkylcarboxamide, alkylthio or haloalkylthio;
R 15 is H, alkyl, halo, alkoxy, carboalkoxy, carboxyl, alkylthio, amino, alkylamino, dialkylamino, or aryl, arylalkyl, cycloalkyl, alkylcycloalkyl, fused aryl-cycloalkyl or alkyl fused aryl-cycloalkyl optionally comprising 1 or more heteroatoms selected from O, N and S; and
W is O or S; or C or N optionally substituted with H, alkyl or aryl.
In a preferred embodiment, X is N and Y is O. In another preferred embodiment, X is O and Y is N. According to several preferred embodiments, R 13 is an optionally substituted phenyl or benzyl; pyridyl, piperidinyl, alkyl or H or a fused ring system such as 3,4-methylenedioxybenzyl; R 14 is optionally substituted amino or an arylalkyloxycarboxamide such as benzyloxycarboxamide; and R 15 is H or halo.
Preferably, R 2 is isopropyl and R 3 is H.
In a preferred embodiment of the invention, R 1 is an optionally substituted aryl or arylalkyl group, such as a α,α-dimethylbenzyl, benzyl or phenyl group. According to several preferred embodiments, the benzene ring is substituted with an alkyl, such as methyl; with a haloalkyl, such as trifluoromethyl; or with a dialkylamino, preferably dimethylamino. In yet another embodiment, R 1 is a fused arylalkyl group such as methylenenaphthyl; or a fused aryl-cycloalkyl or alkyl fused aryl-cycloalkyl such as 3,4-methylenedioxybenzyl. In another embodiment, R 1 is an alkyl group, preferably (C 1 -C 8 )alkyl, either straight chain or branched, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, etc.
The present invention also provides compounds of the formula (Group III): ##STR5## wherein X, Y, R 1 , R 2 , R 3 and B are as described above; and R 6 is of formula (I): ##STR6## where m is 0 or 1; n is 0 or 1; D is a direct bond or an amino acid selected from, but not limited to, proline, isoleucine, cyclohexylalanine, cysteine optionally substituted at the sulfur with alkyl, alkenyl or phenyl optionally substituted with halo, cyano, nitro, haloalkyl, amino, aminoalkyl, dialkylamino, alkyl, alkoxy, haloalkoxy, carboxyl, carboalkoxy, alkylcarboxamide, arylcarboxamide, alkylthio or haloalkylthio; phenylalanine, homophenylalanine, dehydrophenylalanine, indoline-2-carboxylic acid; tetrahydrosioquinoline-2-carboxylic acid optionally substituted with alkyl, alkenyl or phenyl optionally substituted with halo, cyano, nitro, haloalkyl, amino, aminoalkyl, dialkylamino, alkyl, alkoxy, haloalkoxy, carboxyl, carboalkoxy, alkylcarboxamide, arylcarboxamide, alkylthio or haloalkylthio; tryptophan, tyrosine, serine or threonine optionally substituted with alkyl or aryl; histidine methionine, valine, norvaline, norleucine, octahydroindole-2-carboxylic acid; asparagine, glutamine, ornithine and lysine optionally substituted at the side chain nitrogen with alkyl, alkenyl, alkynyl, alkoxyalkyl, alkylthioalkyl, alkylaminoalkyl, dialkylaminoalkyl, carboxyalkyl, alkoxycarbonyl alkyl or aryl, arylalkyl, cycloalkyl, alkylcycloalkyl, fused aryl-cycloalkyl or alkyl fused aryl-cycloalkyl optionally comprising 1 or more heteroatoms selected from N, O and S;
A is a direct bond, --C(O)--, --NH--C(O)--, --S(O) 2 --, --OC(O)-- or --C--; and
R 14 is H, alkyl, alkenyl, amino, alkylamino or dialkylamino; or aryl, arylalkyl, cycloalkyl, alkylcycloalkyl, fused aryl-cycloalkyl or alkyl fused aryl-cycloalkyl optionally comprising 1 or more heteratoms selected from N, O and S, and optionally substituted with alkyl, halo, alkoxy, amino, alkylamino, dialkylamino, carboxy, alkenyl, alkynyl, haloalkoxy, carboalkoxy, alkylcarboxamide, aryl, arylalkyl, arylcarboxamide, alkylthio or haloalkylthio.
Alternatively, R 6 is of formula (II): ##STR7## where W is S or O;
R 8 is alkylamino, dialkylamino or amino;
R 9 is H, alkyl or halo.
In a preferred embodiment, X is N and Y is O. In another preferred embodiment, X is O and Y is N. According to one embodiment, where R 6 is of formula (I), m is 1, n is 0. In another embodiment, m and n are 1. Preferably, R 14 is benzyl, A is --OC(O)-- and D is Val.
Preferably, R 2 is isopropyl and R 3 is H.
In a preferred embodiment of the invention, R 1 is an optionally substituted aryl or arylalkyl group, such as a α,α-dimethylbenzyl, benzyl or phenyl group. According to several preferred embodiments, the benzene ring is substituted with an alkyl, such as methyl; with a haloalkyl, such as trifluoromethyl; or with a dialkylamino, preferably dimethylamino. In yet another embodiment, R 1 is a fused arylalkyl group such as methylenenaphthyl; or a fused aryl-cycloalkyl or alkyl fused aryl-cycloalkyl such as 3,4-methylenedioxybenzyl. In another embodiment, R 1 is an alkyl group, preferably (C 1 -C 8 )alkyl, either straight chain or branched, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, etc.
According to one embodiment, W is S; R 8 is amino and R 9 is H.
In yet a further embodiment of the invention of Group (III) compounds, R 6 is aryl, arylalkyl, cycloalkyl or alkylcycloalkyl. According to one embodiment, R 6 --B is Cbz.
The present invention further provides compounds of the formula (Group IV): ##STR8## wherein X, Y, R 1 , R 2 and R 3 are as described above;
R 10 is (C 5 -C 6 )aryl, (C 5 -C 6 )arylalkyl, (C 5 -C 6 )arylalkenyl, cycloalkyl, fused aryl cycloalkyl optionally comprising one or more heteroatoms selected from N, S and non-peroxide O, and optionally substituted with halo, cyano, nitro, haloalkyl, amino, aminoalkyl, dialkylamino, alkyl, alkenyl, alkynyl, alkoxy, haloalkoxy, carboxyl, carboalkoxy, alkylcarboxamide, alkylthio or haloalkylthio;
D is a direct bond, --C(O)--, or an amino acid selected from, but not limited to, proline, isoleucine, cyclohexylalanine, cysteine optionally substituted at the sulfur with alkyl, alkenyl or phenyl optionally substituted with halo, cyano, nitro, haloalkyl, amino, aminoalkyl, dialkylamino, alkyl, alkoxy, haloalkoxy, carboxyl, carboalkoxy, alkylcarboxamide, arylcarboxamide, alkylthio or haloalkylthio; phenylalanine, homophenylalanine, dehydrophenylalanine, indoline-2-carboxylic acid; tetrahydrosioquinoline-2-carboxylic acid optionally substituted with alkyl, alkenyl or phenyl optionally substituted with halo, cyano, nitro, haloalkyl, amino, aminoalkyl, dialkylamino, alkyl, alkoxy, haloalkoxy, carboxyl, carboalkoxy, alkylcarboxamide, arylcarboxamide, alkylthio or haloalkylthio; tryptophan, tyrosine, serine or threonine optionally substituted with alkyl or aryl; histidine methionine, valine, norvaline, norleucine, octahydroindole-2-carboxylic acid; asparagine, glutamine, ornithine and lysine optionally substituted at the side chain nitrogen with alkyl, alkenyl, alkynyl, alkoxyalkyl, alkylthioalkyl, alkylaminoalkyl, dialkylaminoalkyl, carboxyalkyl, alkoxycarbonyl alkyl or aryl, arylalkyl, cycloalkyl, alkylcycloalkyl, fused aryl-cycloalkyl or alkyl fused aryl-cycloalkyl optionally comprising 1 or more heteratoms selected from N, O and S;
A is a direct bond, --C(O)--, --NH--C(O)--, --S(O) 2 --, --NH--S(O) 2 --, --S(O) 2 --NH--, --OC(O)NH--, --OC(O)-- or --C--; and R 14 is as described above.
In a preferred embodiment, X is N and Y is O. In another preferred embodiment, X is O and Y is N. Preferably, D is Val, A is --OC(O)-- and R 14 is aryl or arylalkyl such as benzyl. In a preferred embodiment, R 10 is (C 5 -C 6 )aryl or (C 5 -C 6 )arylalkyl, preferably benzyl, or a fused aryl-cycloalkyl such as an indanyl group. According to another preferred embodiment, D is --C(O)--, and R 14 --A is pyrrole.
Preferably, R 2 is isopropyl and R 3 is H.
In a preferred embodiment of the invention, R 1 is an optionally substituted aryl or arylalkyl group, such as a α,α-dimethylbenzyl, benzyl or phenyl group. According to several preferred embodiments, the benzene ring is substituted with an alkyl, such as methyl; with a haloalkyl, such as trifluoromethyl; or with a dialkylamino, preferably dimethylamino. In yet another embodiment, R 1 is a fused arylalkyl group such as methylenenaphthyl; or a fused aryl-cycloalkyl or alkyl fused aryl-cycloalkyl such as 3,4-methylenedioxybenzyl. In another embodiment, R 1 is an alkyl group, preferably (C 1 -C 8 )alkyl, either straight chain or branched, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, etc.
The present invention additionally provides compounds of the formula (Group V): ##STR9## wherein X, Y, R 1 , R 2 , R 3 , R' 2 and R' 3 are as described above; and
R 11 , R 12 and E together form a monocyclic or bicyclic ring comprising 5-10 atoms selected from C, N, S and O; said ring containing 1 or more keto groups; and optionally substituted with halo, cyano, nitro, haloalkyl, amino, aminoalkyl, dialkylamino, alkyl, alkenyl, alkynyl, alkoxy, haloalkoxy, carboxyl, carboalkoxy, alkylcarboxamido, alkylthio, haloalkylthio; cycloalkyl, alkylcycloalkyl, alkenylcycloalkyl, (C 5 -C 12 )aryl, (C 5 -C 12 )arylalkyl, ((C 5 -C 12 )arylalkyl)OC(O)NH-- or (C 5 -C 12 )arylalkenyl optionally comprising one or more heteroatoms selected from N, S and non-peroxide O, and optionally substituted with halo, cyano, nitro, haloalkyl, amino, aminoalkyl, dialkylamino, alkyl, alkenyl, alkynyl, alkoxy, haloalkoxy, carboxyl, carboalkoxy, --C(O)O(alkyl), --C(O)(alkyl), alkylcarboxamido, alkylthio or haloalkylthio.
In a preferred embodiment, X is N and Y is O. In another preferred embodiment, X is O and Y is N.
Preferably, R 2 is isopropyl and R 3 is H.
In a preferred embodiment of the invention, R 1 is an optionally substituted aryl or arylalkyl group, such as a α,α-dimethylbenzyl, benzyl or phenyl group. According to several preferred embodiments, the benzene ring is substituted with an alkyl, such as methyl; with a haloalkyl, such as trifluoromethyl; or with a dialkylamino, preferably dimethylamino. In yet another embodiment, R 1 is a fused arylalkyl group such as methylenenaphthyl; or a fused aryl-cycloalkyl or alkyl fused aryl-cycloalkyl such as 3,4-methylenedioxybenzyl. In another embodiment, R 1 is an alkyl group, preferably (C 1 -C 8 )alkyl, either straight chain or branched, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, etc.
According to one embodiment of the invention, R 11 , R 12 , and E together form a ring structure of formulas (I) or (Ia): ##STR10## wherein A is as described above for Group (IV); V 1 , V 2 , V 3 and V 4 are independently or together C or N;
where V 3 is C; R 13 is H, alkyl, halo, alkoxy, carboalkoxy, carboxyl, alkylthio, amino, alkylamino, dialkylamino; or aryl, arylalkyl, cycloalkyl, alkylcycloalkyl, fused aryl-cycloalkyl or alkyl fused aryl-cycloalkyl optionally comprising 1 or more heteroatoms selected from O, N and S, and optionally substituted with halo or alkyl;
R 14 is H, alkyl, alkenyl, amino, alkylamino or dialkylamino; or aryl, arylalkyl, cycloalkyl, alkylcycloalkyl, fused aryl-cycloalkyl or alkyl fused aryl-cycloalkyl, arylalkylxoxycarbonyl or arylalkylcarboxamide optionally comprising 1 or more heteratoms selected from N, O and S, and optionally substituted with alkyl, halo, alkoxy, amino, alkylamino, dialkylamino, carboxy, alkenyl, alkynyl, haloalkoxy, carboalkoxy, alkylcarboxamide, aryl, arylalkyl, arylcarboxamide, alkylthio or haloalkylthio; and
W 1 , W 2 and W 3 are independently selected from N optionally substituted with alkyl; C, S and O.
According to one preferred embodiment, V 4 is N; and V 1 , V 2 and V 3 are C. Preferably, R 13 is H or halo; R 14 --A is CbzNH, amino or H; and R' 2 and R' 3 are H. Preferably, R 11 , R 12 and E together form a ring of formula (I). In a particular embodiment, R 13 is H or F; and R 14 --A-- is H or H 2 N--. Where R 11 , R 12 and E together form a ring of formula (Ia), W 1 is preferably S, and W 2 and W 3 are C.
In another embodiment, R 11 , R 12 and E together form a ring of formula (II) ##STR11## wherein A, R 13 and R 14 are as described above; Preferably, R' 2 and R' 3 are H. According to one embodiment, R 13 is 1-piperidinyl; and R 14 --A is CbzNH. Alternatively, R 13 is H; and R 14 --A is amino, alkylamino or dialkylamino. In another preferred embodiment, R 13 is halo; and R 14 --A is CH 3 --O--C(O)--. In yet another embodiment, R 13 is H; and R 4 --A is CbzNH.
According to another embodiment of the invention, R 11 , R 12 and E form a ring of formula (III) or (IV): ##STR12## wherein A is a direct bond, --C-- or --C(O)--;
R 13 , R 14 and R 15 are as defined above.
According to a particular embodiment, R 11 , R 12 and E form a ring of formula (III); and --A--R 13 is --C(O)phenyl; R 14 is H; and R' 2 and R' 3 are H.
In another embodiment, R 11 , R 12 and E form a ring of formula (IV); and --A--R 13 is --C(O)phenyl; R 15 is H; and R' 2 and R' 3 and H.
In another embodiment of the invention, R 11 , R 12 and E form a ring of formula (V): ##STR13## wherein W is S, SO, SO 2 or C;
n is 0, 1 or 2;
R 13 and R 14 are defined above; and
G is --NHC(O)--, --OC(O)NH--, --C(O)--, --NHS(O) 2 -- or a direct bond.
According to one embodiment, n is O W is S, where preferably R 14 --G is H. Preferably, R 13 is optionally substituted benzyl or phenyl.
In another embodiment, n is 1 and W is C. Preferably, R 14 --G is an arylalkyloxycarboxamide, for example, CbzNH--. In a preferred embodiment, R 13 is H or phenyl substituted with halo. Preferably, R' 2 and R' 3 are H.
The invention further provides compounds wherein R 11 , R 12 and E form a ring of formulas (VI), (VIa), (VII) or (VIII): ##STR14## wherein R 13 is as defined above, or is ═CHR 15 or R 15 where R 15 is pyridinyl, phenyl or benzyl optionally substituted with halo, dialkylamino or --C(O)OCH 3 ;
R 14 and R' 14 are independently or together H, alkyl, alkenyl, CH 3 C(O)--; or aryl, arylalkyl, cycloalkyl, alkylcycloalkyl, fused aryl-cycloalkyl or alkyl fused aryl-cycloalkyl, aryloxycarbonyl or arylalkyloxycarbonyl optionally comprising 1 or more heteratoms selected from N, O and S, and optionally substituted with alkyl, halo, alkoxy, amino, alkylamino, dialkylamino, carboxy, alkenyl, alkynyl, haloalkoxy, carboalkoxy, alkylcarboxamide, aryl, arylalkyl, arylcarboxamide, alkylthio or haloalkylthio; and
R 16 , R 17 , R' 16 and R' 17 are independently or together H, alkyl, alkenyl, alkylthio, alkylthioalkyl; or cycloalkyl, cycloalkenyl, alkylcycloalkyl, aryl, arylalkyl or arylalkenyl optionally substituted with guanidine, carboalkoxy, hydroxyl, haloalkyl, alkylthio, alkylguanidine, dialkylguanidine or amidine.
Preferred compounds are of formula (VI) or (VIa) where R 13 is ═CHR 15 or R 15 ; and R 14 is H, alkyl, CH 3 C(O)--, Cbz or benzyl optionally substituted with alkyl, halo or alkylamino; or 3,4-methylenedioxybenzyl or 3,4-ethylenedioxybenzyl; and R' 2 and R' 3 are H. Preferably, R 13 is ═CHR 15 where R 15 is phenyl or benzyl optionally substituted with halo or --C(O)CH 3 .
In a further embodiment, R 11 , R 12 and E form a ring of formula (IX) or (IXa): ##STR15## wherein U, V, W and Y are independently or together N, C, C(O), N(R 13 ) where R 13 is H, alkyl, halo, alkoxy, carboalkoxy, carboxyl, alkylthio, amino, alkylamino, dialkylamino; or aryl, arylalkyl, cycloalkyl, alkylcycloalkyl, fused aryl-cycloalkyl or alkyl fused aryl-cycloalkyl optionally comprising 1 or more heteroatoms selected from O, N and S, and optionally substituted with halo or alkyl; N(R 14 ) where R 14 is H, alkyl, alkenyl, or aryl, arylalkyl, cycloalkyl, alkylcycloalkyl, fused aryl-cycloalkyl or alkyl fused aryl-cycloalkyl optionally comprising 1 or more heteratoms selected from N, O and S, and optionally substituted with alkyl, halo, alkoxy, amino, alkylamino, dialkylamino, carboxy, alkenyl, alkynyl, haloalkoxy, carboalkoxy, alkylcarboxamide, aryl, arylalkyl, arylcarboxamide, alkylthio or haloalkylthio; or C(R 16 )(R 17 ) where R 16 and R 17 are independently or together H, alkyl, alkylthio, alkylthioalkyl; a carboxylic acid ester of the formula --(CH 2 ) m C(O)OR or an N-substituted alkylamide of the formula --(CH 2 ) m C(O)NRR' where m is 1 to 6 and R and R' are independently or together H or alkyl; or aryl, arylalkyl, cycloalkyl, alkylcycloalkyl, fused aryl-cycloalkyl or alkyl fused aryl-cycloalkyl optionally comprising one or more heteroatoms selected from N, S and non-peroxide O and optionally substituted with amino, alkylamino, dialkylamino, guanidine, carboalkoxy, keto, hydroxyl, alkyl, haloalkyl, alkylthio, alkylguanidine, dialkylguanidine or amidine; or together form a cyclic ring structure comprising 4-8 atoms selected from C, N, O and S.
In one preferred embodiment, U is C(R 16 )(R 17 ), V is N, W is N(R 14 ) and Y is C(O), where preferably R' 2 and R' 3 are H; R 16 is phenyl or benzyl; R 17 is H; and R 14 is H or benzyl optionally substituted with alkyl, halo, or alkylamine.
In another preferred embodiment, U is C(O); V is N, W is N, N(R 13 ) or N(R 14 ); and Y is C(R 16 )(R 17 ), where preferably R' 2 and R' 3 are H; R 14 is H; R 16 is H, alkyl, optionally substituted aryl or arylalkyl, preferably benzyl or phenyl optionally substituted with dialkylamino or hydroxyl; pyridinyl, methylene pyridinyl; fused aryl such as an indolyl; or a carboxylic acid ester or N-substituted alkyl amide, as defined above; and R 17 is H, alkyl, succinimidyl, aryl or arylalkyl.
In yet another preferred embodiment, U is C(O), V is N, W is N, N(R 13 ) or N(R 14 ); and Y is N(R 13 ), where preferably R' 2 and R' 3 are H; W is NH; R 13 is arylalkyl; and R 14 is H.
In a further embodiment, U is C(R 16 )(R 17 ); V is N; W is N or N(R 13 ); and Y is C(O). Preferably, R 13 and R 16 are aryl; and R 17 is H.
Where R 11 , R 12 and E form a ring of formula (IXa); W is typically N(R 13 ) where R 13 is aryl or cycloalkyl such as piperidinyl.
In another embodiment, R 16 and R 17 form a cyclic ring structure, such as a cyclopentyl or cyclohexyl group.
The invention further provides compounds of the formula (Group VI): ##STR16## wherein X, Y, R 1 , R 2 and R 3 are as described above, and R 11 , R 12 and E together form a ring of formula (X): ##STR17## where U and V are independently or together N, C, N(R 13 ) where R 13 is H, alkyl, alkoxy, carboalkoxy, carboxyl, alkylthio, amino, alkylamino, dialkylamino; or aryl, arylalkyl, cycloalkyl, alkylcycloalkyl, fused aryl-cycloalkyl or alkyl fused aryl-cycloalkyl optionally comprising 1 or more heteroatoms selected from O, N and S; or C(R 16 )(R 17 ) where R 16 and R 17 are as defined above; and
and n is 1 or 2.
The present invention further provides methods of synthesizing compounds of formula (A): ##STR18## wherein Z' is defined below;
R 1 is alkyl or alkenyl optionally substituted with 1-3 halo or hydroxyl; -alkyl-C(O)OCH 3 ; alkylamino, dialkylamino, alkyldialkylamino; or cycloalkyl, alkylcycloalkyl, alkenylcycloalkyl, (C 5 -C 12 )aryl, (C 5 -C 12 )arylalkyl, (C 5-C 12 )arylalkenyl, fused (C 5-C 12 )arylcycloalkyl or fused (C 5 -C 12 )aryl-cyclalkylalkyl optionally comprising 1-4 heteroatoms selected from N, O and S, and optionally substituted with halo, cyano, nitro, hydroxyl, haloalkyl, amino, aminoalkyl, dialkylamino, alkyl, alkenyl, alkylenedioxy, alkynyl, alkoxy, haloalkoxy, carboxyl, carboalkoxy, alkylcarboxamide, (C 5 -C 6 )aryl, --O--(C 5 -C 6 )aryl, arylcarboxamide, alkylthio or haloalkylthio;
X and Y are independently O, S or N, wherein N is optionally substituted with alkyl or alkenyl optionally substituted with 1-3 halo atoms; (C 5 -C 6 )aryl, arylalkyl or arylalkenyl optionally comprising 1-3 heteroatoms selected from N, O and S, and optionally substituted with halo, cyano, nitro, hydroxyl, haloalkyl, amino, aminoalkyl, dialkylamino, alkyl, alkenyl, alkynyl, alkoxy, haloalkoxy, carboxyl, carboalkoxy, alkylcarboxamide, arylcarboxamide, alkylthio or haloalkylthio; and
R 2 and R 3 are independently or together H; alkyl or alkenyl optionally substituted with 1-3 halo, hydroxyl, thio, alkylthio, amino, alkylamino, dialkylamino, alkylguanidinyl, dialkylguanidinyl, guanidinyl, or amidylguanidine; --RCOR', --RCOOR', --RNR'R" R o or --RC(O)NR'R" where R is alkyl or alkenyl, and R', R" and R o are independently H, alkyl, alkenyl, cycloalkyl or (C 5 -C 6 )aryl; or cycloalkyl, alkylcycloalkyl, alkenylcycloalkyl, alkyl-oxyaryl, alkyl-thioaryl, alkyl-aminoaryl, (C 5 -C 12 )aryl, (C 5 -C 12 )arylalkyl or (C 5 -C 12 )arylalkenyl optionally comprising 1-4 heteroatoms selected from N, O and S, and optionally substituted with halo, cyano, keto, nitro, hydroxyl, haloalkyl, amino, aminoalkyl, dialkylamino, amidine, alkylamidine, dialkylamidine, alkyl, alkenyl, alkylenedioxy, alkynyl, alkoxy, haloalkoxy, carboxyl, carboalkoxy, alkylcarboxamide, (C 5 -C 6 )aryl, --O--(C 5 -C 6 )aryl, arylcarboxamide, alkylthio or haloalkylthio;
comprising the steps of:
(a) reacting a compound of formula (B): ##STR19## wherein M is Li or MgBr, with an aldehyde of formula (C): ##STR20## where [PrG 1 ] is a protecting group; (b) removing the protecting group from the resulting alcohol (D)
(c) coupling the alcohol obtained from step (b) with an acid of formula (E):
Z'--COOH (E)
and
(d) oxidizing the resulting product and further, if desired, removing the protecting group to yield the final compound.
According to one embodiment, the protecting group [PGR 1 ] is removed from alcohol (D) by reacting the aldehyde of formula (C) with hydrochloric acid in dioxane. The protecting group [PGr 1 ] may be any suitable group, preferably Boc.
According to another embodiment, the oxidation step of (d) is performed using Dess Martin reagent.
In a further embodiment, the compound of formula (B) is synthesized by:
(e) treating an acid of the formula (R 1 )COOH with thionyl chloride or oxalyl chloride;
(f) treating the resulting acid chloride with hydrazine to yield a hydrazide of the formula (R 1 )CONHNH 2 ;
(g) reacting the hydrazide with triethyl orthoformate or trimethyl orthoformate and TsOH to yield a oxadiazole of the formula (F): ##STR21## (h) treating the oxadiazole with butyllithium and further, is desired, reacting with MgBr.OEt 2 to yield the compound B.
In one embodiment, Z' is ##STR22## wherein A is a direct bond, --C(O)--, --NH--C(O)--, --S(O) 2 --, --NH--S(O) 2 --, --OC(O)--, --C-- or an amino acid selected from proline, isoleucine, cyclohexylalanine, cysteine optionally substituted at the sulfur with alkyl, alkenyl or phenyl optionally substituted with halo, cyano, nitro, haloalkyl, amino, aminoalkyl, dialkylamino, alkyl, alkoxy, haloalkoxy, carboxyl, carboalkoxy, alkylcarboxamide, arylcarboxamide, alkylthio or haloalkylthio; phenylalanine, homo-phenylalanine, dehydrophenylalanine, indoline-2-carboxylic acid; tetrahydrosioquinoline-2-carboxylic acid optionally substituted with alkyl, alkenyl or phenyl optionally substituted with halo, cyano, nitro, haloalkyl, amino, aminoalkyl, dialkylamino, alkyl, alkoxy, haloalkoxy, carboxyl, carboalkoxy, alkylcarboxamide, arylcarboxamide, alkylthio or haloalkylthio; tryptophan, tyrosine, serine or threonine optionally substituted with alkyl or aryl; histidine, methionine, valine, norvaline, norleucine, octahydroindole-2-carboxylic acid; asparagine, glutamine, omithine and lysine optionally substituted at the side chain nitrogen with alkyl, alkenyl, alkynyl, alkoxyalkyl, alkylthioalkyl, alkylaminoalkyl, dialkylaminoalkyl, carboxyalkyl, alkoxycarbonyl alkyl or aryl, arylalkyl, cycloalkyl, alkylcycloalkyl, fused aryl-cycloalkyl or alkyl fused aryl-cycloalkyl optionally comprising 1 or more heteroatoms selected from N, O and S; and
R 4 is H, alkyl, alkenyl, or alkynyl; or cycloalkyl, alkylcycloalkyl, (C 5 -C 12 )aryl, (C 5 -C 12 )arylalkyl, fused (C 5 -C 12 )aryl-cycloalkyl or fused (C 5 -C 12 )aryl-cycloalkylalkyl optionally comprising one or more heteroatoms selected from N, O and S, and optionally substituted with alkyl, alkenyl, alkynyl, halo, cyano, nitro, hydroxyl, haloalkyl, alkoxy, amino, alkylamino, dialkylamino, carboxyl, haloalkoxy, carboalkoxy, alkylcarboxamide, aryl, arylalkyl, arylcarboxamido, alkylthio or haloalkylthio or is absent; or
Z' may be ##STR23## wherein R' 2 and R' 3 are independently or together H; alkyl or alkenyl optionally substituted with 1-3 halo, hydroxyl, thio, alkylthio, amino, alkylamino, dialkylamino, alkylguanidinyl, dialkylguanidinyl, guanidinyl or amidylguanidine; --RCOR', --RCOOR', --RNR'R"R o or --RC(O)NR'R" where R is alkyl or alkenyl, and R', R" and R o are independently H, alkyl, alkenyl, cycloalkyl or (C 5 -C 6 )aryl; or cycloalkyl, alkylcycloalkyl, alkenylcycloalkyl, alkyl-oxyaryl, alkyl-thioaryl, alkyl-aminoaryl, (C 5 -C 12 )aryl, (C 5 -C 12 )arylalkyl or (C 5 -C 12 )arylalkenyl optionally comprising 1-4 heteroatoms selected from N, O and S, and optionally substituted with halo, cyano, keto, nitro, hydroxyl, haloalkyl, amino, aminoalkyl, dialkylamino, amidine, alkylamidine, dialkylamidine, alkyl, alkenyl, alkylenedioxy, alkynyl, alkoxy, haloalkoxy, carboxyl, carboalkoxy, alkylcarboxamide, (C 5 -C 6 )aryl, --O--(C 5 -C 6 )aryl, arylcarboxamide, alkylthio or haloalkylthio;
R 13 is H, alkyl, halo, alkoxy, carboalkoxy, carboxyl, alkylthio, amino, alkylamino, dialkylamino, or aryl, arylalkyl, cycloalkyl, alkylcycloalkyl, fused aryl-cycloalkyl or alkyl fused aryl-cycloalkyl optionally comprising 1 or more heteroatoms selected from O, N and S, and optionally substituted with halo or alkyl;
R 14 is H, alkyl, alkenyl, amino, alkylamino, dialkylamino; or aryl, arylalkyl, cycloalkyl, alkylcycloalkyl, fused aryl-cycloalkyl, alkyl fused aryl-cycloalkyl or aryloxycarboxamide optionally comprising 1 or more heteroatoms selected from N, O and S, and optionally substituted with alkyl, halo, alkoxy, amino, alkylamino, dialkylamino, carboxyl, alkenyl, alkynyl, haloalkoxy, carboalkoxy, alkylcarboxamide, aryl, arylalkyl, arylcarboxamide, arylalkylcarboxamide, alkylthio or haloalkylthio; and
R 15 is H, alkyl, halo, alkoxy, carboalkoxy, carboxyl, alkylthio, amino, alkylamino, dialkylamino; or aryl, arylalkyl, cycloalkyl, alkylcycloalkyl, fused aryl-cycloalkyl or alkyl fused aryl-cycloalkyl optionally comprising 1 or more heteroatoms selected from O, N and S.
In yet a further embodiment, Z' is: ##STR24## where m is 0 or 1; n is 0 or 1; D is a direct bond or an amino acid selected from proline, isoleucine, cyclohexylalanine, cysteine optionally substituted at the sulfur with alkyl, alkenyl or phenyl optionally substituted with halo, cyano, nitro, haloalkyl, amino, aminoalkyl, dialkylamino, alkyl, alkoxy, haloalkoxy, carboxyl, carboalkoxy, alkylcarboxamide, arylcarboxamide, alkylthio or haloalkylthio; phenylalanine, homo-phenylalanine, dehydrophenylalanine, indoline-2-carboxylic acid; tetrahydrosioquinoline-2-carboxylic acid optionally substituted with alkyl, alkenyl or phenyl optionally substituted with halo, cyano, nitro, haloalkyl, amino, aminoalkyl, dialkylamino, alkyl, alkoxy, haloalkoxy, carboxyl, carboalkoxy, alkylcarboxamide, arylcarboxamide, alkylthio or haloalkylthio; tryptophan, tyrosine, serine or threonine optionally substituted with alkyl or aryl; histidine methionine, valine, norvaline, norleucine, octahydroindole-2-carboxylic acid; asparagine, glutamine, omithine and lysine optionally substituted at the side chain nitrogen with alkyl, alkenyl, alkynyl, alkoxyalkyl, alkylthioalkyl, alkylaminoalkyl, dialkylaminoalkyl, carboxyalkyl, alkoxycarbonyl alkyl or aryl, arylalkyl, cycloalkyl, alkylcycloalkyl, fused aryl-cycloalkyl or alkyl fused aryl-cycloalkyl optionally comprising 1 or more heteroatoms selected from N, O and S; and
A' is a direct bond, --C(O)--, --NH--C(O)--, --S(O) 2 --, --NH--S(O) 2 --, --OC(O)-- or --C--.
In yet another embodiment, Z' is: ##STR25## where W is S or O;
R 8 is alkylamino, dialkylamino or amino; and
R 9 is H, alkyl or halo; or
Z' is: ##STR26## wherein R 10 is (C 5 -C 6 )aryl, (C 5 -C 6 )arylalkyl, (C 5 -C 6 )arylalkenyl, cycloalkyl, alkylcycloalkyl, fused aryl-cycloalkyl or alkyl fused aryl-cycloalkyl optionally comprising one or more heteroatoms selected from N, S and non-peroxide O, and optionally substituted with halo, cyano, nitro, haloalkyl, amino, aminoalkyl, dialkylamino, alkyl, alkenyl, alkynyl, alkoxy, haloalkoxy, carboxyl, carboalkoxy, alkylcarboxamide, alkylthio or haloalkylthio.
In a preferred embodiment, Z' is: ##STR27## wherein R 11 , R 12 and E together form a monocyclic or bicyclic ring comprising 5-10 atoms selected from C, N, S and O; said ring containing 1 or more keto groups; and optionally substituted with halo, cyano, nitro, haloalkyl, amino, aminoalkyl, dialkylamino, alkyl, alkenyl, alkynyl, alkoxy, haloalkoxy, carboxyl, carboalkoxy, alkylcarboxamide, alkylthio, haloalkylthio or cycloalkyl, alkylcycloalkyl, alkenylcycloalkyl, (C 5 -C 12 )aryl, (C 5 -C 12 )arylalkyl, ((C 5 -C 12 )arylalkyl)OC(O)NH-- or (C 5 -C 12 )arylalkenyl optionally comprising one or more heteroatoms selected from N, S and non-peroxide O, and optionally substituted with halo, cyano, nitro, haloalkyl, amino, aminoalkyl, dialkylamino, alkyl, alkenyl, alkynyl, alkoxy, haloalkoxy, carboxyl, carboalkoxy, --C(O)O(alkyl), --C(O)(alkyl), alkylcarboxamide, alkylthio or haloalkylthio.
In a preferred embodiment, the invention provides a method of synthesizing a compound of formula (G): ##STR28## wherein T is H or NH 2 ;
R 1 is alkyl or alkenyl optionally substituted with 1-3 halo or hydroxyl; a carboxylic acid ester such as -alkyl-C(O)OCH 3 ; alkylamino, dialkylamino, alkyldialkylamino; or cycloalkyl, alkylcycloalkyl, alkenylcycloalkyl, (C 5 -C 12 )aryl, (C 5 -C 12 )arylalkyl, (C 5 -C 12 )arylalkenyl, fused (C 5 -C 12 )aryl-cycloalkyl or fused (C 5-C 12 )aryl-cyclalkylalkyl optionally comprising 1-4 heteroatoms selected from N, O and S, and optionally substituted with halo, cyano, nitro, hydroxyl, haloalkyl, amino, aminoalkyl, dialkylamino, alkyl, alkenyl, alkylenedioxy, alkynyl, alkoxy, haloalkoxy, carboxyl, carboalkoxy, alkylcarboxamide, (C 5 -C 6 )aryl, --O--(C 5 -C 6 )aryl, arylcarboxamide, alkylthio or haloalkylthio; and
Ar is an aryl or arylalkyl optionally substituted with H, alkyl, amino, alkylamino, dialkylamino, halo or hydroxyl;
comprising the steps of:
(a) reacting a compound of formula (B): ##STR29## wherein M is Li or MgBr; with an aldehyde of formula (C): ##STR30## where [PrG 1 ] is a protecting group; (b) removing the protecting group from the resulting alcohol (D)
(c) coupling the alcohol obtained from step (b) with an acid of formula (H): ##STR31## wherein T' is H or [PGr 2 ]NH, where [PGr 2 ] is a protecting group;
(d) oxidizing the resulting product to yield a ketone of formula (J): ##STR32## and further, when T' is [PGr 2 ]NH, (e) removing the protecting group [PGr 2 ] to yield the compound of formula (G). Preferably, [PGr 2 ] is Cbz.
As used herein, the term "optionally substituted" means, when substituted, mono to fully substituted.
As used herein, the term "independently" means that the substituents may be the same or different.
As used herein, the term "alkyl" means C 1 -C 15 , however, preferably C 1 -C 8 .
As used herein, the term "alkenyl" means C 1 -C 15 , however, preferably C 1 -C 8 .
As used herein, the term "alkynyl" means C 1 -C 15 , however, preferably C 1 -C 8 .
It will be understood that alkyl, alkenyl and alkynyl groups, whether substituted or unsubstituted, may be linear or branched.
As used herein, the term "aryl," unless otherwise stated, means aryl groups preferably comprising 5 to 12 carbons, and more preferably 5 to 6 carbons. Unless otherwise indicated, the term includes both mono- and bi-cyclic fused ring systems. As used herein, where the term "arylalkyl" is defined by the general formula (C x -C y )arylalkyl, x and y refer to the number of carbons making up the aryl group. The alkyl group is as defined above. The term include mono-substituted alkyl groups (e.g., benzyl), as well as di-substituted alkyl groups such as -alkyl(aryl) 2 (e.g., --CH(phenyl) 2 ). The terms arylalkyl and alkyl fused arylcycloalkyl include (α,α)-disubstituted groups such as, for example, (α,α)-disubstituted benzyl and (α,α)-disubstituted 3,4-methylenedioxybenzyl groups, wherein the a substituents are preferably alkyl groups such as methyl, ethyl or propyl. Specific examples include (α,α)-dimethylbenzyl and (α,α)-dimethyl-3,4-methylenedioxybenzyl.
As used herein, the term "arylalkenyl" includes aryl groups where the alkenyl group comprises 1-3 or more double bonds. Exemplary arylalkenyl groups include ═CH--CH 2 -aryl and --CH═CH-aryl, where aryl is preferably phenyl.
As used herein, the term "cycloalkyl," unless otherwise stated, means cycloalkyl groups preferably comprising 3 to 12 carbons, and more preferably 3 to 6 carbons. Unless otherwise indicated, the term includes both mono-, bi- and tri-cyclic fused ring systems.
As used herein, the term "Cbz" means benzyloxycarbonyl.
As used herein, the term "carboxamide" is synonymous with amide; i.e., a group of the formula --NHC(O)--.
As used herein, the term "oxycarboxamide" means a group of the formula --O--C(O)NH--.
As used herein, the term "oxycarbonyl" means a group of the formula --OC(O)--.
Pharmaceutically acceptable salts of the compounds described above are within the scope of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic representation of the synthesis of compounds of Group I.
FIG. 2 is a schematic representation of the synthesis of compounds of Group I.
FIG. 3 is a schematic representation of the synthesis of compounds of Group I.
FIG. 4 is a schematic representation of the synthesis of compounds of Group I.
FIG. 5 is a schematic representation of the synthesis of compounds of Group II.
FIG. 6 is a schematic representation of the synthesis of compounds of Group II.
FIG. 7 is a schematic representation of the synthesis of compounds of Group II.
FIG. 8 is a schematic representation of the synthesis of compounds of Group III.
FIG. 9 is a schematic representation of the synthesis of compounds of Group III.
FIG. 10 is a schematic representation of the synthesis of compounds of Group IV.
FIG. 11 is a schematic representation of the synthesis of compounds of Group V.
FIG. 12 is a schematic representation of the synthesis of compounds of Group V.
FIG. 13 is a schematic representation of the synthesis of compounds of Group V.
FIG. 14 is a schematic representation of the synthesis of compounds of Group V.
FIG. 15 is a schematic representation of the synthesis of compounds of Group V.
FIG. 16 is a schematic representation of the synthesis of compounds of Group V.
FIG. 17 is a schematic representation of the synthesis of compounds of Group V.
FIG. 18 is a schematic representation of the synthesis of compounds of Group V.
FIG. 19 is a schematic representation of the synthesis of compounds of Group V.
FIG. 20 is a schematic representation of the synthesis of compounds of Group V.
FIG. 21 is a schematic representation of the synthesis of compounds of Group V.
FIG. 22 is a schematic representation of the synthesis of compounds of Group V.
FIG. 23 shows the activity of certain compounds of Group I.
FIG. 24 shows the activity of certain compounds of Group I.
FIG. 25 shows the activity of certain compounds of Group I.
FIG. 26 shows the activity of certain compounds of Group I.
FIG. 27 shows the activity of certain compounds of Group I.
FIG. 28 shows the activity of certain compounds of Group II and III.
FIG. 29 shows the activity of certain compounds of Groups II, III and IV.
FIG. 30 shows the activity of certain compounds of Group V.
FIG. 31 shows the activity of certain compounds of Group V.
FIG. 32 shows the activity of certain compounds of Group V.
FIG. 33 shows the activity of certain compounds of Group V.
FIG. 34 shows the activity of certain compounds of Group V.
FIG. 35 shows the activity of certain compounds of Group V.
FIG. 36 shows the activity of certain compounds of Group V.
FIG. 37 shows the activity of certain compounds of Group V.
FIG. 38 shows the activity of certain compounds of Group V.
FIG. 39 is a schematic representation of the synthesis of certain compounds of the invention.
DETAILED DESCRIPTION
The compounds of the present invention have been found to be potent inhibitors of the serine protease human neutrophil elastase (HNE). They are reversible inhibitors that presumably form a transition state intermediate with the active site serine residue. The compounds are characterized by their low molecular weights, high selectivity with respect to HNE and stability regarding physiological conditions. Therefore, the compounds can be implemented to prevent, alleviate and/or otherwise treat diseases which are mediated by the degradative effects associated with the presence of HNE. Their usage is of particular importance as they relate to various human treatment in vivo but may also be used as a diagnostic tool in vitro.
The present invention provides, but is not limited to, specific embodiments set forth in the Examples as well as those set forth below. ##STR33##
The nomenclature for the above embodiments is as follows (although the majority of the embodiments disclosed indicate the stereochemistry of the 2-methylpropyl group having the (S)-configuration, it will be understood that both the (R)-configuration and the racemic (R,S) are within the scope of the invention):
CE-2157 2-Oxo-5-(phenyl)-1,4-benzodiazepine-N-[1-(2-[5-(3-methylbenzyl-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2158 3-(S)-[(Benzyloxycarbonyl)amino-(5,6 phenyl-ε-lactam]-N-[1-(3-[5-(3-trifluoromethylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2159 2-(R,S)-[(Methylene-4-pyridyl)piperazine-2,5-dione]-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2160 3-(R,S)-[(Benzyloxycarbonyl)amino-δ-lactam]-N-[1-(3-[5-(3-trifluoromethylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2161 (Pyridyl-3-carbonyl)-L-valyl-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]-L-prolinamide
CE-2162 4-[1-(2-N-Morpholino)ethyl-3-(R)-benzyl piperazine-2,5-dione]-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2163 Methylsulfonyl-L-valyl-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]-L-prolinamide
CE-2164 (Pyrrole-2-carbonyl)-N-(benzyl)glycyl-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]amide
CE-2165 N-Acetyl-2-(L)-(2,3-dihydro-1H-indole)-N[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]amide
CE-2166 1-Phenyl-1,2,4-triazolidine-3,5-dione-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2168 Phenylsulfonyl-L-valyl-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]-L-prolinamide
CE-2170 1-[2-(5-[3-Methylbenzyl]-1,3,4-oxadiazolyl]-2-(S)-[(benzyloxycarbonyl)amino]-3-methylbutan-1-one
CE-2171 (3-Pyridylcarbonyl)-L-valyl-N-[1-(3-[5-(3-trifluoromethylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]-L-prolinamide
CE-2172 Methylsulfonyl-L-valyl-N-[1-(3-[5-(3-trifluoromethylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]-L-prolinamide
CE-2173 1-(3-Morpholinoethyl)-5-(R)-benzyl-2,4-imidazolidinedione-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(R,S)-methylpropyl]acetamide
CE-2174 4-(R)-Isopropyl-2,5-imidazolidinedione-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2176 1-Benzyl-1,2,4-triazolidine-3,5-dione-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2177 (Benzyloxycarbonyl)-L-valyl-N-[1-(2-[5-(3,4-methylenedioxybenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]-L-prolinamide
CE-2178 (Benzyloxycarbonyl)-L-valyl-N-[1-(3-[5-(3,4-methylenedioxybenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]-L-prolinamide
CE-2179 5-(R,S)-Phenyl-1-methyl-2,4-imidazolidinedione-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2180 1-(N-Morpholinoethyl)-5-(R)-benzyl-2,4-imidazolidinedione-N-[1-(3-[5-(3 trifluoromethylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(R,S)-methylpropyl]acetamide
CE-2181 1-(N-Morpholinoethyl)-5-(S)-benzyl-2,4-imidazolidinedione-N-[1-(3-[5-(3 trifluoromethylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(R,S)-methylpropyl]acetamide
CE-2182 5-(R,S)-Phenyl-1-methyl-2,4-imidazolidinedione-N-[1-(3-[5-(3trifluoromethylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2183 Benzyloxycarbonyl-L-(1,2,3,4-tetrahydroisoquinoline)-3-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(R,S)-methylpropyl]amide
CE-2184 1-(N-Morpholinoethyl)-5-(S)-benzyl-2,4-imidazolidinedione-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(R,S)-methylpropyl]acetamide
CE-2185 4-Pyridylmethyleneoxycarbonyl-L-valyl-N-[1-(3-[5-(3-trifluoromethylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]-L-prolinamide
CE-2186 4-Pyridylmethyleneoxycarbonyl-L-valyl-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]-L-prolinamide
CE-2187 4-[1-(3,4-Ethylenedioxybenzyl)-3-(S)-benzyl-piperazine-2,5-dione-N-[1-(3-[5-(3-trifluoromethylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2188 1-Benzyl-4-(S)-benzyl-2,5-imidazolidinedione-N-[1-(3-[5-(3-trifluoromethylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2189 1-Benzyl-2,4-imidazolidinedione-N-[1-(3-[5-(3-trifluoromethylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2190 [1-Benzyloxycarbonyl-5-(R)-benzylpiperazin-3-one]-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2191 1-Benzyl-4-(S)-benzyl-2,5-imidazolidinedione-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(R,S)-methylpropyl]acetamide
CE-2192 1-(N-Morpholinoethyl)-5-(R,S)-phenyl-2,4-imidazolidinedione-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(R,S)-methylpropyl]acetamide
CE-2193 1-(N-Morpholinoethyl)-5-(R,S)-phenyl-2,4-imidazolidinedione-N-[1-(3-[5-(3-trifluoromethylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(R,S)-methylpropyl]acetamide
CE-2194 [4-(R,S)-(4-Dimethylaminophenyl)]-2,5-imidazolidinedione-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2195 (Pyrrole-2-carbonyl)-N-(1-(R,S)-indanyl)glycol-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]amide
CE-2196 (6-(R)-Benzylpiperazin-2-one)-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(R,S)-methylpropyl]acetamide
CE-2197 4-[1-(3,4-Methylenedioxybenzyl)-3-(R)-benzylpiperazine-2,5-dione]-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2198 4-(R,S)-Phenyl-2,5-imidazolidinedione-N-[1-(3-[5-(3-trifluoromethylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2200 [4-(R,S)-(4-Dimethylaminophenyl)]-2,5-imidazolidinedione-N-[1-(3-[5-(3-trifluoromethylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2202 Isopropyloxycarbonyl-L-valyl-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]-L-prolinamide
CE-2203 [4-(R)-(3-pyridylmethylene)]-2,5-imidazolidinedione-N-[1-(3-[5-(3-trifluoromethylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2204 1-Benzyloxycarbonyl-(2-(R)-phenylpiperazin-5-one)-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2205 [4-(R)-(3-pyridylmethyl)]-2,5-imidazolidinedione-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2206 [4-(R,S)-(4-pyridyl)-4-(R,S)-N-succinimidyl]-2,5-imidazoldinedione-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2207 Isopropyloxycarbonyl-L-valyl-N-[1-(3-[5-(3-trifluoromethylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]-L-prolinamide
CE-2208 (2-(R)-Phenylpiperazin-5-one)-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(R,S)-methylpropyl]acetamide
CE-2209 [4-(R,S)-(4-pyridyl)-4-(R,S)-N-succinimidyl]-2,5-imidazoldinedione-N-[1-(3-[5-(3-trifluoromethylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2210 (N-Benzylcarbonyl)-N-(benzyl)glycyl-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]amide
CE-2211 (R,S)-3-Amino-2-oxo-5-phenyl-1,4-(6-2'-chlorobenzodiazepine)-N-[1-(2-[5-phenyl-1,3,4-oxadiazolyl]carbonyl)-2-(R,S)-propyl]acetamide
CE-2212 3-[1-(4-Piperidine)]-benzimidazolidin-2-one-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2213 Methyloxycarbonyl-L-valyl-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]-L-prolinamide
CE-2214 Methyloxycarbonyl-L-valyl-N-[1-(3-[5-(3 trifluoromethylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]-L-prolinamide
CE-2215 1,4-Quinazolin-2-one-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2216 [4-(R,S)-(2-Pyridyl)-4-(R,S)-methyl]-2,5-imidazolidinedione-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2217 2-Oxo-5-(2-pyridyl)-1,4-benzodiazepine-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2218 (R,S)-3-Amino-2-oxo-5-(2-pyridyl)-1,4-benzodiazepine-N-[1-(2-[5-(3-methylpropyl)-1,3,4-oxadiazolyl]carbonyl)-2-(R,S)-methylpropyl]acetamide
CE-2219 1,4-Quinazolin-2-one-N-[1-(3-[5-(3-trifluoromethylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2220 (2S,5S)-5-Amino-1,2,4,5,6,7-hexahydroazepino-[3.2.1]-indole-4-one-carbonyl-N-[1-(3-[5-(3-methylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(R,S)-methylpropyl]amide
CE-2221 (R,S)-3-Amino-2-oxo-5-phenyl-1,4-benzodiazepine-N-[1-(3-[5-(3-methylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(R,S)-methylpropyl]acetamide
CE-2223 (R,S)-3-Amino-2-oxo-5-phenyl-1,4-(2'-chlorobenzodiazepine)-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(R,S)-methylpropyl]acetamide
CE-2224 (R,S)-3-Amino-2-oxo-5-(4-chlorophenyl)-1,4-benzodiazepine-N-[1-(2-[5- (3-methybenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(R,S)-methylpropyl]acetamide
CE-2225 (R,S)-3-Amino-2-oxo-5-methyl-1,4-(2',3'-methylenedioxy) benzodiazepine)-N-[1-(2-[5-(3-methybenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(R,S)-methylpropyl]acetamide
CE-2226 (R,S)-3-Amino-2-oxo-5-methyl-1,4-benzodiazepine-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(R,S)-methylpropyl]acetamide
CE-2227 4-(S)-(2-Isobutyl)-2,5-imidazolidinedione-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2228 3-(R,S)-Amino-quinolin-2-one-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolylcarbonyl)-2-(R,S)-methylpropyl]acetamide
CE-2229 (R,S)-3-Amino-2-oxo-5-(2-chlorophenyl)-1,4-(2'-chlorobenzodiazepine)-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(R,S)-methylpropyl]acetamide
CE-2230 (R,S)-3-Benzyloxycarbonylamino-2-oxo-5-(2-chlorophenyl)-1,4-(2'-chlorobenzodiazepine)-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(R,S)-methylpropyl]acetamide
CE-2231 4-Spirocyclopentane-2,5-imidazolidinedione-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2232 Benzyloxycarbonyl-L-valyl-N-(phenyl)glycyl-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]amide
CE-2233 2-Oxo-5-(4-piperidinyl)-1,4-benzodiazepine-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2234 2-(2-Pyridyl)-benzimidazole-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2235 (R,S)-3-Amino-2-oxo-5-methyl-1,4-(2',3'-dimethoxybenzodiazepine)-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(R,S)-methylpropyl]acetamide
CE-2236 (R,S)-3-Amino-2-oxo-5-methyl-1,4-(1-thiophenodiazepine)-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2237 2-Oxo-5-(4-trifluoromethylphenyl)-1,4 benzodiazepine-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2238 2,5-Imidazolidinedione-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2239 4,4-Dimethyl-2,5-imidazolidinedione-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2240 4-(S)-(2-Isopropyl)-2,5-imidazolidinedione-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2241 4-Spirocyclohexane-2,5-imidazolidinedione-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2242 2-Oxo-5-phenyl-1,4-(4'-methylbenzodiazepine)-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2243 4-(R)-(3-Indolyl)-2,5-imidazolidinedione-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2244 2-Oxo-5-methyl-1,4-(1-thiophenodiazepine)-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2245 2-Oxo-5-methyl-1,4-(2-phenyl-1-thiophenodiazepine)-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2246 4-(R)-(2-Isobutyl)-2,5-imidazolidinedione-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2247 4-(R)-(2-N,N-Dimethylcarboxamido)-2,5-imidazolidinedione-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2248 2-Oxo-5-(3,4-methylendioxyphenyl)-1,4-benzodiazepine-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2249 4-(R)-(3-Carbomethoxy)propyl-2,5-imidazolidinedione-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2250 2-Oxo-5-(2-methoxyphenyl)-1,4-benzodiazepine-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2251 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyridinyl]-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2252 4,4-Diphenyl-2,5-imidazolidinedione-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2253 4-Spiro-(2-indanyl)-2,5-imidazolidinedione-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2254 2-[(4-Fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2255 4-(R)-(4-Hydroxybenzyl)-2,5-imidazolidinedione-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2256 4-(R)-(4-Hydroxybenzyl)-2,5-imidazolidinedione-N-[1-(2-[5-(3,4-methylenedioxybenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2257 4-(R)-(2-Imidazolyl)-2,5-imidazolidinedione-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2258 2-Oxo-5-phenyl-1,4-(2'-dimethylaminobenzodiazepine)-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2259 4,4-Diphenyl-2,5-imidazolidinedione-N-[1-(2-[5-(3,4-methylenedioxybenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2260 2-[5-Amino-6-oxo-2-phenyl-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2261 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyridinyl]-N-[1-(2-[5-(3,4-methylenedioxybenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2262 2-[5-Amino-6-oxo-2-thiophenyl-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
CE-2263 2-[5-Amino-6-oxo-2-(3-pyridyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
ONO-PO-690 2-[5-(Benzyloxycarbonyl)amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(α,α-dimethylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
ONO-PO-691 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(α,α-dimethylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
ONO-PO-692 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(α,α-dimethyl-3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
ONO-PO-693 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(R)-methylpropyl]acetamide
ONO-PO-694 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-phenyl-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
ONO-PO-695 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(3-pyridyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
ONO-PO-696 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-tert-butyl-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
ONO-PO-697 2-[5-(Benzyloxycarbonyl)amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-phenyl-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
ONO-PO-698 2-[5-(Benzyloxycarbonyl)amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-tert-butyl-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
ONO-PO-699 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(4-methoxyphenyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
ONO-PO-700 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(α,α-dimethyl-3,4-methylenedioxybenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
ONO-PO-701 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(α,α-dimethyl-3,4-dihydroxybenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
ONO-PO-702 2-[5-(Methylsulfonyl)amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
ONO-PO-703 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-benzyl-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
ONO-PO-704 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-methyl-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
ONO-PO-705 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-isopropyl-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
ONO-PO-706 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-butyl-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
ONO-PO-707 2-[5-Amino-6-oxo-2-phenyl-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-tert-butyl-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
ONO-PO-708 4-(S)-(2-Isobutyl)-2,5-imidazolidinedione-N-[1-(2-[5-tert-butyl-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
ONO-PO-709 4-(S)-(2-Isobutyl)-2,5-imidazolidinedione-N-[1-(2-[5-(α,α-dimethylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
ONO-PO-710 Methylsulfonyl-L-valyl-N-[1-(2-[5-(α,α-dimethylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]-L-prolinamide
ONO-PO-711 2-[5-Amino-6-oxo-2-phenyl-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(α,.alpha.-dimethylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
ONO-PO-712 2-[5-Amino-6-oxo-2-(3-pyridyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-tert-butyl-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
ONO-PO-713 Methylsulfonyl-L-valyl-N-[1-(2-[5-(tert-butyl-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]-L-prolinamide
ONO-PO-714 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(1-methylcyclopropyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
ONO-PO-715 2-[5-Amino-6-oxo-2-(3-pyridyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(.alpha.,α-dimethylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
ONO-PO-716 2-[6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(tert-butyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
ONO-PO-717 2-Oxo-5-(4-chlorophenyl)-1,4-benzodiazepine-N-[1-(2-[5-tert-butyl-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
ONO-PO-718 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(tert-butyl)-1,3,4-oxadiazolylcarbonyl)-2-(R)-methylpropyl]acetamide
ONO-PO-719 4-(R)-Isopropyl-2,5-imidazolidinedione-N-[1-(2-[5-tert-butyl-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
ONO-PO-720 4-(R)-Isopropyl-2,5-imidazolidinedione-N-[1-(2-[5-(α,α-dimethylbenzyl)-1,3,4-oxadiazolylcarbonyl)-2-(S)-methylpropyl]acetamide
ONO-PO-721 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(α,α-dimethylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(R)-methylpropyl]acetamide
ONO-PO-722 2-[6-Oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(α,α-dimethylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
ONO-PO-723 4-(R)-(3-Indolyl)-2,5-imidazolidinedione-N-[1-(2-[5-tert-butyl-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
ONO-PO-724 4-(R)-(3-Indolyl)-2,5-imidazolidinedione-N-[1-(2-[5-(α,α-dimethylbenzyl)-1,3,4-oxadiazolylcarbonyl)-2-(S)-methylpropyl]acetamide
ONO-PO-725 2-[6-Oxo-2-phenyl-1,6-dihydro-1-pyridinyl]-N-[1-(2-[5-tert-butyl-1,3,4-oxadiazolylcarbonyl)-2-(S)-methylpropyl]acetamide
ONO-PO-726 2-[6-Oxo-2-phenyl-1,6-dihydro-1-pyridinyl]-N-[1-(2-[5-(α,α-dimethylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
ONO-PO-727 2-[6-Oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-tert-butyl-1,3,4-oxadiazolylcarbonyl)-2-(R)-methylpropyl]acetamide
ONO-PO-728 2-[5-Amino-6-oxo-2-phenyl-1,6-dihydro-1-pyrimidinyl]-N -[1-(2-[5-(1-methylcyclopropyl)-1,3,4-oxadiazolylcarbonyl)-2-(S)-methylpropyl]acetamide
ONO-PO-729 2-[5-Amino-6-oxo-2-phenyl-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-tert-butyl-1,3,4-oxadiazolyl]carbonyl)-2-(R)-methylpropyl]acetamide
ONO-PO-730 2-[6-Oxo-2-phenyl-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-tert-butyl-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
ONO-PO-731 2-[6-Oxo-2-phenyl-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-α,α-dimethylbenzyl-1,3,4-oxadiazolylcarbonyl)-2-(S)-methylpropyl]acetamide
ONO-PO-732 2-[6-Oxo-2-phenyl-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-tert-butyl-1,3,4-oxadiazolyl]carbonyl)-2-(R)-methylpropyl]acetamide
ONO-PO-733 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-tert-butyl-1,3,4-oxadiazolyl]carbonyl)-2-(R,S)-methylpropyl]acetamide
ONO-PO-734 2-[6-Oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(1-methylcyclopropyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
ONO-PO-735 2-[6-Oxo-2-phenyl-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(1-methylcyclopropyl)- 1 ,3,4 -oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
ONO-PO-736 2-[5-Amino-6-oxo-2-phenyl-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-tert-butyl-1,3,4-oxadiazolyl]carbonyl)-2-(R,S)-methylpropyl]acetamide
ONO-PO-737 2-[6-Oxo-2-phenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-butyl-1,3,4-oxadiazolyl]carbonyl)-2-(R,S)-methylpropyl acetamide
The compounds of the present invention are not limited to use for inhibition of human elastase. Elastase is a member of the class of enzymes known as serine proteases. This class also includes, for example, the enzymes chymotrypsin, cathepsin G, trypsin and thrombin. These proteases have in common a catalytic triad consisting of Serine-195, Histidine-57 and Aspartic acid-102 (chymotrypsin numbering system). The precise hydrogen bond network that exists between these amino acid residues allows the Serine-195 hydroxyl to form a tetrahedral intermediate with the carbonyl of an amide substrate. The decomposition of this intermediate results in the release of a free amine and the acylated enzyme. In a subsequent step, this newly formed ester is hydrolyzed to give the native enzyme and the carboxylic acid. It is this carboxyl component that helps characterize the specificity for the enzyme. In the example in which the carboxyl component is a peptide, the alpha-substituent of the amino acid is predominately responsible for the specificity toward the enzyme. Utilizing the well accepted subset nomenclature by Schechter and Berger (Biochem. Biophy. Res. Commun., 27:157 (1967) and Biochem. Biophys. Res. Commun., 32:898 (1968)), the amino acid residues in the substrate that undergo the cleavage are defined as P 1 . . . P n toward the N-terminus and P 1 ' . . . P n ' toward the C-terminus. Therefore, the scissile bond is between the P 1 and the P 1 ' residue of the peptide subunits. A similar nomenclature is utilized for the amino acid residues of the enzyme that make up the binding pockets accommodating the subunits of the substrate. The difference is that the binding pocket for the enzyme is designated by S 1 . . . S n instead of P 1 . . . P n as for the substrate.
The characteristics for the P 1 residue defining serine proteinase specificity is well established. The proteinases may be segregated into three subclasses: elastases, chymases and tryptases based on these differences in the P 1 residues. The elastases prefer small aliphatic moieties such as valine whereas the chymases and tryptases prefer large aromatic hydrophobic and positively charged residues respectively.
One additional proteinase that does not fall into one of these categories is propyl endopeptidase. The P 1 residue defining the specificity is a proline. This enzyme has been implicated in the progression of memory loss in Alzheimer's patients. Inhibitors consisting of α-keto heterocycles have recently been shown to inhibit propyl endopeptidase; Tsutsumi et al., J. Med. Chem., 37: 3492-3502 (1994). By way of extension, α-keto heterocycles as defined herein allow for an increased binding in P' region of the enzyme.
TABLE 1______________________________________P.sub.1 Characteristics for Proteinase Specificity Proteinase Class Representative Enzyme P.sub.1 Characteristic______________________________________Elastases Human Neutrophil small aliphatic residues Elastase Chymases alpha-Chymotrypsin, aromatic or large Cathepsin G hydrophobic residues Tryptases Thrombin, Trypsin, positively charged residues Urokinase, Plasma Kallikrein, Plasminogen Activator, Plasmin Other Prolyl Endopeptidase proline______________________________________
Since the P 1 residue predominately defines the specificity of the substrate, the present invention relates to P 1 -P n ' modifications, specifically, certain alpha-substituted keto-heterocycles composed of 1,3,4 oxadiazoles, 1,2,4-oxadiazoles, 1,3,4-thiadiazoles, 1,2,4-thiadiazoles, 1-substituted, and 4-substituted 1,2,4-triazoles. By altering the alpha-substituent and the substituent on the heterocycle, the specificity of these compounds can be directed toward the desired proteinase (e.g., small aliphatic groups for elastase).
The efficacy of the compounds for the treatment of various diseases can be determined by scientific methods which are known in the art. The following are noted as examples for HNE mediated conditions:
for acute respiratory distress syndrome, the method according to human neutrophil elastase (HNE) model (AARD, 141:227-677 (1990)); the endotoxin induced acute lung injury model in minipigs (AARD, 142:782-788 (1990));or the method according to human polymorphonuclear elastase-induced lung hemorrage model in hamsters (European Patent Publication No. 0769498) may be used;
in ischemia/reperfusion, the method according to the canine model of reperfusion injury (J. Clin. Invest., 81: 624-629 (1988)) may be used.
The compounds of the present invention, salts thereof, and their intermediates can be prepared or manufactured as described herein or by various processes known to be present in the chemical art (see also, WO 96/16080). For example, compounds of Group I may be synthesized according to the schemes set forth in FIGS. 1-2 (1,3,4 oxadiazoles) and FIGS. 3-4 (1,2,4 oxadiazoles). FIGS. 5-7 describe the synthesis of compounds of Group II. FIGS. 8-9 describe the synthesis of compounds of Group III; FIG. 10 describes synthesis of Group IV compounds. The several classes of Group V compounds are described in FIGS. 11-22.
Alternatively, the compounds of the present invention may be prepared as described in FIG. 39. The 2-substituted 1,3,4-oxadiazole (3) may be prepared via formation of the acid chloride from an acid (1) utilizing, for example, thionyl chloride or oxalyl chloride, followed by treatment with hydrazine in a suitable solvent to yield the hydrazide (2). Reaction of (2) with triethyl orthoformate or trimethyl orthoformate and TsOH gives the requisite 2-substituted 1,3,4-oxadiazole (3).
Formation of the compound (3') utilizing standard conditions (ie. butyllithium at low temperature in a polar aprotic solvent, and further, if desired, reacting with MgBr.OEt 2 ) followed by addition of the aldehyde (4) yields the alcohol (5).
Deprotection of the protected amine of (5) using hydrochloric acid in dioxane gives the amino hydrochloride (6) which is then coupled to the acid (7) by methods available to one skilled in the art to give intermediate (8). Oxidation using Dess-Martin's Periodinane or other methods as described in Oxidation in Organic Chemistry by Milos Hudlicky, ACS Monograph 186 (1990) yields the ketone (9).
The final step requires removal of the protecting group from the amine. This may be carried out by a number of methods. For example, one may utilize aluminum chloride, anisole and nitromethane in a suitable solvent such as dichloromethane to give the final compound (10). Compound (10) can then be treated with an electrophile (e.g., methanesulfonyl chloride) with added base to give (14).
The aldehyde (4) may be prepared via either of three methods described. The Weinreb amide (12) is prepared from the amino acid (11) which is subsequently reduced to the aldehyde using diisobutylalluminum hydride (DIBAL). Alternatively, one may generate the ester of the amino acid (13) followed by reduction with DIBAL to afford the aldehyde (4). Further, one may generate the alcohol (13-1) followed by oxidation with SO 3 -Py in DMSO.
The activity of the compounds is presented in FIGS. 23-38 as K i values (nM). K i values were determined, unless otherwise indicated, essentially as described in WO 96/16080, incorporated herein by reference.
Although the compounds described herein and/or their its salts may be administered as the pure chemicals, it is preferable to present the active ingredient as a pharmaceutical composition. The invention thus further provides the use of a pharmaceutical composition comprising one or more compounds and/or a pharmaceutically acceptable salt thereof, together with one or more pharmaceutically acceptable carriers thereof and, optionally, other therapeutic and/or prophylactic ingredients. The carrier(s) must be `acceptable` in the sense of being compatible with the other ingredients of the composition and not deleterious to the recipient thereof.
Pharmaceutical compositions include those suitable for oral or parenteral (including intramuscular, subcutaneous and intravenous) administration. The compositions may, where appropriate, be conveniently presented in discrete unit dosage forms and may be prepared by any of the methods well known in the art of pharmacy. Such methods include the step of bringing into association the active compound with liquid carriers, solid matrices, semi-solid carriers, finely divided solid carriers or combination thereof, and then, if necessary, shaping the product into the desired delivery system.
Pharmaceutical compositions suitable for oral administration may be presented as discrete unit dosage forms such as hard or soft gelatin capsules, cachets or tablets each containing a predetermined amount of the active ingredient; as a powder or as granules; as a solution, a suspension or as an emulsion. The active ingredient may also be presented as a bolus, electuary or paste. Tablets and capsules for oral administration may contain conventional excipients such as binding agents, fillers, lubricants, disintegrants, or wetting agents. The tablets may be coated according to methods well known in the art., e.g., with enteric coatings.
Oral liquid preparations may be in the form of, for example, aqueous or oily suspension, solutions, emulsions, syrups or elixirs, or may be presented as a dry product for constitution with water or other suitable vehicle before use. Such liquid preparations may contain conventional additives such as suspending agents, emulsifying agents, non-aqueous vehicles (which may include edible oils), or preservative.
The compounds may also be formulated for parenteral administration (e.g., by injection, for example, bolus injection or continuous infusion) and may be presented in unit dose form in ampules, pre-filled syringes, small bolus infusion containers or in multi-does containers with an added preservative. The compositions may take such forms as suspensions, solutions, or emulsions in oily or aqueous vehicles, and may contain formulatory agents such as suspending, stabilizing and/or dispersing agents. Alternatively, the active ingredient may be in powder form, obtained by aseptic isolation of sterile solid or by lyophilization from solution, for constitution with a suitable vehicle, e.g., sterile, pyrogen-free water, before use.
For topical administration to the epidermis, the compounds may be formulated as ointments, creams or lotions, or as the active ingredient of a transdermal patch. Suitable transdermal delivery systems are disclosed, for example, in Fisher et al. (U.S. Pat. No. 4,788,603) or Bawas et al. (U.S. Pat. Nos. 4,931,279, 4,668,504 and 4,713,224). Ointments and creams may, for example, be formulated with an aqueous or oily base with the addition of suitable thickening and/or gelling agents. Lotions may be formulated with an aqueous or oily base and will in general also contain one or more emulsifying agents, stabilizing agents, dispersing agents, suspending agents, thickening agents, or coloring agents. The active ingredient can also be delivered via iontophoresis, e.g., as disclosed in U.S. Pat. Nos. 4,140,122, 4383,529, or 4,051,842.
Compositions suitable for topical administration in the mouth include unit dosage forms such as lozenges comprising active ingredient in a flavored base, usually sucrose and acacia or tragacanth; pastilles comprising the active ingredient in an inert base such as gelatin and glycerin or sucrose and acacia; mucoadherent gels, and mouthwashes comprising the active ingredient in a suitable liquid carrier.
When desired, the above-described compositions can be adapted to provide sustained release of the active ingredient employed, e.g., by combination thereof with certain hydrophilic polymer matrices, e.g., comprising natural gels, synthetic polymer gels or mixtures thereof.
The pharmaceutical compositions according to the invention may also contain other adjuvants such as flavorings, coloring, antimicrobial agents, or preservatives.
It will be further appreciated that the amount of the compound, or an active salt or derivative thereof, required for use in treatment will vary not only with the particular salt selected but also with the route of administration, the nature of the condition being treated and the age and condition of the patient and will be ultimately at the discretion of the attendant physician or clinician.
In general, however, a suitable dose will be in the range of from about 0.5 to about 100 mg/kg/day, e.g., from about 1 to about 75 mg/kg of body weight per day, such as 3 to about 50 mg per kilogram body weight of the recipient per day, preferably in the range of 6 to 90 mg/kg/day, most preferably in the range of 15 to 60 mg/kg/day.
The compound is conveniently administered in unit dosage form; for example, containing 0.5 to 1000 mg, conveniently 5 to 750 mg, most conveniently, 10 to 500 mg of active ingredient per unit dosage form.
Ideally, the active ingredient should be administered to achieve peak plasma concentrations of the active compound of from about 0.5 to about 75 μM, more preferably, about 1 to 50 μM, most preferably, about 2 to about 30 μM. This may be achieved, for example, by the intravenous injection of a 0.05 to 5% solution of the active ingredient, optionally in saline, or orally administered as a bolus containing about 0.5-500 mg of the active ingredient. Desirable blood levels may be maintained by continuous infusion to provide about 0.01-5.0 mg/kg/hr or by intermittent infusions containing about 0.4-15 mg/kg of the active ingredient(s).
The desired dose may conveniently be presented in a single dose or as divided doses administered at appropriate intervals, for example, as two, three, four or more sub-doses per day. The sub-dose itself may be further divided, e.g., into a number of discrete loosely spaced administrations; such as multiple inhalations from an insufflator or by application of a plurality of drops into the eye.
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.
The following examples are given to illustrate the invention and are not intended to be inclusive in any manner:
EXAMPLES
The following abbreviations are used below: TFA-trifluoroacetic acid; HOBT--hydroxybenzotriazole; DIEA--diisopropylethylamine; NMM--4-methylmorpholine; DMF--N,N-dimethylformamide; TEA--triethylamine; EDCI--1-(3-dimethylaminopropyl-3-ethylcarbodiimide; BOPCl--bis(2-oxo-3-oxazolidinyl)phosphinic chloride; FMOC--9-fluorenyl methoxycarbonyl; BTD--bicyclic turned dipeptide (see, e.g., Tetrathedron, 49:3577-3592 (1993)); THF--tetrahydrofuran
Example 1
(CE-2072) (Benzyloxycarbonyl)-L-valyl-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]-L-prolinamide.
To a mixture containing 0.79 g (5.94 mmol) of N-chlorosuccinimide in 40 mL of anhydrous toluene at 0° C. under a nitrogen atmosphere was added 0.65 mL (8.85 mmol) of dimethyl sulfide. The reaction was cooled to -25° C. using a carbon tetrachloride/dry ice bath, followed by the dropwise addition of a solution containing (benzyloxycarbonyl)-L-valyl-N-[1-(2-[5-(3-methylbenzyl)-1,3,4 oxadiazolyl]hydroxymethyl)-2-(S)-methylpropyl]-L-prolinamide (0.90 g, 1.49 mmol) in 17 mL of anhydrous toluene. The reaction was allowed to stir for 2 hours at -25° C. followed by the addition of 1.0 mL (7.17 mmol) of triethylamine. The cold bath was removed and the mixture allowed to warm to room temperature and maintained for 20 minutes. The reaction mixture was diluted with ethyl acetate and washed with water. The organic phase was dried over magnesium sulfate, filtered and the solvent removed under reduced pressure. The residue was purified by column chromatography on silica gel with 70% ethyl acetate/hexane to give 0.90 g of material which was further purified via preparative HPLC to afford 665 mg (73.9%) of the title compound as a white solid. FAB MS [M+H] m/z; Calcd: 604, Found 604.
The intermediate (benzyloxycarbonyl)-L-valyl-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]hydroxymethyl)-2-(S)-methylpropyl]-L-prolinamide was prepared as follows:
a. 3-(S)-Amino-2-(R,S)-hydroxy-4-methyl pentanoic acid.
To a solution containing 3-(S)-[(benzyloxycarbonyl)amino]-2-acetoxy-4-methylpentanenitrile (see example 1 of WO 96/16080) (15.2 g, 50.0 mmol) in 183 mL of dioxane was added 183 mL of concentrated hydrochloric acid and 7.45 mL of anisole. The reaction mixture was heated to reflux overnight. The hydrolysis reaction was allowed to cool to room temperature and then concentrated in vacuo. The resulting aqueous solution was extracted with ether (2X). The aqueous phase was placed on a Dowex 50X8-100 column (H + form, preeluted with deionized water to pH=7). The column was eluted with 2.0 N ammonium hydroxide and the pure fractions concentrated to afford 5.53 g (75%) of 3-(S)-amino-2-(R,S)-hydroxy-4-methylpentanoic acid as a pale yellow solid. FAB MS [M+H] m/z; Calcd: 148, Found: 148.
b. 3-(S)-[(Benzyloxycarbonyl)amino]-2-(R,S)-hydroxy-4-methylpentanoic acid.
To a solution under an atmosphere of nitrogen containing 1.0 g (6.8 mmol) of 3-(S)-amino-2-(R,S)-hydroxy-4-methylpentanoic acid in 9.5 mL of 1 N NaOH and 10 mL of dioxane was added 1.43 g (8.4 mmol) of benzyl chloroformate. The pH was maintained above pH 8 with 1 N NaOH as needed. The reaction mixture was allowed to stir at room temperature overnight. The reaction was diluted with water and washed with ether. The aqueous layer was acidified with 1 N HCl to pH=2 and extracted with ether (2X). The combined organic layers were dried over magnesium sulfate, filtered and evaporated in vacuo to afford 1.75 g (92%) of 3-(S)-[(benzyloxycarbonyl)amino]-2-(R,S)-hydroxy-4-methylpentanoic acid as a light yellow viscous oil. FAB MS [M+H] m/z; Calcd: 282, Found: 282.
c. 3-(S)-[(Benzyloxylcarbonyl)amino]-2-(R,S)-acetoxy-4-methyl pentanoic acid.
To a solution of 3-(S)-[(benzyloxycarbonyl)amino]-2-(R,S)-hydroxy-4-methylpentanoic acid (1.70 g, 6.04 mmol) and pyridine (4.9 mL) was added acetic anhydride (5.7 mL, 6.17 g, 60.4 mmol) dropwise at room temperature. The reaction was allowed to stir overnight and was diluted with ethyl acetate and washed with water (2X). The organic layer was dried over magnesium sulfate, filtered and evaporated in vacuo to give a thick oil. The residue was purified by column chromatography on silica gel with 15% methanol/dichloromethane to afford 1.56 g (80%) of 3-(S)-[(benzyloxycarbonyl)amino]-2-(R,S)-acetoxy-4-methyl pentanoic acid as a light yellow viscous oil. FAB MS [M+H] m/z; Calcd: 324, Found: 324.
d. 1-[(3-Methylphenylacetyl)-2-(2-(R,S)-acetoxy)-3-(S)-[(benzyloxycarbonyl)amino]-4-methylpentanoyl]hydrazine.
To a solution containing 3-(S)-[(benzyloxycarbonyl)amino]-2-(R,S)-acetoxy-4-methylpentanoic acid (2.3 g, 7.11 mmol) in 40 mL of DMF under a nitrogen atmosphere at 0° C. was added 1.31 g (9.69 mmol) of HOBT and 1.36 g (7.09 mmol) of EDCI. After stirring for 30 minutes, 1.20 g (7.31 mmol) of 3-methylphenyl acetic hydrazide (prepared analogously to the monoacid hydrazides cited by Rabins et. al. (J. Org. Chem, 30:2486 (1965)) and 1.0 mL (9.10 mmol) of NMM were added. The reaction was allowed to warm to room temperature and stir overnight. The reaction was diluted with ethyl acetate and washed with 5% potassium hydrogen sulfate, saturated sodium bicarbonate, brine and water. The organic phase was dried over magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by column chromatography on silica gel with 10% methanol/dichloromethane to afford 2.31 g (89.0%) of the title compound as a white solid. FAB MS [M+H] m/z; Calcd: 470, Found: 470.
e. 1-[2-((5-(3-methylphenyl))-1,3,4-oxadiazolyl]-1-acetoxy-2-(S)-[(benzyloxycarbonyl)amino]-3-methylbutane.
A solution containing 2.31 g (4.92 mmol) of 1-[(3-methylphenylacetyl)-2-(2-(R,S)-acetoxy)-3-(S)-[(benzyloxycarbonyl)amino]-4-methyl pentanoyl]hydrazine in 25 mL of pyridine and 1.88 g (9.86 mmol) of toluene sulfonyl chloride was heated at reflux under a nitrogen atmosphere for 72 hours. The solvent was removed under reduced pressure and the residue dissolved in ethyl acetate and washed with water. The organic phase was dried over magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by column chromatography on silica gel with 5% ethyl acetate/hexane to afford 1.41 g (63.5%) of the title compound. FAB MS [M+H] m/z; Calcd: 452, Found: 452.
f. 1-[2-(5-[3-Methylbenzyl]-1,3,4-oxadiazolyl)]-2-(S)-[(benzyloxycarbonyl)amino]-3-methylbutan-1-ol.
A solution containing 1.80 g (3.99 mmol) of 1-[2-(5-[3-methylbenzyl]-1,3,4-oxadiazolyl)]-1-acetoxy-2-(S)-[(benzyloxycarbonyl)amino]-3-methylbutane and 0.72 g (5.21 mmol) of potassium carbonate in 30 mL of methanol and 8 mL of water was allowed to stir at room temperature for 30 minutes. The solvent was removed under reduced pressure and the residue dissolved in ethyl acetate and washed with water. The organic phase was dried over magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by column chromatography on silica gel with 50% ethyl acetate/hexane to afford 1.46 g (89.3%) of the title compound. FAB MS [M+H] m/z; Calcd: 410, Found: 410.
g. 1-[2-(5-[3-Methylbenzyl])-1,3,4-oxadiazolyl]-2-(S)-Amino-3-methylbutan-1-ol hydrochloride.
To a solution containing 1.31 g (3.20 mmol) of 1-[2-(5-[3-methylbenzyl])-1,3,4-oxadiazolyl]-2-(S)-[(benzyloxycarbonyl)amino]-3-methylbutan-1-ol in 25 mL of trifluoroacetic acid under a nitrogen atmosphere at 0° C. was added 0.43 mL (3.94 mmol) of thioanisole. The reaction was allowed to warm to room temperature overnight. The solvent was removed under reduced pressure and the residue dissolved in ether and cooled to -78° C. under a nitrogen atmosphere. To this solution was added 3 mL (3 mmol) of 1 N hydrochloric acid in ether. The resulting white solid was allowed to settle and the ether decanted. Additional ether was added and decanted (3X). The solid was dried under vacuum to afford 0.92 g (92.2%) of the title compound. FAB MS [M+H] m/z; Calcd: 276, Found: 276.
h. (Benzyloxycarbonyl)-L-valyl-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]hydroxylmethyl)-2-(S)-methylpropyl]-L-prolinamide.
To a solution containing 1.30 g (3.38 mmol) of Cbz-Val-Pro-OH in 25 mL of anhydrous dichloromethane under a nitrogen atmosphere at 0° C. was added 0.90 g (3.54 mmol) of BOPCl and 0.60 g (3.44 mmol) of DIEA. After stirring for 30 minutes, 0.90 g (2.89 mmol) of 1-[2-(5-[3-methylbenzyl])-1,3,4-oxadiazolyl]-2-(S)-amino-3-methyl butan-1-ol hydrochloride in 15 mL of dichloromethane and 0.6 mL (3.94 mmol) of DIEA was added. The reaction was allowed to stir at 0° C. overnight. The reaction was diluted with dichloromethane and washed with a saturated sodium bicarbonate solution. The organic phase was dried over magnesium sulfate, filtered and evaporated. The residue was purified by column chromatography on silica gel with 5% methanol/dichloromethane to afford 1.0 g (57.3%) of the title compound as a tan solid. FAB MS [M+H] m/z; Calcd: 606, Found: 606.
Example 2
(CE-2074)(Benzyloxycarbonyl)-L-valyl-N-[1-(2-[5-(methyl)-1,3,4-oxadiazoly]carbony)]-2-(S)-methylpropyl]-L-prolinamide. Prepared similar to Example 1. FAB MS [M+H] m/z; Calcd: 514, Found: 514.
Example 3
(CE-2075)(Benzyloxycarbonyl)-L-valyl-N-[1-(2-[5-(3-trifluoromethylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]-L-prolinamide. Prepared similar to Example 1. FAB MS [M+H] m/z; Calcd: 658, Found: 658.
Example 4
(CE-2100)(Benzyloxycarbonyl)-L-valyl-N-[1-(2-[5-(4-Dimethylamino benzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]-L-prolinamide. Prepared similar to Example 1. FAB MS [M+H] m/z; Calcd: 633, Found: 633.
Example 5
(CE-2124)(Benzyloxycarbonyl)-L-valyl-N-[1-(2-[5-(1-napthylenyl)-1,3,4-xadiazolyl]carbonyl)-2-(S)-methylpropyl]-L-prolinamide. Prepared similar to Example 1. FAB MS [M+H] m/z; Calcd: 640, Found: 640.
Example 6
(CE-2177)(Benzyloxycarbonyl)-L-valyl-N-[1-(2-[5-(3,4-methylenedioxybenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]-L-prolinamide. Prepared similar to Example 1. FAB MS [M+H] m/z; Calcd: 634, Found: 634.
Example 7
(CE-2178)(Benzyloxycarbonyl)-L-valyl-N-[1-(3-[5-(3,4-methylenedioxybenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]-L-prolinamide. Prepared similar to Example 1 of WO 96/16080. FAB MS [M+H] m/z; Calcd: 634, Found: 634.
Example 8
(CE-2052)(Benzyloxycarbonyl)-L-valyl-N-[1-(3-[5-(3,5-dimethylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]-L-prolinamide. Prepared similar to Example 1 of WO 96/16080. FAB MS [M+H] m/z; Calcd: 618, Found: 618.
Example 9
(CE-2053)(Benzyloxycarbonyl)-L-valyl-N-[1-(3-[5-(3,5-dimethoxybenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]-L-prolinamide. Prepared similar to Example 1 of WO 96/16080. FAB MS [M+H] m/z; Calcd: 650, Found: 650.
Example 10
(CE-2054)(Benzyloxycarbonyl)-L-valyl-N-[1-(3-[5-(3,5-ditrifluoromethylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]-L-prolinamide. Prepared similar to Example 1 of WO 96/16080. FAB MS [M+H] m/z; Calcd: 726, Found: 726.
Example 11
(CE-2055)(Benzyloxycarbonyl)-L-valyl-N-[1-(3-[5-(3-methylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]-L-prolinamide. Prepared similar to Example 1 of WO 96/16080. FAB MS [M+H] m/z; Calcd: 604, Found: 604.
Example 12
(CE-2057)(Benzyloxycarbonyl)-L-valyl-N-[1-(3-[5-biphenylmethine)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]-L-prolinamide. Prepared similar to Example 1 of WO 96/16080. FAB MS [M+H] m/z; Calcd: 666, Found: 666.
Example 13
(CE-2058)(Benzyloxycarbonyl)-L-valyl-N-[1-(3-[5-(4-phenylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]-L-prolinamide. Prepared similar to Example 1 of WO 96/16080. FAB MS [M+H] m/z; Calcd: 666, Found: 666.
Example 14
(CE-2062)(Benzyloxycarbonyl)-L-valyl-N-[1-(3-[5-(3-phenylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]-L-prolinamide. Prepared similar to Example 1 of WO 96/16080. FAB MS [M+H] m/z; Calcd: 666, Found: 666.
Example 15
(CE-2066)(Benzyloxycarbonyl)-L-valyl-N-[1-(3-[5-(3-phenoxybenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]-L-prolinamide. Prepared similar to Example 1 of WO 96/16080. FAB MS [M+H] m/z; Calcd: 682, Found: 682.
Example 16
(CE-2069)(Benzyloxycarbonyl)-L-valyl-N-[1-(3-[5-cyclohexylmethylene)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]-L-prolinamide. Prepared similar to Example 1 of WO 96/16080. FAB MS [M+H] m/z; Calcd: 596, Found: 596.
Example 17
(CE-2073)(Benzyloxycarbonyl)-L-valyl-N-[1-(3-[5-(α,α-dimethyl-3-trifluoromethylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]-L-prolinamide. Prepared similar to Example 1 of WO 96/16080. FAB MS [M+H] m/z; Calcd: 686, Found: 686.
Example 18
(CE-2077)(Benzyloxycarbonyl)-L-valyl-N-[1-(3-[5-(1-napthylmethylene)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]-L-prolinamide. Prepared similar to Example 1 of WO 96/16080. FAB MS [M+H] m/z; Calcd: 640, Found: 640.
Example 19
(CE-2078)(Benzyloxycarbonyl)-L-valyl-N-[1-(3-[5-(3-pyridylmethyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]-L-prolinamide. Prepared similar to Example 1 of WO 96/16080. FAB MS [M+H] m/z; Calcd: 591, Found: 591.
Example 20
(CE-2096)(Benzyloxycarbonyl)-L-valyl-N-[1-(3-[5-(3,5-diphenylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]-L-prolinamide. Prepared similar to Example 1 of WO 96/16080. FAB MS [M+H] m/z; Calcd: 742, Found: 742.
Example 21
(CE-2115)(Benzyloxycarbonyl)-L-valyl-N-[1-(3-[5-(4-dimethylaminobenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]-L-prolinamide. Prepared similar to Example 1 of WO 96/16080. FAB MS [M+H] m/z; Calcd: 633, Found: 633.
Example 22
(CE-2089) 2-[5-[(Benzyloxycarbonyl)amino]-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(3-[5-(3-trifluoromethylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-(S)-2-methylpropyl]acetamide.
To a mixture containing 1.15 g (8.60 mmol) of N-chlorosuccinimide in 43 mL of anhydrous toluene at 0° C. under a nitrogen atmosphere was added 0.95 mL (12.9 mmol) of dimethyl sulfide. The reaction was cooled to -25° C. using a carbon tetrachloride/dry ice bath, followed by the dropwise addition of a solution containing 2-[5-[(benzyloxycarbonyl)amino]-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(3-[5-(3-trifluoromethylbenzyl)-1,2,4-oxadiazolyl]hydroxymethyl)-(S)-2-methylpropyl]acetamide (1.52 g, 2.15 mmol) in 15 mL of anhydrous toluene. The reaction was allowed to stir for 2 hours at -25° C. followed by the addition of 1.2 mL (8.60 mmol) of triethylamine. The cold bath was removed and the mixture allowed to warm to room temperature over 20 minutes. The reaction mixture was diluted with ethyl acetate and washed with water. The organic phase was dried over magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by column chromatography on silica gel using a gradient elution of 2 to 10% methanol/dichloromethane to afford 1.19 g of material which was further purified via preparative HPLC to afford 629 mg (41%) of the title compound as a white solid. FAB MS [M+H] m/z; Calcd: 707, Found: 707.
The intermediate 2-[5-[(benzyloxycarbonyl)amino]-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(3-[5-(3-trifluoromethylbenzyl)-1,2,4-oxadiazolyl]hydroxymethyl)-(S)-2-methylpropyl]acetamide was prepared as follows: to a solution containing 1.35 g (3.7 mmol) of 1-[3-[5-(3-methylbenzyl)-1,2,4-oxadiazolyl]-2-(S)-amino-3-methylbutan-1-ol hydrochloride and [5-[(benzyloxycarbonyl)amino]-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]acetic acid (J. Med. Chem. 38:98-108 (1995)) in 10 mL of anhydrous DMF was added 1.0 mL (7.44 mmol) of TEA and 0.76 g (4.94 mmol) of HOBT. The mixture was cooled to 0° C. and 0.95 g (4.94 mmol) of EDC was added and the reaction mixture was allowed to stir overnight. An additional 1.0 mL (7.44 mmol) of TEA was added and the reaction again allowed to stir overnight. The reaction was diluted with dichloromethane and washed with a saturated ammonium chloride solution (2X) and water. The organic phase was dried over magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by column chromatography on silica gel with 2% methanol/dichloromethane to afford 1.52 g (87%) of the title compound. FAB MS [M+H] m/z; Calcd: 709, Found: 709.
Example 23
(CE-2090) 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-1-(3-[5-(3-trifluoromethylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide.
To a mixture containing 0.41 g (0.56 mmol) of 2-[5-[(benzyloxycarbonyl)amino]-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(3-[5-(3-trifluoromethylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-(S)-2-methylpropyl]acetamide in 4 mL of trifluoracetic acid at room temperature under a nitrogen atmosphere was added 87 mg (0.70 mmol) of thioanisole. The reaction mixture was allowed to stir for 3 days and concentrated in vacuo. The residue was purified via preparative HPLC to afford 269 mg (47%) of the title compound as a white solid. FAB MS [M+H] m/z; Calcd: 573, Found: 573.
Example 24
(CE-2095) 2-[5-[(Benzyloxycarbonyl)amino]-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl]-(S)-2-methylpropyl]acetamide.
To a mixture containing 0.83 g (6.23 mmol) of N-chlorosuccinimide in 32 mL of anhydrous toluene at 0° C. under a nitrogen atmosphere was added 0.7 mL (9.35 mmol) of dimethyl sulfide. The reaction was cooled to -25° C. using a carbon tetrachloride/dry ice bath, followed by the dropwise addition of a solution containing 2-[5-[(benzyloxycarbonyl)amino]-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]hydroxymethyl)-(S)-2-methylpropyl]acetamide (1.02 g, 1.56 mmol) in 12 mL of anhydrous toluene. The reaction was allowed to stir for 2 hours at -25° C. followed by the addition of 0.9 mL (6.23 mmol) of triethylamine. The cold bath was removed and the mixture allowed to warm to room temperature over 20 minutes. The reaction mixture was diluted with ethyl acetate and washed with water. The organic phase was dried over magnesium sulfate, filtered and evaporated. The residue was purified by column chromatography on silica gel using 1% methanol/dichloromethane to afford 1.37 g of material which was further purified via preparative HPLC to give 368 mg (36%) of the title compound as a white solid. FAB MS [M+H] m/z; Calcd: 653, Found: 653.
The intermediate 2-[5-[(benzyloxycarbonyl)amino]-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]hydroxymethyl)-(S)-2-methylpropyl]acetamide was prepared as follows: to a solution containing 1.35 g (3.7 mmol) of 1-[2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]-2-(S)-amino-3-methyl butane hydrochloride and [5-[(benzyloxycarbonyl)amino]-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]acetic acid (J. Med. Chem., 38:98-108 (1995)) in 10 mL of anhydrous DMF was added 0.73 mL (6.6 mmol) of NMM and 0.46 g (3.0 mmol) of HOBT. The mixture was cooled to 0° C. and 0.50 g (2.6 mmol) of EDCI was added and the reaction mixture was allowed to stir for 2 days. The reaction was diluted with dichloromethane and washed with a saturated ammonium chloride solution (2X) and water. The organic phase was dried over magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by column chromatography on silica gel using a gradient elution of 2 to 5% methanol/dichloromethane to afford 1.02 g (77%) of the title compound. FAB MS [M+H] m/z; Calcd: 655, Found: 655.
Example 25
(CE-2101) 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide.
To a mixture containing 0.219 g (0.335 mmol) of 2-[5-[(benzyloxycarbonyl)amino]-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(3methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-(S)-2-methylpropyl]acetamide in 3 mL of trifluoroacetic acid at room temperature under a nitrogen atmosphere was added 0.05 mL (0.402 mmol) of thioanisole. The reaction mixture was allowed to stir for 3 days and concentrated in vacuo. The residue was purified via preoperative HPLC to afford 187 mg (88%) of the title compound as a white solid. FAB MS [M+H} m/z; Calcd: 519, Found: 519.
Example 26
(CE-2164)(Pyrrole-2-carbonyl)-N-(benzyl)glycyl-N-[-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl-2-(S)-methylpropyl]amide.
To a mixture containing 1.97 g (14.7 mmol) of N-chlorosuccinimide on 60 mL of anhydrous toluene at 0° C. under a nitrogen atmosphere was added 1.54 mL (21.0 mmol) of dimethyl sulfide. The mixture was allowed to stir for 1 hr. The reaction was cooled to -25° C. using a carbon tetrachloride/dry ice bath, followed by the dropwise addition of a solution contain (0.90 g, 1.49 mmol) of (pyrrole-2-carbonyl)-N-(benzyl)glycyl-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]hydroxymethyl)]-2-(S)-methylpropyl]amide in 30 mL of anhydrous toluene. The reaction was allowed to stir for 1 hour at -25° C. followed by the addition of 2.16 mL (15.5 mmol) of triethylamine. The cold bath was removed and the mixture allowed to warm to room temperature over 20 minutes. The reaction mixture was diluted with ethyl acetate and washed with water. The organic phase was dried over magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by column chromatography on silica gel with ethyl acetate/hexane (4:1). The material was further purified via preparative HPLC to afford 1.20 g (63.4%) of the title compound as a white solid. FAB MS [M+H] m/z; Calcd: 514, Found: 514.
The intermediate (pyrrole-2-carbonyl)-N-(benzyl)glycyl-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]hydroxymethyl)]-2-(S)-methylpropyl]amide was prepared by the following method:
a. (Pyrrole-2-carbonyl)-N-(benzyl)glycine-t-butyl ester.
To a suspension containing 3.00 g (27.0 mmol) of pyrrole-2-carboxylic acid in 75 mL of anhydrous dichloromethane under a nitrogen atmosphere at 0° C. was added 6.96 g (27.0 mmol) of BOPCl and 14.1 mL (81.0 mmol) of DIEA. After stirring for 30 minutes, 5.97 g (27.0 mmol) of N-(benzyl)gylcine-t-butyl ester was added and the reaction allowed to warm to room temperature overnight. The reaction was diluted with ethyl acetate and washed with a 5% potassium hydrogensulfate, saturated sodium bicarbonate solution and brine. The organic phase was dried over magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by column chromatography on silica gel using a gradient of 100% hexane to 60% hexane/ethyl acetate to afford 2.92 g (34.4%) of the title compound as a white solid. FAB MS [M+H] m/z Calcd: 315, Found: 315.
b. (Pyrrole-2-carbonyl)-N-(benzyl)glycine.
To a solution containing 2.85 g (9.01 mmol) of (Pyrrole-2-carbonyl)-N-(benzyl)glycine-t-butyl ester in 50 mL of anhydrous dichloromethane cooled to 0° C. was added 25 mL of TFA dropwise. After 90 minutes an additional 25 mL of TFA was added and allowed to stir for 30 minutes. The mixture was evaporated in vacuo to afford 2.19 g of (Pyrole-2-carbonyl)-N-(benzyl)glycine as a tan solid. FAB MS [M+H] m/z; Calcd. 259, Found 259.
c. (Pyrrole-2-carbonyl)-N-(benzyl)glycyl-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]hydroxymethyl)]-(S)-2-methylpropyl]amide.
To a solution containing 1.90 g (7.35 mmol) of (Pyrrole-2-carbonyl)-N-(benzyl)glycine in 75 mL of anhydrous DMF was added 2.4 mL (22.1 mmol) of NMM and 1.29 g (9.56 mmol) of HOBT. The mixture was cooled to 0° C. and 1.69 g (8.82 mmol) of EDCI was added and the reaction mixture was allowed to stir. After 30 minutes 2.17 g (6.99 mmol) of 1-[2-(5-[3-methylbenzyl])-1,3,4-oxadiazolyl]-2-(S)-amino-3-methyl butan-1-ol hydrochloride in 25 mL of anhydrous DMF was added and the mixture was allowed to warm to room temperature overnight. The reaction was diluted with ethyl acetate and washed with 5% potassium hydrogen sulfate and water. The organic phase was dried over magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by column chromatography on silica gel using a gradient elution of 20 to 80% ethyl acetate/hexane to afford 2.02 g (56%) of the title compound. FAB MS [M+H] m/z Calcd: 516, Found: 516.
Example 27
(CE-2097)(Pyrrole-2-carbonyl)-N-(benzyl)glycyl-N-[1-(3-[5-(3-trifluoromethylbenzyl)]-1,2,4-oxadiazolyl]carbonyl)-(S)-methylpropyl]amide was prepared in a similar manner to Example 25. FAB MS [M+H] m/z; Calcd: 568, Found: 568.
Example 28
(CE-2130)(2S,5S)-5-Amino-1,2,4,5,6,7-hexahydroazepino-[3,2,1]-indole-4-one-carbonyl-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-(R,S)-2-methylpropyl]amide.
To a solution containing 0.93 g (1.28 mmol) of (2S,5S)-Fmoc-5-amino-1,2,4,5,6,7-hexahydroazepino [3,2,1]indole-4-one-carbonyl-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-(S)-2-methylpropyl]amide in 4.5 mL of anhydrous DMF under an atmosphere of nitrogen was added 0.45 mL of diethylamine. After stirring at room temperature for 15 min the mixture was concentrated under high vacuum. The residue was purified via preparative HPLC to afford 0.57 g (72%) of the title compound as a white solid. FAB MS [M+H] m/z; Calcd: 502, Found 502.
The intermediate (2S,5 S)-Fmoc-5-amino-1,2,4,5,6,7-hexahydroazepino-[3,2,1]-indole-4-one-carbonyl-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-(R,S)-2-methylpropyl]amide was prepared as follows:
a. (2S,5S)-Fmoc-5-amino-1,2,4,5,6,7-hexahydroazepino-[3,2,1]-indole-4-one-carbonyl-N-[1]-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]hydroxymethyl)-(S)-2-methylpropyl]amide.
To a solution containing 1.25 g (2.67 mmol) of (2S,5S)-Fmoc-5-amino-1,2,4,5,6,7-hexahydroazepino [3,2,1]indole-4-one-carboxylic acid in 200 mL of anhydrous dichloromethane and 1 mL of anhydrous DMF under a nitrogen atmosphere at 0° C. was added 0.71 g (2.80 mmol) of BOPCl and 0.6 mL (3.45 mmol) of DIEA. After stirring for 1 hr 1.14 g (3.66 mmol) of 1-[2-(5-[3-methylbenzyl])-1,3,4-oxadiazolyl]-2-(S)-amino-3-methylbutan-1-ol hydrochloride in 10 mL of anhydous dichloromethane was added and the reaction mixture allowed to stir at 4° C. overnight. The reaction was diluted with dichloromethane and washed with water. The organic phase was dried over -magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by column chromatograph on silica gel using 3% methanol/dichloromethane to afford 1.30 g (67%) of the title compound as tan solid.
b. (2S, 5S)-Fmoc-5-amino-1,2,4,5,6,7-hexahydroazepino-[3,2,1]-indole-4-one-carbonyl-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)]-(S)-2-methylpropyl]amide.
To a mixture containing 0.95 g (7.16 mmol) of N-chlorosuccinimide in 150 mL of anhydrous toluene at 0° C. under a nitrogen atmosphere was added 0.79 mL (10.7 mmol) of dimethyl sulfide. The mixture was allowed to stir for 30 minutes. The reaction was cooled to -25° C. using a carbon tetrachloride/dry ice bath, followed by the dropwise addition of a solution containing 1.30 g (1.79 mmol) of (2S, 5S)-Fmoc-5-amino-1,2,4,5,6,7-hexahydroazepino-[3,2,1]-indole-4-one-carbonyl-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]hydroxymethyl)]-(S)-2-methylpropyl]amide in 10 mL of anhydrous toluene. The reaction was allowed to stir for 2 hours at -25° C. followed by the addition of 1.17 mL (8.4 mmol) of triethylamine. The cold bath was removed and the mixture was allowed to warm to room temperature over 30 minutes. The reaction mixture was diluted with ethyl acetate and washed with water. The organic phase was dried over magnesium sulfate. The residue was filtered, concentrated under reduced pressure and purified by column chromatography on silica gel with 10% ethyl acetate/hexane to give 0.93 g (72%) as a tan foam.
Example 29
(CE-2126) BTD-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]amide.
To a solution containing 0.41 g (0.59 mmol) of FMOC-BTD-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazole]carbonyl)-2-(S)-methylpropyl]amide in 4.5 mL of anhydrous DMF under an atmosphere of nitrogen was added 0.5 mL of diethylamine. After stirring at room temperature for 30 min the mixture concentrated under high vaccum. The residue was purified via preparative HPLC to afford 0.23 g (66%) of the title compound as a white solid. FAB MS [M+H] m/z; Calcd: 472, Found 472.
The intermediate Fmoc-BTD-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]amide was prepared as follows:
a. (2S, 5S)-Fmoc-BTD-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]hydroxymethyl)-2-(S)-methylpropyl]amide.
To a solution containing 1.25 g (2.85 mmol) of FMOC-BTD in 80 mL of anhydrous dichloromethane and 2.5 mL of anhydrous DMF under a nitrogen atmosphere at 0° C. was added 0.76 g (2.99 mmol) of BOPCl and 0.6 mL (3.45 mmol) of DIEA. After stirring for 30 minutes and 1.14 g (3.66 mmol) of 1-[2-(5-[3-methylbenzyl])-1,3,4-oxadiazolyl]-2-(S)-amino-3-methylbutan-1-ol hydrochloride and 0.6 mL of DIEA in 10 mL of anhydrous dichloromethane was added and the reaction mixture allowed to stir at 0° C. overnight. The reaction was diluted with dichloromethane and washed with water. The organic phase was dried over magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by column chromatography on silica gel using 3% methanol/dichloromethane to afford 1.13 g (55%) of the title compound as a tan foam.
b. Fmoc-BTD-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)]-2-(S)-methylpropyl]amide.
To a mixture containing 0.81 g (6.09 mmol) of N-chlorosuccinimide in 110 mL of 1:1 anhydrous dichloromethane/toluene at 0° C. under a nitrogen atmosphere was added 0.67 mL (9.1 mmol) of dimethyl sulfide. The mixture was allowed to stir for 30 minutes. The reaction was cooled to -25° C. using a carbon tetrachloride/dry ice bath, followed by the dropwise addition of a solution containing 1.06 g (1.52 mmol) of Fmoc-BTD-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]hydroxymethyl)-2-(S)-methylpropyl]amide in 10 mL of anhydrous toluene. The reaction was allowed to stir for 2 hours at -25° C. followed by the addition of 1.0 mL (7.6 mmol) of triethylamine. The cold bath was removed and the mixture was allowed to warm to room temperature over 40 minutes. The reaction mixture was diluted with ethyl acetate and washed with water. The organic phase was dried over magnesium sulfate. The resulting mixture was filtered, concentrated under reduced pressure and purified by column chromatography on silica gel with 70% ethyl acetate/hexane to give 0.53 g of the product as a yellow oil. The material was further purified by preparative HPLC to afford 0.41 g (38.8%) of the title compound as a white solid.
Example 30
(CE-2134)(R,S)-3-Amino-2-oxo-5-phenyl-1,4,-benzodiazepine-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide.
To a solution containing 0.93 g (1.19 mmol) of (R,S)-FMOC-3-amino-2-oxo-5-phenyl-1,4,-benzodiazepine-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide in 6.0 mL of anhydrous DMF under an atmosphere of nitrogen was added 0.45 mL of diethylamine. After stirring at room temperature for 2.5 hr the mixture was concentrated under high vaccum. The residue was purified via preparative HPLC to afford 0.030 g (4.5%) of the title compound as a white solid. FAB MS [M+H] m/z; Calcd: 565, Found 565.
The intermediate (R,S)-FMOC-3-amino-2-oxo-5-phenyl-1,4,-benzodiazepine-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide was prepared as follows:
a. (R,S)-FMOC-3-amino-2-oxo-5-phenyl-1,4,-benzodiazepine-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]hydroxymethyl)-2-(S)-methylpropyl]acetamide.
To a solution containing 0.75 g (1.41 mmol) of(R,S)-FMOC-3-amino-N-1-carboxymethyl-2-oxo-5-phenyl-1,4,-benzodiazepine in 30 mL of anhydrous dichloromethane under a nitrogen atmosphere at 0° C. was added 0.36 g (1.41 mmol) of BOPCl and 0.25 mL (1.41 mmol) of DIEA. After stirring for 1 hr 0.48 g (1.55 mmol) of 1-[2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]-2-(S)-amino-3-methyl butan-1-ol hydrochloride and 0.49 mL (2.82 mmol) of DIEA in 10 mL of anhydous dichloromethane was added and the reaction mixture allowed to stir at 4° C. overnight. The reaction was diluted with ethyl acetate and washed with water. The organic phase was dried over magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by column chromatography on silica gel using a gradient of 2 to 6% methanol/dichloromethane to afford 1.00 g (89%) of the title compound as a yellow solid.
b. (R,S)-FMOC-3-amino-2-oxo-5-phenyl-1,4,-benzodiazepine-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide.
To a mixture containing 0.71 g (7.6 mmol) of N-chlorosuccinimide in 40 mL of anhydrous toluene at 0° C. under a nitrogen atmosphere was added 0.84 mL (11.4 mmol) of dimethyl sulfide. The reaction was cooled to -25° C. using a carbon tetrachloride/dry ice bath followed by the dropwise addition of a solution containing 1.50 g (1.90 mmol) of (R,S)-FMOC-3-amino-2-oxo-5-phenyl-1,4,-benzodiazepine-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]hydroxymethyl)-2-(S)-methylpropyl]acetamide in 10 mL of anhydrous toluene. The reaction was allowed to stir for 2 hours at -25° C. followed by the addition of 1.0 mL (7.6 mmol) of triethylamine. The cold bath was removed and the mixture was allowed to warm to room temperature over 1 hour. The reaction mixture was diluted with ethyl acetate and washed with water. The organic phase was dried over magnesium sulfate. The residue was filtered, concentrated under reduced pressure to afford 0.94 g (62%) of material which was used without further purification. FAB MS [M+H] m/z; Calcd: 787, Found: 787.
Example 31
(CE-2145)(Benzyloxycarbonyl)-L-valyl-2-L-(2,3-dihydro-1H-indole)-N-[-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]amide.
To a mixture containing 0.48 g (3.67 mmol) of N-chlorosuccinimide in 30 mL of anhydrous toluene at 0° C. under a nitrogen atmosphere was added 0.40 mL (5.41 mmol) of dimethyl sulfide. After stirring for 1 hr the reaction mixture was cooled to -25° C. using a carbon tetrachloride/dry ice bath followed by the dropwise addition of a solution containing 0.95 g (1.90 mmol) of(benzyloxycarbonyl)-L-valyl-2-L-(2,3-dihydro-1H-indole)-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]hydroxymethyl)-2-(S)-methylpropyl]amide in 20 mL of anhydrous toluene. The reaction was allowed to stir for 2 hours at -25° C. followed by the addition of 0.50 mL (3.6 mmol) of triethylamine. The cold bath was removed and the mixture was allowed to warm to room temperature. The reaction mixture was diluted with dichloromethane and washed with 1 N HCl (2X), saturated sodium bicarbonate (2X) and water. The organic phase was dried over magnesium sulfate. The mixture was filtered and concentrated under reduced pressure to afford 0.61 g. The residue was purified by column chromatography on silica gel with 50% ethyl acetate/hexane to afford 0.27 g of material which was further purified via preparative HPLC to afford 196 mg (33.4%) of the title compound as a white solid. FAB MS [M+H] m/z Calcd: 652, Found 652.
The intermediate (benzyloxycarbonyl)-L-valyl-2-L-(2,3-dihydro-1H-indole)-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]hydroxymethyl)-2-(S)-methylpropyl]amide was prepared by the following procedures:
a. 2-L-Methyl (2,3-dihydroindole)carboxylate.
To a suspension containing 5.00 g (30.6 mmol) of 2-L-(2,3-dihydroindole)carboxylic acid in 100 mL of anhydrous MEOH cooled to 0° C. was added a slow stream of HCl gas over 20 minutes. The resulting homogeneous solution was allowed to stir overnight warming to room temperature. The mixture was evaporated and the residue was crystallized from methanol/ether to afford, after drying, 5.58 g (85%) of 2-L-methyl (2,3-dihydroindole)carboxylate.
b. 2-Methyl [(S)-1-(N-[benzyloxycarbonyl]-L-valyl)-2,3-dihydro-1 H-indole]carboxylate.
To a solution containing 3.00 g (14.0 mmol) of methyl (2,3-dihydroindole)-L-2-carboxylate in 60 mL of anhydrous dichloromethane, under a nitrogen atmosphere at 0° C., 7.15 g (28.8 mmol) of BOPCl and 7.72 mL (70.2 mmol) of DIEA was added a solution of 7.06 g (28.08 mmol) of Cbz-Val-OH in 40 mL of anhydrous dichloromethane and 3 mL of DMF. After stirring for 3 days at 5° C. the mixture was diluted with ethyl acetate and washed with 1 N HCl (2X) and brine. The mixture was filtered and evaporated under reduced pressure. The residue was purified by column chromatography on silica gel using a gradient of 9:1 to 1:1 hexane/ethyl acetate to afford 4.85 g (87%) of the title compound as a white foam.
c. 2-[(S)-1-(N-[Benzyloxycarbonyl]-L-valyl)-2,3-dihydro-1 H-indole]carboxylic acid.
To a solution containing 4.85 g (12.17 mmol) of 2-methyl [(S)-1-(N-[benzyloxycarbonyl]-L-valyl)-2,3-dihydro-1 H-indole]carboxylate in 45 mL of THF and 15 mL of MeOH at 0° C. was added 15.8 mL of 1 N LiOH dropwise. After 30 minutes 1 N HCl was added to pH 2 and the mixture extracted with ethyl acetate (3X). The combined organic phases were dried over magnesium sulfate, filtered and evaporated under reduced pressure to afford 4.51 g (93%) of the title compound as a white solid.
d. (Benzyloxycarbonyl)-L-valyl-2-L-(2,3-dihydro-1H-indole)-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]hydroxymethyl)-2-(S)-methylpropyl]amide.
To a solution containing 1.09 g (3.96 mmol) of 1-[2-(5-[3-methylbenzyl])-1,3,4-oxadiazolyl]-2-(S)-amino-3-methylbutan-1-ol and 1.31 g (3.3 mmol) of 2-[(S)-1-(N-[benzyloxycarbonyl]-L-valyl)-2,3-dihydro-1H-indole]carboxylic acid in 30 mL of anhydrous dichloromethane was added 1.21 mL (6.93 mmol) of DIEA and 0.49 g (3.63 mmol) of HOBT. The mixture was cooled to 0° C. and 0.70 g (3.63 mmol) of EDCI was added and the reaction mixture was allowed to stir overnight. An additional 1.0 mL (7.44 mmol) of TEA was added and the reaction again allowed to stir overnight. The reaction was diluted with dichloromethane and washed with 1 N HCl (2X), saturated sodium bicarbonate (2X) and water. The organic phase was dried over magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by column chromatography on silica gel with 80% ethyl acetate/hexane to afford 0.66 g (30%) of the title compound.
Example 32
(CE-2125)(Benzyloxycarbonyl)-L-valyl-2-L-(2,3-dihydro-1H-indole)-N-[1-(3-[5-(3-trifluoromethylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]amide. Prepared in a similar manner as in Example 30. FAB MS [M+H] m/z; Calcd: 706, Found: 706.
Example 33
(CE-2143) Acetyl-2-L-(2,3-dihydro-1H-indole)-N-[1-(3-[5-(3-trifluoromethylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]amide. Prepared in a similar manner as in Example 30. FAB MS [M+H] m/z; Calcd: 515, Found: 515.
Example 34
(CE-2165) N-Acetyl-2-(L)-(2,3-dihydro-1H-indole)-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]amide. Prepared in a similar manner as in Example 30. FAB MS [M+H] m/z; Calcd: 461; Found: 461.
Example 35
(CE-2104)(Morpholino-N-carbonyl)-L-valyl-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]-L-prolinamide.
To a mixture containing 0.69 g (5.17 mmol) of N-chlorosuccinimide in 60 mL of anhydrous toluene at 0° C. under a nitrogen atmosphere was added 0.60 mL (8.17 mmol) of dimethyl sulfide. The reaction was cooled to -25° C. using a carbon tetrachloride/dry ice bath, followed by the addition of a solution containing (morpholino-N-carbonyl)-L-valyl-N-[1-(2-[5-(3-methyl benzyl)-1,3,4-oxadiazolyl]hydroxymethyl)-2-(S-)methyl propyl]-L-prolinamide (0.75 g, 1.28 mmol) in 10 mL of anhydrous toluene. The reaction was allowed to stir for 2 hours at -25° C. followed by the addition of 1.1 mL (0.83 g, 7,89 mmol) of triethylamine. The cold bath was removed and the reaction was allowed to warm to room temperature over 20 minutes. The reaction was diluted with ethyl acetate and washed with water. The organic phase was dried over magnesium sulfate and filtered. The solvents were evaporated in vacuo and the residue purified by column chromatography, 70% ethyl acetate/hexane on silica gel. Final purification was performed by preparative HPLC to afford 405 mg (54.3%) of the title compound as a white solid. FAB MS [M+H] m/z; Calcd: 583, Found: 583.
The intermediate (Morpholino-N-carbonyl)-L-valyl-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]hydroxymethyl)-2-(S)-methylpropyl]-L-prolinamide was prepared as follows:
a. (Morpholino-N-carbonyl)-L-valyl-L-proline-O-t-butyl ester.
To a solution containing L-valyl-L-proline-O-t-butyl-ester (1.80 g, 5.87 mmol) in 80 mL of anhydrous methylene chloride and 1.5 mL (13.64 mmol) of N-methyl morpholine under a nitrogen atmosphere at 0° C. was added morpholine carbonyl chloride dropwise. The mixture was allowed to warm to room temperature overnight. The reaction was diluted with methylene chloride and washed with water. The organic layer was dried over magnesium sulfate, filtered and evaporated. The residue was purified by column chromatography on silica gel with 10% methanol/dichloromethane to afford 1.98 g (88%) of the title compound as a white solid. FAB MS [M+H] m/z; Calcd: 384, Found 384.
b. (Morpholino-N-carbonyl)-L-valyl-L-proline.
To a solution containing (morpholino-N-carbonyl)-L-valyl-L-proline-O-t-butyl ester (2.0 g, 5.22 mmol) in 80 mL of anhydrous methylene chloride under a nitrogen atmosphere at 0° C. was added trifluoroacetic acid (13 mL, 130 mmol). The mixture was allowed to warm to room temperature overnight and the solvents were evaporated in vacuo to give 2.26 g of a viscous oil. The material was used without further purification.
c. (Morpholino-N-carbonyl)-L-valyl-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]hydroxymethyl)-2-(S)-methylpropyl]-L-prolinamide.
To a solution containing 0.95 g (2.90 mmol) of (morpholino-N-carbonyl)-L-valyl-Proline in 25 mL of anhydrous dichloromethane under a nitrogen atmosphere at 0° C. was added 0.80 g (3.14 mmol) of BOPCI and 1.5 mL (8.61 mmol) of DIEA. After 30 minutes, 0.75 g (2.41 mmol) of 1-[2-(5-[3-methylbenzyl])-1,3,4-oxadiazolyl]-2-(S)-amino-3-methylbutan-1-ol hydrochloride in 10 mL of dichloromethane and 1.1 mL (6.31 mmol) of DIEA were added. The reaction was allowed to stir at 0° C. overnight. The reaction was diluted with dichloromethane and washed with a saturated NaHCO 3 solution. The organic phase was dried over magnesium sulfate and filtered. The mixture was concentrated in vacuo and the residue purified by column chromatography on silica gel using 6% methanol/dichloromethane to afford 0.77 g (54.84%) of the title compound as a white solid. FAB MS [M+H] m/z; Calcd: 585, Found: 585.
Example 36
(CE-2079) 3-(S)-(Benzyloxycarbonyl)amino)-ε-lactam-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide.
To a mixture containing 2.37 g (17.75 mmol) of N-chlorosuccinimide in 100 mL of anhydrous toluene at 0° C. under a nitrogen atmosphere was added 1.94 mL (2.64 mmol) of dimethyl sulfide. The reaction was cooled to -25° C. using a carbon tetrachloride/dry ice bath, followed by the dropwise addition of a solution containing 2.5 g (4.44 mmol) of 3-(S)-[(benzyloxycarbonyl)amino]-ε-lactam-N-[1-(2-[5-(3-methylbenzyl)-1,2,4-oxadiazolyl]hydroxymethyl)-2-(S)-methyl propyl]acetamide in 20 mL of anhydrous toluene. Upon complete addition, the reaction was allowed to stir at -25° C. for 2 hours, followed by the addition of 3.0 mL (21.52 mmol) of triethylamine. The cold bath was removed and the reaction warmed to room temperature and stirred for 30 minutes. The reaction was diluted with ethyl acetate and washed with water. The organic phase was dried over magnesium sulfate. Filtration, removal of solvent and column chromatography of the residue on silica gel with 5% methanol/dichloromethane afforded 1.8 g of a pale yellow solid. Subsequent preparative HPLC gave 950 mg (38.1%) of the title compound as a white solid. FAB MS [M+H] m/z; Calcd: 562, Found: 562.
The intermediate 3-(S)-[(benzyloxycarbonyl)amino]-ε-lactam-N-[1-(2-[5-(3-methylbenzyl)-1,2,4-oxadiazolyl]hydroxymethyl)-2-(S)-methyl propyl]acetamide was prepared as follows:
a. 3-(S)-[(Benzyloxycarbonyl)amino]-ε-lactam.
To a mixture containing 9.9 g (37.18 mmol) of Cbz-ornithine in 150 mL of acetonitrile under a nitrogen atmosphere was added 78 mL (369.70 mmol) of hexamethyldisilazane. The reaction was heated at reflux for 48 hours. The reaction mixture was cooled to room temperature and poured into 250 mL of cold methanol. The solvent was removed under reduced pressure. Chloroform was added and the mixture filtered through a plug of celite. The filtrate was concentrated under reduced pressure and the residue dissolved in ethyl acetate. Hexane was added until the solution was slightly turbid and then allowed to stand overnight. The resultant solid was filtered and dried to afford 8.37 g (90.7%) of the title compound.
b. N-[3-(S)-(Benzyloxycarbonyl)amino]-ε-lactam-t-butyl acetate.
To a solution containing 1.0 g (4.03 mmol) of 3-(S)-[(benzyloxylcarbonyl)amino]-ε-lactam in 20 mL of anhydrous DMF under a nitrogen atmosphere was added 1.50 mL (10.16 mmol) of bromo-t-butyl acetate and 1.17 g (5.05 mmol) of silver oxide. The reaction was heated to 45° C. for 5 hours, diluted with acetonitrile and filtered through a pad of celite. The filtrate was concentrated under reduced pressure and the residue dissolved in ethyl acetate and washed with water. The organic phase was dried over magnesium sulfate. Filtration, removal of solvent and column chromatography of the residue on silica get with 60% ethyl acetate/hexane afforded 1.18 g (80.79%) of the title compound. FAB MS [M+H] m/z; Calcd: 363, Found: 363.
c. N-[3-(S)-(Benzyloxycarbonyl)amino)-ε-lactam-carboxymethane.
To a solution containing 0.55 g (1.52 mmol) of N-[3-(S)-(Benzyloxy carbonyl)amino]-ε-lactam-t-butyl acetate in 20 mL (15.58 mmol) of trifluoroacetic acid. The reaction was allowed to warm to room temperature overnight. The solvent was removed under reduced pressure. The residue was dissolved in ether acetate and washed with water. The organic phase was dried over magnesium sulfate. Filtration and removal of solvent afforded 0.50 of the title compound. FAB MS [M+H] m/z; Calcd: 307, Found: 307.
d. 3-(S)-[Benzyloxycarbonyl)amino)-ε-lactam-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]hydroxymethyl)-2-(S)-methylpropyl]acetamide.
To a solution containing 2.72 g (8.88 mmol) of N-[3-(S)-(Benzyloxycarbonyl) amino]-ε-lactam-carboxymethane in 80 mL of dichloromethane under a nitrogen atmosphere at 0° C. was added 2.37 g (9.31 mmol) of BOPCI and 1.60 mL (9.91 mmol) of DIEA. The reaction was allowed to stir at 0° C. for 30 minutes followed by the addition of 2.37 g (7.60 mmol) of 1-[3-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]-2-(S)-amino-3methyl butan-1-ol hydrochloride in 20 mL of dichloromethane and 1.60 mL (9.19 mmol) of DIEA. The reaction was allowed to stir at 0° C. overnight. The reaction was diluted with dichloromethane and washed with water. The organic phase was dried over magnesium sulfate. Filtration, removal of solvent and column chromatography of the residue on silica get with 10% methanol/dichloromethane afforded 2.58 g (50.23%) of the title compound. FAB MS [M+H] m/z; Calcd: 564, Found: 564.
Example 37
(CE-2080) 3-(S-(Amino)-ε-lactam-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide trifluoroacetic acid salt.
This compound was prepared via deprotection of 3-(S)-[benzyloxycarbonyl)amino)-ε-lactam-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methyl propyl]acetamide under standard conditions to one skilled in the art to afford the title compound. FAB MS [M+H] m/z; Calcd: 428, Found: 428.
Example 38
(CE-2091) 3-(S)-[(4-Morpholino carbonyl-butanoyl)amino]-ε-lactam-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(R,S)-methylpropyl]acetamide.
To a solution containing 0.089 g (0.475 mmol) of 4-morpholino carbonyl butanoic acid in 10 mL of dichloromethane under a nitrogen atmosphere at 0° C. was added 0.127 g (0.498 mmol) of BOPCI and 0.09 mL (0.492 mmol) of DIEA. The reaction was allowed to stir for 30 minutes followed by the addition of 0.22 g (0.406 mmol) of 3-(S)-amino-ε-lactam-N-[1-(2-[5-(3-methyl benzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(R,S)-methyl propyl]acetamide trifluoroacetic acid salt. The reaction was allowed to stir at 0° C. overnight. The reaction was diluted with dichloromethane and washed with water. The organic phase was dried over magnesium sulfate. Filtration, removal of solvent and purification via preparative HPLC afforded 0.044 g (18%) of the title compound. FAB MS [M+H] m/z; Calcd: 597, Found: 597.
Example 39
(CE-2087) 6-[4-Fluorophenyl]-ε-lactam-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide.
To a mixture containing 0.70 g (5.24 mmol) and N-chlorosuccinimide in 30 mL of anhydrous toluene at 0° C. under a nitrogen atmosphere was added 0.60 mL (8.17 mmol) of dimethyl, sulfide. The reaction was cooled to -25° C. using a carbon tetrachloride/dry ice bath, followed by the dropwise addition of a solution containing 0.67 g (1.32 mmol) of 6-[4-fluorophenyl]-ε-lactam-N-[1-(2-[5-(3-methyl benzyl)-1,3,4-oxadiazolyl]hydroxymethyl)-2-(S)-methylpropyl]acetamide in 15 mL of anhydrous toluene. Upon complete addition, the reaction was allowed to stir at -25° C. for 2 hours followed by the addition of 0.90 mL (6.46 mmol) of triethylamine. The cold bath was removed and the reaction allowed to warm to room temperature and maintained for 20 min. The reaction was diluted with ethyl acetate and washed with water. The organic phase was dried over magnesium sulfate. Filtration, removal of solvent under reduced pressure and column chromotography of the residue on silica gel with 10% methanol/dichloromethane afforded 0.61 g of a pale yellow solid. Subsequent preparative HPLC gave 338 mg (50.5%) of the title compound. FAB MS [M+H] m/z; Calcd: 507, Found: 507.
The intermediate 6-[4-fluorophenyl]-ε-lactam-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]hydroxymethyl)-2-(S)-methylpropyl]acetamide was prepared as follows:
a. 6-[4-Fluorophenyl]-6-carboxymethylene-2-piperidinone.
To a solution containing 2.15 g (8.11 mmol) of 6-[4-fluorophenyl]-1-carbomethoxymethylene-2-piperidinone, prepared in a similar fashion to that reported by Compernolle (Tetrahedron, 49:3193 (1993)) in 70 mL of methanol and 20 mL of water under a nitrogen atmosphere was added 0.55 g (13.11 mmol) of lithium hydroxide. The reaction was allowed to stir at room temperature for 2 hours. The solvent was removed under reduced pressure. The residue was diluted with water and washed with ethyl acetate. The aqueous phase was acidified with 1 N hydrochloric acid and extracted with ethyl acetate. The organic phase was dried over magnesium sulfate. Filtration and removal of solvent afforded 2.0 g (98.2%) of the title compound. FAB MS [M+H] m/z; Calcd: 252, Found: 252.
b. 6-[4-Fluorophenyl]ε-lactam-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]hydroxymethyl)-2-(S)-methylpropyl]acetamide.
To a solution containing 1.04 g (4.14 mmol) of 6-[4-fluorophenyl]-6-carboxymethylene-2-piperidinone in 25 mL of anhydrous dichloromethane under a nitrogen atmosphere at 0° C. was added 1.10 g (4.32 mmol) of BOPCI and 0.80 mL (4.59 mmol) of DIEA. After stirring for 30 minutes, a solution containing 1.1 g (3.53 mmol) of 1-[2-(5-[3-methylbenzyl])-1,3,4-oxadiazolyl]-2-(S)-amino-3-methylbutan-1-ol hydrochloride in 10 mL of dichloromethane and 1.10 mL (6.31 mmol) of DIEA. The reaction was allowed to stir at 0° C. overnight. The reaction was diluted with dichloromethane and washed with a saturated sodium bicarbonate solution. The organic phase was dried over magnesium sulfate. Filtration, removal of solvent under reduced pressure and column chromotography of the residue on silica gel with 10% methanol/dichloromethane afforded 736 mg (41.0%) of the title compound. FAB MS [M+H] m/z; Calcd: 509, Found: 509.
Example 40
(CE-2121) 2-[2-(R,S)-Phenyl-4-oxothiazolidin-3-yl]-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl] acetamide.
To a mixture containing 2.05 g (15.38 mmol) of N-chlorosuccinimide in 250 mL of anhydrous toluene at 0° C. under a nitrogen atmosphere was added 1.70 mL (23.06 mmol) of dimethyl sulfide. The reaction was cooled to -25° C. using a carbon tetrachloride/dry ice bath, followed by the addition of 1.90 g (3.84 mmol) of 2-[2-(R,S)-phenyl-4-oxothiazolidin-3-yl]-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]hydroxymethyl)-2-(S)-methylpropyl]acetamide in 20 mL of anhydrous toluene dropwise. The reaction was allowed to stir at -25° C. for 2 hours, followed by the addition of 2.52 mL (18.07 mmol) of triethylamine. The cold bath was removed and the reaction allowed to warm to room temperature over 40 minutes. The reaction was diluted with ethyl acetate and washed with water. The organic phase was dried over magnesium sulfate. Filtration, removal of solvent and column chromatography of the residue on silica gel with 60% ethyl acetate/hexane afforded 1.10 g of a yellow oil. This was further purified via preparative HPLC to give 0.45 g (24%) of the title compound as an off-white solid. FAB MS [M+H] m/z; Calcd: 493, Found 493.
The intermediate 2-[2-(R,S)-phenyl-4-oxothiazolidin-3-yl]-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]hydroxymethyl)-2-(S)-methypropyl]acetamide was prepared as follows: to a solution containing 1.78 g (7.51 mmol) of 2-(2-phenyl-4-oxothiazolidin-3-yl)acetic acid, prepared according to Holmes (J. Org. Chem, 60:7328 (1995)), in 80 mL of dichloromethane under a nitrogen atmosphere at 0° C. was added 2.04 g (8.02 mmol) of BOPCI and 1.35 mL (7.76 mmol) of DIEA. After stirring for 30 minutes, 2.0 g (6.41 mmol) of 1-[3-[5-(3-methylbenzyl)]-1,3,4-oxadiazolyl]-2-(S)-amino-3-methyl-butan-1-ol hydrochloride in 50 mL of dichloromethane and 1.35 mL (7.76 mmol) of DIEA was added. The reaction was allowed to stir at 0° C. overnight. The reaction mixture was diluted with dichloromethane and washed with water. The organic phase was dried over magnesium sulfate, filtered and concentrated under reduced pressure. Column chromatography of the residue on silica gel with 4% methanol/dichloromethane afforded 2.30 g of a yellow foam. Subsequent preparative HPLC gave 1.9 g of the title compound. FAB MS [M+H] m/z; Calcd: 495, Found: 495.
Example 41
(CE-2122) 2-[2-(R,S)-Benzyl-4-oxothiazolidin-3-yl]-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide was prepared in a similar manner as in Example 39. FAB MS [M+H] m/z; Calcd: 507, Found: 507.
Example 42
(CE-2136) 2-[(2-(R,S)-Benzyl-4-oxothiazolidin-3-yl oxide]-N-[1-(2-[5-methyl benzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(R,S,)-methylpropyl]acetamide.
To a solution containing 1.31 g (2.59 mmol) of 2-[2-(R,S)-benzyl-4-oxothiazolidin-3-yl)-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methyl propyl]-acetamide in 15 mL of methanol under a nitrogen atmosphere was added 0.51 mL (5.17 mmol) of 30% hydrogen peroxide. The reaction was allowed to stir at room temperature overnight and then partitioned between brine and dichloromethane. The organic phase was dried over magnesium sulfate. Filtration, removal of solvent under reduced pressure and column chromatography of the residue on silica gel with 85% ethyl acetate/hexane afforded 0.73 g of a tan oil. Subsequent preparative HPLC gave 0.54 g (48%) of the title compound. FAB MS [M+H] m/z; Calcd: 523, Found 523.
Example 43
(CE-2137) 2-[2-(R,S)-Benzyl-4-oxothiazolidin-3-yl oxide]-N-[1-(3-[5-(3-trifluoromethylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(R,S,)-methylpropyl]acetamide. Prepared in a similar manner as in Example 41. FAB MS [M+H] m/z; Calcd: 577, Found 577.
Example 44
(CE-2118) 2-[2-(R,S)-Phenyl-4-oxometathiazan-3yl]-N-[1-(2-[5(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide. Prepared in a similar manner as in Example 39. FAB MS [M+H] m/z; Calcd: 507, Found: 507.
Example 45
(CE-2140)(1-Benzoyl-3,8-quinazolinedione)-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide.
To a mixture containing 1.70 g (2.74 mmol) of N-chlorosuccinimide in 75 mL of anhydrous toluene at 0° C. under a nitrogen atmosphere was added 1.70 mL (23.15 mmol) of dimethyl sulfide. The reaction was cooled to -25° C. using a carbon tetrachloride/dry ice bath, followed by the addition of 1.90 g (3.27 mmol) of (1-Benzoyl-3,8-quinazolinedione)-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]hydroxymethyl)-2-(S)-methyl propyl]acetamide in 10 mL of toluene dropwise. The reaction was allowed to stir at -25° C. for 2 hours, followed by the addition of 3.20 mL (22.96 mmol) of triethylamine. The cold bath was removed and the reaction allowed to warm to room temperature and maintained for 15 minutes. The reaction was diluted with ethyl acetate and washed with water. The organic phase was dried over magnesium sulfate, filtered, and the solvent removed under reduced pressure. The residue was chromatographed on silica gel with 5% methanol/dichloromethane to afford 1.37 g of a brown oil. This was further purified via preparative HPLC to give 450 mg (40.1%) of the title compound. FAB MS [M+H] m/z; Calcd: 580, Found: 580.
The intermediate (1-benzoyl-3,8-quinazolinedione)-N-[1-(2-[5-(3-methylbenzyl)-1,2,4-oxadiazolyl]hydroxymethyl)-2-(S)-methylpropyl]acetamide was prepared as follows:
a. 1-Benzoyl-3,8-quinazolinedione-2-t-butyl acetate.
To a solution containing 5.0 g (18.78 mmol) of 1-Benzoyl-3,8-quinazolinidione prepared in a similar manner to that reported by Melnyk et al. (Tetrahedron Lett., 37:4145 (1996)), in 100 mL of DMF under a nitrogen atmosphere was added 4.30 mL (29.12 mmol) of bromo t-butylacetate and 5.4 g (23.30 mmol) of silver oxide. The reaction was heated to 50° C. overnight, diluted with ethyl acetate and washed with water. The organic phase was dried over magnesium sulfate. Filtration, removal of solvent under reduced pressure and column chromatography of the residue on silica gel with 40% ethyl acetate/hexane gave 5.25 g (73.49%) of product. FAB MS [M+H] m/z; Calcd: 381, Found: 381.
b. 1-Benzoyl-2-carboxymethylene-3,8-quinazolinedione.
To a solution containing 5.20 g (13.67 mmol) of 1-benzoyl-3,8-quinazolinedione-2-t-butyl acetate in 300 mL of dichloromethane under a nitrogen atmosphere at 0° C. was added 21.0 mL (211.44 mmol) of trifluroacetic acid. The reaction was allowed to warm to room temperature overnight. The solvent was removed under reduced pressure and the residue dissolved in ethyl acetate and washed with water. The organic phase was dried over magnesium sulfate. Filtration and removal of solvent afforded 4.32 g (97.45%) of the title compound. FAB MS [M+H] m/z; Calcd: 325, Found: 325.
c. (1-Benzoyl-3,8-quinazolinedione)-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]hydroxymethyl)-2-(S)-methylpropyl]acetamide.
To a solution containing 1.80 g (5.55 mmol) of 1-benzoyl-2-carboxymethylene-3,8-quinazolinedione in 100 mL of anhydrous dichloromethane and 5 mL of DMF under a nitrogen atmosphere at 0° C. was added 1.90 g (7.46 mmol) of BOPCI and 1.40 mL (8.05 mmol) of DIEA. After stirring for 30 minutes, a solution containing 1.70 g (5.45 mmol) of 1-[2-(5-[3-methylbenzyl])-1,3,4-oxadiazolyl]-2-(S)-amino-3-methylbutan-1-ol hydrochloride in 20 mL of dichloromethane and 3.80 mL (21.84 mmol) of DIEA was added. The reaction was allowed to stir at 0° C. overnight, diluted with dichloromethane and washed with water. The organic phase was dried over magnesium sulfate. Filtration, removal of solvent under reduced pressure and column chromatography of the residue on silica gel with 10% methanol/dichloromethane afforded 1.93 g (60.9%) of the title compound. FAB MS[M+H] m/z; Calcd: 582, Found: 582.
Example 46
(CE-2138)(1-Benzoyl-3,6-piperazinedione)-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide. Prepared in a similar manner as in Example 44. FAB MS [M+H] m/z; Calcd: 532, Found: 532.
Example 47
(CE-2147)(1-Phenyl-3,6-piperazinedione)-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide. Prepared in a similar manner as in Example 44. FAB MS [M+H] m/z; Calcd: 504, Found: 504.
Example 48
(CE-2148)(1-Phenyl-3,6-piperazinedione)-N-[1-(3-[5-(3-trifluoromethylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide. Prepared in a similar manner as in Example 44. FAB MS [M+H] m/z; Calcd:558, Found: 558.
Example 49
(CE-2108) 3-[(Benzyloxycarbonyl)amino]-quinoline-2-one-N-[1-(2-[5-(3-methybenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide.
To a mixture containing 0.16 g (1.18 mmol) of N-chlorosuccinimide in 20 mL of anhydrous toluene at 0° C. under a nitrogen atmosphere was added 0.13 mL (1.77 mmol) of dimethyl sulfide. The reaction was cooled to -25° C. using a carbon tetrachloride/dry ice bath followed by the addition of a solution containing 0.18 g (0.30 mmol) of 3-[(benzyloxycarbonyl)amino]-quinoline-2-one-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-Oxadiazolyl]hydroxymethyl)-2-(S)-methylpropyl]acetamide in 20 mL of methylene chloride dropwise. The reaction was allowed to stir at -25° C. for 2 hours, followed by the addition of 0.19 mL (1.38 mmol) of triethylamine. The cold bath was removed and the reaction was allowed to warm to room temperature and maintained for 30 minutes. The reaction was diluted with ethyl acetate and washed with water. The organic phase was dried over magnesium sulfate. Filtration, removal of solvent under reduced pressure and column chromatography of the residue on silica gel with 3% methanol/dichloromethane afforded 0.23 g of an oil. Further purification via preparative HPLC gave 100 mg of the title compound.
FAB MS [M+H} m/z; Calcd: 608, Found: 608
The intermediate 3-[(benzyloxycarbonyl)amino]-quinoline-2-one-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]hydroxymethly)-2-(S)-methylpropyl]acetamide was prepared as follows:
a. 3-[(Benzyloxycarbonyl)amino]-quinoline-2-one.
To a solution containing 0.5 g (3.10 mmol) of 3-amino-quinoline-2-(1H)-one described by Anderson, et. al. (J. Heterocyclic Chem., 30:1533 (1993)) in 40 mL of dioxane under a nitrogen atmosphere was added 0.14 g (3.4 mmol) of sodium hydroxide in 14 mL of water. The reaction mixture was cooled to 0° C., followed by the addition of 0.50 mL (3.4 mmol) of benzylchloroformate. The pH of the reaction was maintained above 8.0 with additional 1 N sodium hydroxide. The reaction was allowed to warm to room temperature and stirred for 2 hours. The reaction was diluted with methylene chloride and washed with water. The organic phase was dried over magnesium sulfate. Filtration, removal of solvent under reduced pressure and column chromatography of the residue on silica gel with 2% methanol/dichloromethane afforded 0.32 g (35%) of product as a white solid. FAB MS [M+H] m/z; Calcd: 295, Found: 295
b. 3-[(Benzyloxycarbonyl)amino]-quinoline-2-one-N-t-butyl-acetate.
To a solution containing 0.30 g (1.02 mmol) of 3-[(benzyloxycarbonyl)amino]-quinoline-2-one in 20 mL of DMF under a nitrogen atmosphere was added 0.15 mL (1.02 mmol) of t-butyl bromoacetate and 0.24 g (1.02 mmol) of silver oxide. The reaction was heated to 70° C. and maintained overnight. The reaction mixture was diluted with acetonitrile and filtered through a pad of celite. The filtrate was concentrated under reduced pressure and the residue partitioned between ethyl acetate and water. The organic phase was dried over magnesium sulfate. Filtration, removal of solvent under reduced pressure and column chromatography of the residue on silica gel with dichloromethane afforded 0.20 g (48%) or product as a white solid. FAB MS [M+H] m/z; Calcd: 409, Found: 409.
c. 3-[(Benzyloxycarbonyl)amino]-1-carboxymethylene-quinoline-2-one.
To a solution containing 1.30 g (3.18 mmol) of 3-[(benzyloxycarbonyl)amino]-quinoline-2-one-N-t-butyl-acetate in 35 mL of dichloromethane under a nitrogen atmosphere at 0° C. was added 2.45 mL (31.84 mmol) of trifluoroacetic acid. The reaction was allowed to warm to room temperature overnight. The solvent was removed under reduced pressure to afford 1.09 g (97%) of the title compound. FAB MS [M+H] m/z; Calcd: 353, Found: 353
d. 3-[(Benzyloxycarbonyl)amino]-quinoline-2-one-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]hydroxymethyl)-2-(S)-methylpropyl]acetamide.
To a solution containing 1.09 g (3.09 mmol) of 3-[(benzyloxycarbonyl)amino]-1-carboxymethylene-quinoline-2-one in 50 mL of anhydrous dichloromethane and 3 mL of DMF under a nitrogen atmosphere at 0° C. was added 0.84 (3.31 mmol) of BOPCI and 1.10 mL (6.31 mmol) of DIEA. After stirring for 30 minutes, 0.82 g (2.65 mmol) of 1-[2-(5-[3-methylbenzyl])-1,3,4-oxadiazolyl]-2(S)-amino-3-methylbutan-1-ol hydrochloride in 8 mL of dichloromethane and 0.56 mL (3.20 mmol) of DIEA was added. The reaction was allowed to stir at 0° C. overnight, diluted with dichloromethane and washed with water. The organic phase was dried over magnesium sulfate. Filtration, removal of solvent under reduced pressure and column chromatography of the residue on silica gel with 5% methanol/dichloromethane afforded 0.37 g (30.3%) of product. FAB MS [M+H] m/z; Calcd: 610, Found: 610
Example 50
(CE-2107) 3-[(Benzyloxycarbonyl)amino]-7-piperidinyl-quinoline-2-one-N-[1-(2-[5-(3-methybenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide. Prepared in a similar manner as shown in Example 48. FAB MS [M+H] m/z; Calcd: 691, Found: 691.
Example 51
(CE-2117) 3-Carbomethoxy-4-fluoro-quinoline-2-one-N[1-(2-[5-(3-methybenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide. Prepared in a similar manner as shown in Example 48. FAB MS [M+H] m/z; Calcd: 535, Found: 535
Example 52
(CE-2113) 3-(Amino-quinoline-2-one)-N[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide.
To a solution containing 2.30 g (3.79 mmol) of 3-[(benzyloxycarbonyl)amino]-quinoline-2-one-N-[1-(2-[5-(3-methyl benzyl)-1,3,4-oxadiazolyl]-carbonyl)-2-(S)-methyl propyl]acetamide in 60 mL of trifluoroacetic acid under a nitrogen atmosphere at 0° C. was added 0.53 mL (4.54 mmol) of thioanisole. The reaction was allowed to warm to room temperature overnight. The solvent was removed under reduced pressure. Subsequent preparative HPLC afforded 0.61 g (27%) of the title compound. FAB MS [M+H] m/z; Calcd: 474, Found: 474.
Example 53
(CE-2116) 3-[(4-Morpholino)aceto]amino-quinoline-2-one-N[1-(2-[5-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide.
To a solution containing 0.32 g (1.22 mmol) of 4-morpholino acetic acid in 18 mL of dichloromethane under a nitrogen atmosphere at 0° C. was added 0.33 g (1.30 mmol) of BOPCI and 0.22 mL (1.26 mmol) of DIEA. After stirring for 1.5 hours, a solution containing 0.61 g (1.04 mmol) of 3-(amino-quinoline-2-one)-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methypropyl]acetamide in 20 mL of dichloromethane was added followed by 0.22 mL (1.26 mmol) of DIEA. The reaction was allowed to stir at 0° C. overnight, diluted with dichloromethane and washed with water. The organic phase was dried over magnesium sulfate. Filtration, removal of solvent under reduced pressure and preparative HPLC afforded 0.20 g (27%) of the title compound. FAB MS [M+H] m/z; Calcd: 602, Found: 602.
Example 54
(CE-2088) 3,4-Dihydro-quinoline-2-one-N[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-N-methylpropyl]acetamide from commercially available 3,4-Dihydro-2(1H)-quinoline-2-one. Prepared in a similar manner as shown in Example 52. FAB MS [M+H] m/z; Calcd: 461, Found: 461.
Example 55
(CE-2099) 1-Acetyl-3-benzylidene piperazine-2,5-dione-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide.
To a solution containing 0.55 g (4.15 mmol) of N-chlorosuccinimide in 35 mL of anhydrous toluene at 0° C. under a nitrogen atmosphere was added 0.46 mL (6.22 mmol) of dimethyl sulfide. The reaction was cooled to -25° C. using a carbon tetrachloride/dry ice bath, followed by the addition of a solution containing 0.58 g (1.04 mmol) of 1-acetyl-3-benzylidene piperazine-2,5-dione-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]hydroxymethyl)-2-(S)-methylpropyl]acetamide in 8 mL of toluene. The reaction was allowed to stir at -25° C. for 2 h, followed by the addition of 0.68 mL (4.87 mmol) of triethylamine. The cold bath was removed and the reaction allowed to warm to room temperature and maintained for 40 minutes. The reaction was partitioned between ethyl acetate and water. The organic phase was dried over magnesium sulfate. Filtration, removal of solvent under reduced pressure and column chromatography of the residue on silica gel 60% ethyl acetate/hexane gave 0.54 g of a brown oil which was further purified via preparative HPLC to give 146 mg (25%) of the title compound. FAB MS [M+H] m/z; Calcd: 558, Found: 558.
The intermediate 1-acetyl-3-benzylidene piperazine-2,5-dione-N1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]hydroxymethyl)-2-(S)-methylpropyl]acetamide was prepared as follows:
a. 1-Acetyl-3-benzylidene piperazine-2,5-dione-N-t-butyl acetate.
To a solution containing 6.36 g (26.00 mmol) of 1-Acetyl-3-benzylidene piperazine-2,5-dione described by D. Villemn, et al. (Synthetic Communications, 20:3325 (1990)), in 100 mL of DMF under a nitrogen atmosphere was added 9.62 mL (65.10 mmol) of t-butyl bromoacetate and 7.55 g (32.60 mmol) of silver oxide. The reaction was heated to 45° C. overnight. The reaction was filtered through a plug of celite and the filtrate concentrated under reduced pressure. The residue was diluted with ethyl acetate and washed with water. The organic phase was dried over magnesium sulfate. Filtration, removal of solvent under reduced pressure and column chromatography of the residue on silica gel with 1% methanol/dichloromethane gave 5.37 g of a tan solid. Further purification via preparative HPLC gave 2.5 g (27%) of the title compound. FAB MS[M+H] m/z; Calcd: 359, Found: 359.
b. 1-Acetyl-3-benzylidene-4-carboxymethylene-piperazine-2,5-dione.
To a solution containing 2.50 g (6.98 mmol) of 1-acetyl-3-benzylidene piperazine-2,5-dione-N-t-butyl acetate in 100 mL of dichloromethane under a nitrogen atmosphere at 0° C. was added 5.40 mL (69.80 mmol) of trifluoroacetic acid. The reaction was allowed to warm to room temperature overnight. The solvent was removed under reduced pressure and the residue diluted with ethyl acetate and washed with a saturated sodium bicarbonate solution. The aqueous phase was acidified with 1 N hydrochloric acid and extracted with ethyl acetate. The organic phase was dried over magnesium sulfate. Filtration and removal of solvent under reduced pressure gave 1.96 g (96%) of product as a tan solid. FAB MS [M+H] m/z; Calcd: 303, Found: 303.
c. 1-Acetyl-3-benzylidene piperazine-2,5-dione-N-[1-(2[5-(3-methylphenyl)-1,3,4-oxadiazolyl]hydroxymethyl)-2-(S)-methylpropyl]acetamide.
To a solution containing 0.65 g (2.14 mmol) of 1-acetyl-3-benzylidene-4-carboxymethylene-piperazine-2,5-dione in 40 mL of anhydrous dichloromethane and 3 mL of DMF under a nitrogen atmosphere at 0° C. was added 0.57 g (2.24 mmol of BOPCI and 0.39 mL (2.21 mmol) of DIEA. After stirring for 30 minutes, a solution containing 0.57 g (1.83 mmol) of 1-[2-(5-[3-methylbenzyl])-1,3,4-oxadiazolyl]-2-(S)-amino-3-methylbutan-1-ol hydrochloride in 10 mL of dichloromethane and 0.39 mL (2.21 mmol) of DIEA. The reaction was allowed to stir at 0° C. overnight, diluted with dichloromethane and washed with water. The organic phase was dried over magnesium sulfate. Filtration, removal of solvent under reduced pressure and column chromatography of the residue on silica gel with 5% methanol/dichloromethane gave 0.13 g (58%) of product. FAB MS [M+H] m/z; Calcd: 560, Found: 560.
Example 56
(CE-2105) 1-Acetyl-3-(4-fluorobenzylidene)piperazine-2,5-dione-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide. Prepared in a similar manner as shown in Example 54. FAB MS [M+H] m/z; Calcd: 576, Found: 576.
Example 57
(CE-2111) 1-Acetyl-3-(4-dimethylamino benzylidene)piperazine-2,5-dione-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide. Prepared in a similar manner as shown in Example 54. FAB MS [M+H] m/z; Calcd: 601, Found: 601.
Example 58
(CE-2112) 1-Acetyl-3-(4-carbomethoxy benzylidene)piperazine-2,5-dione-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolylcarbonyl)-2-(S)-methylpropyl]acetamide. Prepared in a similar manner as shown in Example 54. FAB MS [M+H] m/z; Calcd: 616, Found: 616.
Example 59
(CE-2114) 1-Acetyl-3-[(4-pyridyl)methylene]piperazine-2,5-dione-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide. Prepared in a similar manner as shown in Example 54. FAB MS[M+H] m/z; Calcd: 559, Found: 559.
Example 60
(CE-2144) 4-[1-Benzyl-3-(R)-benzyl-piperazine-2,5,-dione]-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide.
To a mixture containing 2.20 g (16.48 mmol) of N-chlorosuccinimide in 100 mL of anhydrous toluene under a nitrogen atmosphere at 0° C. was added 2.1 mL (28.59 mmol) of dimethyl sulfide. The reaction was cooled to -25° C. using a carbon tetrachloride/dry ice bath, followed by the addition of a solution containing 2.5 g (4.10 mmol) of 4-[1-benzyl-3-(R)-benzyl piperazine-2,5,-dione]-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]hydroxymethyl)-2-(S)-methylpropyl]acetamide in 15 mL of toluene. The reaction was allowed to stir at -25° C. for 2 hours, followed by the addition of 4.0 mL (28.70 mmol) of triethylamine. The cold bath was removed and the reaction allowed to warm to room temperature and maintained for 30 minutes. The reaction was diluted with ethyl acetate and washed with water. The organic phase was dried over magnesium sulfate. Filtration, removal of solvent under reduced pressure, and column chromatography of the residue on silica gel with 5% methanol/dichloromethane afforded 2.27 g of a light brown solid which was further purified via preparative HPLC to give 350 mg (14.4%) of the title compound. FAB MS [M+H] m/z; Calcd: 608, Found: 608.
The intermediate 4-[1-benzyl-3-(R)-benzyl piperazine-2,5,-dione]-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]hydroxymethyl)-2-(S)-methylpropyl]acetamide was prepared as follows:
a. 1-Benzyl-3-(R)-benzylpiperazine-2,5-dione-4-t-butyl acetate.
To a solution containing 7.0 g (23.78 mmol) of 1-benzyl-3-(R)-benzyl piperazine-2,5-dione described by Steele, et al. (J. Biorg, Med. Chem. Lett., 5:47 (1995)) in 125 mL of DMF under a nitrogen atmosphere was added 5.30 mL (35.89 mmol) of t-butyl bromoacetate and 6.80 g (29.34 mmol) of silver oxide. The reaction was heated to 50° C. overnight, diluted with ethyl acetate and washed with water. The organic phase was dried over magnesium sulfate. Filtration, removal of solvent under reduced pressure and column chromatography of the residue on silica gel with 50% ethyl acetate/hexane afforded 7.74 g (79.7%) of the title compound as a white solid. FAB MS [M+H] m/z; Calcd:409,Found: :409.
b. 1-Benzyl-3-(R)-benzyl-4-carboxymethylene-piperazine-2,5-dione.
To a solution containing 7.70 g (18.85 mmol) of 1-Benzyl-3-(R)-benzyl piperazine-2,5-dione-4-t-butyl acetate in 300 mL of dichoromethane under a nitrogen atmosphere at 0° C. was added 19.0 mL(191.30 mmol) of trifluroacetic acid. The reaction was allowed to warm to room temperature overnight. The solvent was removed under reduced pressure and the residue dissolved in ethyl acetate and washed with water. The organic phase was dried over magnesium sulfate. Filtration and removal of solvent under reduced pressure afforded 6.69 g of product. FAB MS [M+H] m/z; Calcd:353,Found:353.
c. 4-[1-Benzyl-3(R)-benzyl piperazine-2,5,-dione]-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]hydroxymethyl)-2-(S)-methylpropyl]acetamide.
To a solution containing 2.0 g (5.68 mmol) of 1-Benzyl-3-(R)-benzyl-4-carboxymethylene-piperazine-2,5-dione in 100 mL of dichloromethane and 2 mL of DMF under a nitrogen atmosphere at 0° C. was added 2.0 g (7.86 mmol) of BOPCI and 1.50 mL (8.62 mmol) of DIEA. After stirring for 30 minutes, a solution containing 1.80 g (5.7 mmol) of 1-[2-(5-[3-methylbenzyl])-1,3,4-oxadiazolyl]-2-(S)-amino-3-methylbutan-1-ol hydrochloride in 10 mL of dichloromethane and 4.0 mL (22.99 mmol) of DIEA. The reaction was allowed to stir at 0° C. overnight, diluted with dichloromethane and washed with water. The organic phase was dried over magnesium sulfate. Filtration, removal of solvent under reduced pressure and column chromatography of the residue on silica gel with 7% methanol/dichloromethane afforded 2.69 g (77.7%) of product. FAB MS[M+H] m/z; Calcd:610, Found: 610.
Example 61
(CE-2128) 4-[1-Benzyl-3-(S)-benzylpiperazine-2,5,-dione]-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide. Prepared in a similar manner as shown in Example 59. FAB MS [M+H] m/z; Calcd:608, Found: 608.
Example 62
(CE-2146) 4-[1-Benzyl-3-(R)-benzylpiperazine-2,5,-dione]-N-[1-(3-[5-(3-trifluoromethylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide. Prepared in a similar manner as shown in Example 59. FAB MS [M+H] m/z; Calcd:662, Found: 662.
Example 63
CE-2129) 4-[1-Benzyl-3-(S)-benzylpiperazine-2,5,-dione]-N-[-(3-[5-(3-trifluoromethylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide. Prepared in a similar manner as shown in Example 59. FAB MS [M+H] m/z; Calcd:662, Found: 662.
Example 64
(CE-2133) 4-[1-Benzyl-3-(S)-benzylpiperazine-2,5,-dione]-N-[1-(3-[5-(2-dimethylaminoethyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide. Prepared in a similar manner as shown in Example 59. FAB MS [M+H] m/z; Calcd:575, Found: 575.
Example 65
(CE-2084) 4-[1-Methyl-3-(R,S)-phenylpiperazine-2,5,-dione]-N-[1-(3-[5-(3-trifluoromethylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide. Prepared in a similar manner as shown in Example 59. FAB MS [M+H] m/z; Calcd:572, Found: 572.
Example 66
(CE-2106) 4-[1-Methyl-3-(R,S)-phenylpiperazine-2,5,-dione]-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide. Prepared in a similar manner as shown in Example 59. FAB MS [M+H] m/z; Calcd:518, Found: 518.
Example 67
(CE-2162) 4-[1-(2-N-Morpholino ethyl)-3-(R)-benzyl piperazine-2,5, -dione]-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide. Prepared in a similar manner as shown in Example 59. FAB MS [M+H] m/z; Calcd:631, Found: 631.
Example 68
(CE-2149) 5-(R,S)-Phenyl-2,4-imidazolidinedione-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide.
To a mixture containing 0.28 g (2.10 mmol) of N-chlorosuccinimide in 50 mL of anhydrous toluene under a nitrogen atmosphere at 0° C. was added 0.23 mL (3.13 mmol) of dimethyl sulfide. The reaction was cooled to -25° C. using a carbon tetrachloride/dry ice bath, followed by the addition of a solution containing 0.26 g (0.52 mmol) of 5-(R,S)-phenyl-2,4-imidazolidinedione-N-[1-(2-[5(3-methylbenzyl)-1,3,4-oxadiazolyl]hydroxymethyl)-2-(S)-methylpropyl]acetamide in 10 mL of toluene. The reaction was allowed to stir at -25° C. for 2 hours, followed by the addition of 0.30 mL (2.15 mmol) of triethylamine. The cold bath was removed and the reaction allowed to warm to room temperature and maintained for 30 minutes. The reaction was diluted with ethyl acetate and washed with water. The organic phase was dried over magnesium sulfate. Filtration, removal of solvent under reduced pressure and column chromatography of the residue of silica gel with 10% methanol/dichloromethane, followed by preparative HPLC gave 120 mg (47.2%) of the title compound. FAB MS [M+H] m/z; Calcd:490, Found: 490.
The intermediate 5-(R,S)-phenyl-2,4-imidazolidinedione-N-[1-(2-[5(3-methylbenzyl)-1,3,4-oxadiazolyl]hydroxymethyl)-2-(S)-methylpropyl]acetamide was prepared as follows:
a. (R)-N-(Ethoxy carbonylmethyl)-N'-(1-methoxy carbonyl-2-phenyl)urea.
To a solution containing 18.45 g (91.49 mmol) of (R)-2-phenylglycine methylester in 250 mL of ethyl acetate and 13.4 mL (96.12 mmol) of triethylamine under a nitrogen atmosphere at 0° C. was added 10 mL (91.49 mmol) of ethyl isocyanatoacetate. After stirring for 1 h, the reaction was diluted with ethyl acetate and washed with water. The organic phase was dried over magnesium sulfate. Filtration and removal of solvent under reduced pressure afforded 29.28 g (97.6%) of product as a white solid. FAB MS [M+H] m/z; Calcd: 235, Found: 235.
b. (R)-5-Phenyl-3-carboxymethyl hydantoin.
A mixture containing 29.28 g (99.49 mmol) of (R)-N-(ethoxy carbonylmethyl)-N'-(1-methoxy carbonyl-2-phenyl)urea in 500 mL of concentrated hydrochloric acid was heated to reflux overnight. The reaction mixture was cooled to room temperature and extracted with ethyl acetate. The organic phase was dried over magnesium sulfate. Filtration and removal of solvent under reduced pressure afforded 14.01 g (60%) of the title compound. FAB MS [M+H] m/z; Calcd: 295, Found: 295.
c. 5-(R,S)-phenyl-2,4-imidazolidinedione-N-[1-(2-[5(3-methylbenzyl)-1,3,4-oxadiazolyl]hydroxymethyl)-2-(S)-methylpropyl]acetamide
To a solution containing 2.55 g (10.89 mmol) of (R)-5-phenyl-3-carboxymethyl hydantoin in 100 mL of dichloromethane and 10 mL of DMF under a nitrogen atmosphere at 0° C. was added 2.30 g (12.00 mmol) of EDCI and 1.62 g (11.99 mmol) of HOBT. After stirring 30 minutes, a solution containing 4.43 g (14.21 mmol) of 1-[2-(5-[3-methylbenzyl])-1,3,4-oxadiazolyl]-2-(S)-amino-3-methylbutan-1-ol hydrochloride in 20 mL of dichloromethane and 4.78 mL (43.50 mmol) of NMM. The reaction was allowed to warm to room temperature overnight, diluted with dichloromethane and washed with water. The organic phase was dried over magnesium sulfate. Filtration, removal of solvent under reduced pressure and column chromatography of the residue on silica gel with 50% acetone/dichloromethane afforded 1.90 g (35.5%) of the title compound. FAB MS [M+H] m/z; Calcd: 490, Found: 490.
Example 69
(CE-2154) 5-(S)-Benzyl-2,4-imidazolidinedione-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide. Prepared in a similar manner as shown in Example 67. FAB MS [M+H] m/z; Calcd: 504, Found: 504.
Example 70
(CE-2142) 5-(R)-Benzyl-2,4-imidazolidinedione-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide. Prepared in a similar manner as shown in Example 67. FAB MS [M+H] m/z; Calcd: 504, Found: 504.
Example 71
(CE-2141) 5-(R)-Benzyl-2,4-imidazolidinedione-N-[1-(3-[5-(3-trifluoromethylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide. Prepared in a similar manner as shown in Example 67. FAB MS [M+H] m/z; Calcd: 558, Found: 558.
Example 72
(CE-2155) 5-(S)-Benzyl-2,4-imidazolidinedione-N-[1-(3-[5-(3-trifluoromethylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide. Prepared in a similar manner as shown in Example 67. FAB MS [M+H] m/z; Calcd: 558, Found: 558.
Example 73
(CE-2151) 1-Benzyl-4-(R)-benzyl-2,5-imidazolidinedione-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide. Prepared in a similar manner as shown in Example 67. FAB MS [M+H] m/z; Calcd: 594, Found: 594.
Example 74
(CE-2150) 1-Benzyl-4-(R)-benzyl-2,5-imidazolidinedione-N-[1-(3-[5-(3-trifluoromethylbenzyl)-1,2,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide. Prepared in a similar manner as shown in Example 67. FAB MS [M+H] m/z; Calcd: 648, Found: 648.
Example 75
(ONO-PO-698) 2-[5-(Benzyloxycarbonyl)amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-tert-butyl-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide.
To a mixture containing 410 mg (0.744 mmol, 77% purity) of Dess-Martin Reagent (1,1,1-triacetoxy-1,1-dihydro-1,2,benziodoxol-3-(1H)-one) in 4 mL of dichloromethane was added dropwise a solution containing 410 mg (0.676 mmol) of 2-[5-benzyloxycarbonyl)amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-tert-butyl-1,3,4-oxadiazolyl]hydroxymethyl)-2-(S)-methylpropyl]acetamide in 5 mL of dichloromethane. The reaction mixture was allowed to stir for 1 hour. The reaction was quenched by addition of water, extracted with ethyl acetate (x2). The extract was washed with water and a saturated sodium chloride solution. The organic phase was dried over anhydrous sodium sulfate, filtered and evaporated under reduced pressure. The residue was purified by column chromatography on silica gel using a elution of 33% ethyl acetate/hexane to afford 372 mg of the title compound. APCI, Pos, 40V [M+H] m/z; Calcd: 605, Found: 605.
The intermediate 2-[5-(Benzyloxycarbonyl)amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-tert-butyl-1,3,4-oxadiazolyl]hydroxymethyl)-2-(S)-methylpropyl]acetamide was prepared as follows: to a solution containing 265 mg (1.01 mmol) of [1-[5-tert-butyl-1,3,4-oxadiazol-2-yl]-2-(S)-amino-1-hydroxy-3-methylbutane hydrochloride and 336 mg (0.843 mmol) of 5-[(Benzyloxycarbonyl)amino]-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]acetic acid (J. Med. Chem., 38:98-108 (1995)) in 2 mL of anhydrous DMF was added 155 mg (1.01 mmol) of HOBT and 231 mg (1.01 mmol) of EDCl. The mixture was cooled to 0° C. and 0.11 mL (1.0 mmol) of NMM was added dropwise and the reaction mixture was allowed to stir for 3 hours. The reaction was quenched by addition of water and extracted with ethyl acetate (x3). The extract was washed with aqueous 10% citric acid solution, a saturated sodium hydrogencarbonate solution and a saturated sodium chloride solution. The organic phase was dried over anhydrous sodium sulfate, filtered and evaporated under reduced pressure. The residue was purified by column chromatography on silica gel using a gradient elution of 0 to 1% methanol/chloroform to afford 418 mg of the title compound. APCI, Pos, 40V [M+H] m/z; Calcd: 607, Found: 607.
Example 76
(ONO-PO-690) 2-[5-(Benzyloxycarbonyl)amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(α,α-dimethylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide was prepared in a similar manner to Example 75. APCI, Pos, 40V [M+H] m/z; Calcd: 667, Found: 667.
Example 77
(ONO-PO-697) 2-[5-(Benzyloxycarbonyl)amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-phenyl-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide was prepared in a similar manner to Example 75. El, Pos, [M+H] m/z; Calcd: 624, Found: 624.
Example 78
(ONO-PO-716) 2-[6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-tert-butyl-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide was prepared in a similar manner to Example 75. APCI, Neg, 40V [M-H] m/z; Calcd: 454, Found: 454.
Example 79
(ONO-PO-722) 2-[6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(α,α-dimethylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide was prepared in a similar manner to Example 75. APCI, Neg, 40V [M-H] m/z; Calcd: 516, Found: 516.
Example 80
(ONO-PO-727) 2-[6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-tert-butyl-1,3,4-oxadiazolyl]carbonyl)-2-(R)-methylpropyl]acetamide was prepared in a similar manner to Example 75. APCI, Pos, 40V [M+H] m/z; Calcd: 456, Found: 456.
Example 81
(ONO-PO-730) 2-[6-oxo-2-phenyl-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-tert-butyl-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide was prepared in a similar manner to Example 75. APCI, Neg, 40V [M-H] m/z; Calcd: 436, Found: 436.
Example 82
(ONO-PO-731) 2-[6-oxo-2-phenyl-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(α,α-dimethylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide was prepared in a similar manner to Example 75. APCI, Neg, 40V [M-H] m/z; Calcd: 498, Found: 498.
Example 83
(ONO-PO-732) 2-[6-oxo-2-phenyl-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-tert-butyl-1,3,4-oxadiazolyl]carbonyl)-2-(R)-methylpropyl]acetamide was prepared in a similar manner to Example 75. APCI, Pos, 40V [M+H] m/z; Calcd: 438, Found: 438.
Example 84
(ONO-PO-734) 2-[6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(1-methylcyclopropyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide was prepared in a similar manner to Example 75. APCI, Pos, 40V [M+H] m/z; Calcd: 454, Found: 454.
Example 85
(ONO-PO-735) 2-[6-Oxo-2-phenyl-1,6-dihydro-1-pyrimidinyl]-N-[1-(1-methylcyclopropyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide was prepared in a similar manner to Example 75. APCI, Pos, 40V [M+H] m/z; Calcd: 436, Found: 436.
Example 86
(ONO-PO-737) 2-[6-oxo-2-phenyl-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-tert-butyl-1,3,4-oxadiazolyl]carbonyl)-2-(R,S)-methylpropyl]acetamide was prepared in a similar manner to Example 75. APCI, Pos, 40V [M+H] m/z; Calcd: 438, Found:438.
Example 87
(ONO-PO-696) 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-tert-butyl-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide.
To a mixture containing 296 mg (0.49 mmol) of 2-[5-(benzyloxycarbonyl)amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-tert-butyl-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide and 0.32 mL (2.9 mmol) of anisole in 8 mL of dichloromethane at OEC was added dropwise a solution containing 392 mg (2.9 mmol) of aluminum chloride in 4 mL of nitromethane. The reaction mixture was allowed to stir for 1.5 hours, quenched by addition of ice water, extracted with ethyl acetate (x3). The extract was washed with water and a saturated sodium chloride solution. The organic phase was dried over anhydrous magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by column chromatography on silica gel using a elution of 66% ethyl acetate/hexane to afford 175 mg of the title compound as a white solid. APCI, Pos, 40V [M+H] m/z; Calcd: 471, Found: 471.
Example 88
(ONO-PO-691) 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(α,α-dimethylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide was prepared in a similar manner to Example 91. FAB, Pos, [M+H] m/z; Calcd: 533, Found: 533.
Example 89
(ONO-PO-692) 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[ -(2-[5-(α,α-dimethyl-3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide was prepared in a similar manner to Example 91. FAB, Pos, [M+H] m/z; Calcd: 547, Found: 547.
Example 90
(ONO-PO-693) 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(R)-methylpropyl]acetamide was prepared in a similar manner to Example 91. FAB, Pos, [M+H] m/z; Calcd: 519, Found: 519.
Example 91
(ONO-PO-694) 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-phenyl-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide was prepared in a similar manner to Example 91. APCI, Pos, 40V [M+H] m/z; Calcd: 491, Found: 491.
Example 92
(ONO-PO-695) 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(3-pyridyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide was prepared in a similar manner to Example 91. APCI, Pos, 40V [M+H] m/z; Calcd: 492, Found: 492.
Example 93
(ONO-PO-699) 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(4-methoxyphenyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide was prepared in a similar manner to Example 91. FAB, Pos [M+H] m/z; Calcd: 521, Found: 521.
Example 94
(ONO-PO-701) 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(α,α-dimethyl)-3,4-dihydroxybenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide was prepared in a similar manner to Example 91. APCI, Pos, 40V [M+H] m/z; Calcd: 565, Found: 565.
Example 95
(ONO-PO-703) 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-benzyl-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide was prepared in a similar manner to Example 91. APCI, Pos, 40V [M+H] m/z; Calcd: 505, Found: 505.
Example 96
(ONO-PO-704) 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-methyl-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide was prepared in a similar manner to Example 91. FAB, Pos [M+H] m/z; Calcd: 429, Found: 429.
Example 97
(ONO-PO-705) 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-isopropyl-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide was prepared in a similar manner to Example 91. APCI, Pos, 40V [M+H] m/z; Calcd: 457, Found: 457.
Example 98
(ONO-PO-706) 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-butyl-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide was prepared in a similar manner to Example 91. FAB, Pos [M+H] m/z; Calcd: 471, Found: 471.
Example 99
(ONO-PO-707) 2-[5-Amino-6-oxo-2-phenyl-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-tert-butyl-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide was prepared in a similar manner to Example 91. FAB, Pos [M+H] m/z; Calcd: 453, Found: 453.
Example 100
(ONO-PO-711) 2-[5-Amino-6-oxo-2-phenyl-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-α,.alpha.-dimethybenzyl-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide was prepared in a similar manner to Example 91. FAB, Pos [M+H] m/z; Calcd: 515, Found: 515.
Example 101
(ONO-PO-712) 2-[5-Amino-6-oxo-2-(3-pyridyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-tert-butyl-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide was prepared in a similar manner to Example 91. APCI, Pos, 40V [M+H] m/z; Calcd:454, Found:454.
Example 102
(ONO-PO-714) 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(1-methylcyclopropyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide was prepared in a similar manner to Example 91. APCI, Pos, 40V [M+H] m/z; Calcd: 469, Found: 469.
Example 103
(ONO-PO-715) 2-[5-Amino-6-oxo-2-(3-pyridyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(.alpha.,α-dimethylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide was prepared in a similar manner to Example 91. APCI, Pos, 40V [M+H] m/z; Calcd: 516, Found: 516.
Example 104
(ONO-PO-718) 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-tert-butyl-1,3,4-oxadiazolyl]carbonyl)-2-(R)-methylpropyl]acetamide was prepared in a similar manner to Example 91. APCI, Pos, 40V [M+H] m/z; Calcd: 471, Found: 471.
Example 105
(ONO-PO-721) 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(α,α-dimethylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(R)-methylpropyl]acetamide was prepared in a similar manner to Example 91. APCI, Pos, 40V [M+H] m/z; Calcd: 533, Found: 533.
Example 106
(ONO-PO-728) 2-[5-Amino-6-oxo-2-phenyl-1,6-dihydro-1-pyrimidinyl]-[1-(2-[5-(1-methylcyclopropyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide was prepared in a similar manner to Example 91. APCI, Neg, 40V [M-H] m/z; Calcd:449, Found:559.
Example 107
(ONO-PO-729) 2-[5-Amino-6-oxo-2-phenyl-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-tert-butyl-1,3,4-oxadiazolyl]carbonyl)-2-(R)-methylpropyl]acetamide was prepared in a similar manner to Example 91. APCI, Pos, 40V [M+H] m/z; Calcd:453, Found:453.
Example 108
(ONO-PO-733) 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-tert-butyl-1,3,4-oxadiazolyl]carbonyl)-2-(R,S)-methylpropyl]acetamide was prepared in a similar manner to Example 91. APCI, Pos, 40V [M+H] m/z; Calcd:471, Found:471.
Example 109
(ONO-PO-736) 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-tert-butyl-1,3,4-oxadiazolyl]carbonyl)-2-(R,S)-methylpropyl]acetamide was prepared in a similar manner to Example 91. APCI, Pos, 40V [M+H] m/z; Calcd:453, Found:453.
Example 110
(ONO-PO-700) 2-[5-Amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(α,α-dimethyl-3,4-methylenedioxybenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
To a mixture containing 66 mg (0.093 mmol) of 2-[5-(benzyloxycarbonyl)amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(α,α-dimethyl-3,4-methylenedioxybenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide (the compound prepared in a similar manner to Example 75) was added 2.5 mL of 30% hydrobromic acid in acetic acid solution. The reaction mixture was allowed to stir for 1 hour, quenched by addition of ice water, extracted with ethyl acetate (x3). The extract was washed with water (x2) and a saturated sodium chloride solution. The organic phase was dried over anhydrous sodium sulfate, filtered and evaporated under reduced pressure. The residue was purified by column chromatography on silica gel using a gradient elution of 0 to 1% methanol/chloroform to afford 41 mg of the title compound. El, Pos, [M+] m/z; Calcd:576, Found:576.
Example 111
(ONO-PO-702) 2-[5-(Methylsulfonyl)amino-6-oxo-2-(4-fluorphenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide
To a mixture containing 187 mg (0.36 mmol) of 2-[5-amino-6-oxo-2-(4-fluorophenyl)-1,6-dihydro-1-pyrimidinyl]-N-[1-(2-[5-(3-methylbenzyl)-1,3,4-oxadiazolyl]carbonyl)-2-(S)-methylpropyl]acetamide (the compound prepared in Example 25) in 3.5 mL of pyridine at OEC under an atmosphere of argon was added 0.028 mL (0.36 mmol) of mesyl chloride. The reaction mixture was allowed to stir for 17 hours at room temperature, 15 hours at 50EC and 1 hour at 70EC. The reaction mixture was quenched by addition of ice water, extracted with dichloromethane. The extract was washed with a saturated sodium chloride solution. The organic phase was dried over anhydrous sodium sulfate, filtered and evaporated under reduced pressure. The residue was purified by column chromatography on silica gel using a gradient elution of 50 to 66% ethyl acetate/hexane to afford 60 mg of the title compound. APCI, Pos, 40V [M+H] m/z; Calcd: 597, Found: 597.
Example 112
In Vitro Inhibition of Elastase
The following protocol was used to determine inhibitory activity of ONO-PO series of compounds. The elastase used in the protocol was derived from human sputum (HSE). A mother solution of the HSE enzyme was prepared from commercially available HSE (875 U/mg protein, SE-563, Elastin Product Co., Inc, Missouri, U.S.A.) by diluting with saline to 1,000 U/ml, which was further diluted to 2 U/ml at 0° C. prior to use.
A solution was prepared by mixing 100 μl 0.2 M HEPES-NaOH buffer (pH 8.0), 40 μl 2.5 M NaCl, 20 μl 1% polyethyleneglycol 6000, 8 μl distilled water, 10 gl of a DMSO solution of inhibitor and 2 μl solution of N-methoxysuccinyl-Ala-Ala-Pro-Val-p-nitroaniline (SEQ ID NO: 1) (at concentrations of 100, 200 and 400 [μM). The solution was incubated for 10 minutes at 37° C. To this was added an enzyme solution of HSE (elastase derived from human sputum). The resulting mixture was subjected to the following rate assay.
Optical density (SPECTRA MAX 250, Molecular Devices) at 405 nm due to p-nitroaniline generated by the enzyme reaction was measured at 37° C. in order to measure the reaction rate during the period that the production rate of p-nitroaniline remains linear. The rate, mO.D./min., was measured for 10 minutes at 30 second intervals immediately after the addition of the enzyme solution. IC 50 values were determined by log-logit method and converted to K i values by Dixson plot method. The values are presented in Table 2 below. Table 2.
______________________________________Compound Ki (nM) Compound K.sub.i (nM)______________________________________ONO-PO-690 78.3 ONO-PO-710 2.39 ONO-PO-691 0.52 ONO-PO-711 2.55 ONO-PO-692 1.37 ONO-PO-712 16.6 ONO-PO-693 2.71 ONO-PO-713 12 ONO-PO-694 24.8 ONO-PO-714 15.3 ONO-PO-695 13.9 ONO-PO-715 3.54 ONO-PO-696 6.38 ONO-PO-716 44.3 ONO-PO-697 27.3 ONO-PO-717 57.8 ONO-PO-698 0.77 ONO-PO-718 26.2 ONO-PO-699 21.2 ONO-PO-719 836.3 ONO-PO-700 1.18 ONO-PO-720 25.9 ONO-PO-701 2.98 ONO-PO-721 13.5 ONO-PO-702 1.78 ONO-PO-722 3.35 ONO-PO-703 2.25 ONO-PO-723 163.1 ONO-PO-704 14.0 ONO-PO-724 14.4 ONO-PO-705 10.7 ONO-PO-725 4281.4 ONO-PO-706 6.76 ONO-PO-726 589.5 ONO-PO-707 3.59 ONO-PO-727 132.8 ONO-PO-708 729.9 ONO-PO-728 8.75 ONO-PO-709 25.7 ONO-PO-729 29.1 ONO-PO-730 23.5 ONO-PO-731 4.02 ONO-PO-732 62.2 ONO-PO-733 11.8 ONO-PO-734 43.8 ONO-PO-735 26.4 ONO-PO-736 6.43 ONO-PO-737 36.3______________________________________
CE compounds were tested as described in WO 96/16080. Results are presented in Table 2 below. As shown, the compounds of the invention are potent inhibitors of elastase, with certain compounds showing subnanomolar levels of inhibitory activity.
Example 113
Blood Level Screening
The inhibitors were dissolved or suspended in polyethylene glycol (PEG), PEG-400 or PEG:H 2 O:EtOH at a concentration of 10 mg/ml. Unfasted male Sprague-Dawley rats were given an oral dose of this solution by gavage. Rats received 10 mg inhibitor/kg body weight in a volume of 1 ml/kg. After 1, 3 or 6 hr., the rats were killed with an overdose of urethane (2.5 g/kg; i.p.) and the blood collected in a heparinized tube via cardiac puncture. Red blood cells were separated from the plasma by centrifugation.
Depending on the inhibitor, one of four organics (ethyl acetate, toluene, isopropyl ether or methyl t-butyl ether) was used to extract the compound from the plasma. Inhibitor concentrations were measured by HPLC or LC/MS analysis. The results are presented in Table 3 below. Certain compounds of the invention demonstrate high levels of oral bioavailability as shown by their blood level concentrations over time.
Example 114
Extracellular Matrix (ECM) Assay Procedure
Forty-eight well plates on which extracellular matix had been established were supplied to Cortech by Dr. Simon's group at the State University of New York at Stony Brook. Briefly, the plates were prepared as follows: R22 rat heart smooth muscle cells were seeded into wells at 2.5×10 4 cells/cm. The cells were fed every 4 days with Eagle's Minimal Essential Media supplemented with fetal bovine serum, tryptose phosphate broth, cefotaxime and streptomycin. At confluence, daily supplements of 50 ug/ml ascorbic acid were added for 8 to 10 days during the synthesis of the ECM layer. [ 35 S]sulfate and [ 3 H]proline were also added to the culture media to incorporate radiolabel into the matrix. Cells were later lysed with 25 mM NH 4 OH. Plates were washed three times with water and once with phosphate-buffered saline containing 0.02% NaN 3 . Plates were stored at 4° C. until use.
Matrix degradation assays were performed as follows: 0.40 ml of Hanks balance salt solution (HBSS) containing 1 or 5 uM test inhibitor (final concentration; diluted from DMSO stock solution; <2% DMSO final concentration) was added to the wells. After 30 minutes, 50 ul of a polymorphoneucleocyte (PMN) suspension was added resulting in 5×10 5 cells/well. PMN's were stimulated with opsonized zymosan. Zymosan particles were washed and suspended in 0.5 ml human serum for 1 hr at 37° C., vortexing every 15 min. The particles were then washed three times with HBSS and added to wells at a ratio of 10 particles/PMN in a volume of 50 ul. After a 4 hr incubation at 37° C., a 100 ul aliquot of the supernatant was withdrawn for scintillation counting. Following removal of the remaining supernatant, the residual ECM was solubilized with 0.5 ml 2M NaOH. The amount of tritium in this solubilized ECM was accessed by scintillation. ECM degradation data are expressed as (soluble counts released/total ECM counts)--(basal counts released without PMN's/total ECM counts). The results are presented in Table 3 below.
TABLE 3______________________________________HNE K.sub.i ECM Data % Inhibition Plasma Levels (μM)CE # (nM) 1 uM 5 uM 1 hr 3 hr 6 hr______________________________________CE2048 0.2 CE2049 0.5 CE2050 1.84 CE2051 1.56 CE2052 0.37 CE2053 0.41 CE2054 0.29 CE2055 0.49 0.002 CE2056 0.98 CE2057 0.375 CE2058 0.564 CE2061 71600 CE2062 0.3 CE2064 0.44 CE2065 0.47 CE2066 0.98 CE2067 3.6 CE2068 800 CE2069 4.4 CE2072 0.025 64.8 74.55 0.277 0.115 0.061 CE2073 0.235 CE2074 1 CE2075 0.039 CE2076 1.5 CE2077 0.15 CE2078 1.05 CE2079 34 CE2080 62 CE2082 53 CE2083 73 CE2084 133 CE2087 20 CE2088 66 0.801 0.755 CE2089 1.5 CE2090 2.7 CE2091 270 CE2092 6.3 CE2093 0.26 CE2094 10 CE2095 0.21 60.43 55.63 CE2096 0.79 CE2097 115 CE2098 85 CE2099 1.9 0.042 CE2100 0.069 57.63 56.56 0.064 CE2101 0.64 44.582 51.18 1.238 1.369 1.042 CE2102 258 CE2103 12.4 CE2104 0.33 CE2105 0.72 CE2106 41 CE2107 17 CE2108 10.5 CE2109 126 CE2110 0.13 CE2111 20 0.69 CE2112 1.2 CE2113 39 1.835 0.909 CE2114 25 CE2115 1 CE2116 76 CE2117 586 CE2118 13.2 CE2119 7.7 CE2120 51 CE2121 28 CE2122 63 CE2123 15 CE2124 0.033 CE2125 0.4 0.011 CE2126 5 0.161 CE2127 34 CE2128 64 CE2129 300 CE2130 2.1 16.32 29.02 0.162 CE2131 265 CE2132 23.5 CE2133 33000 CE2134 2 21.71 25.724 5.02 CE2135 17.5 0 37 CE2136 104 CE2137 558 CE2138 294 CE2139 41 CE2140 204 CE2141 64 0.005 CE2142 8.7 CE2143 11.5 CE2144 9.3 CE2145 0.038 CE2146 67 CE2147 1600 CE2149 0.28 51.275 55.9 0 0 0 CE2151 59 14.25 -8.3 CE2152 0.24 CE2154 10 54.6 65.4 CE2155 57 CE2156 512 CE2157 1.4 9.96 13.42 3.81 CE2159 52 CE2160 260 CE2161 0.082 25 55 CE2162 10.6 0.025 CE2163 0.75 54.7 64 0.316 CE2164 17 0.034 CE2165 2.6 0.067 CE2166 145 CE2168 0.15 CE2170 297 CE2171 0.64 CE2172 2.2 0.021 CE2173 6.5 35.9 47.1 CE2174 15.2 1.49 18.3 1.86 0.97 CE2176 52 CE2177 0.016 74.2 76.78 0.393 0.41 0 CE2178 0.29 34 0.185 CE2179 7.6 48.8 45.9 1.229 0.599 CE2180 44 CE2181 46 CE2182 54 CE2183 0.23 CE2184 8.2 30.5 32.4 0.57 CE2185 0.27 CE2186 0.037 CE2187 42 CE2189 99 CE2190 29 CE2191 85 29.35 30.5 CE2192 7.3 40.8 49.7 CE2193 36 CE2194 2.4 41 58.7 1.11 0.553 CE2195 10.6 CE2196 96 CE2197 4.8 CE2198 3.1 CE2200 13.7 CE2202 0.12 CE2203 79 0.004 CE2204 7.4 0.48 CE2205 37 0.475 CE2206 8.7 47.4 62.3 CE2207 1.2 0 CE2208 40 CE2209 36.4 0 CE2210 22.7 CE2211 348 CE2212 124 CE2213 0.14 0.19 CE2214 0.92 0 CE2215 163 1.16 0.83 0.63 CE2216 4.1 32.1 37.15 0.77 0.47 0.25 CE2217 5.5 28.1 41.2 1.99 0.521 CE2218 1.6 30.5 33.15 CE2219 537 CE2220 52 CE2221 34 CE2223 0.93 34.15 36.15 CE2224 1 43.25 66.8 1.843 1.943 1.961 CE2225 8.2 30.85 43.45 CE2226 10.3 27.55 52.25 CE2227 40 1.276 0.74 0.962 CE2228 40 0.714 1.393 0.409 CE2229 9.5 31.25 48.2 CE2230 2.6 37.7 37.8 0 CE2231 16 1.226 0.787 0.531 CE2232 0.15 0.44 0.44 0.26 CE2233 41.6 54.7 55.4 0.07 0.065 0.036 CE2234 796 39.7 35 CE2235 9.5 19.75 13.25 CE2236 7.1 31.9 31.75 CE2237 3 34.6 42.6 1.02 1.8 0.84 CE2238 162 10.1 18.8 2.573 1.739 1.028 CE2239 43 11.9 11.3 1.46 1.15 0.71 CE2240 30 16.8 13.5 1.12 0.5 0.29 CE2241 14 18.6 31.7 0.598 0.289 0.078 CE2242 27 29.4 40.7 CE2243 11 48 54.9 2.801 2.104 1.598 CE2244 78.5 CE2245 24 34.7 39.3 CE2246 18.5 -2.3 32.6 1.182 0.837 0.496 CE2247 62.4 13.3 21.2 1.017 0.572 0.186 CE2248 3.1 39.4 63.2 1.65 1.58 1.22 CE2249 13 22.4 42.4 1.179 0.704 0.213 CE2250 6.9 27.4 48.6 CE2251 0.43 54.1 74.5 1.63 1.11 0.73 CE2252 1.9 45.4 65.2 0.114 0.188 0.1 CE2253 11 31.9 45.9 0.282 0.246 0.163 CE2254 2.4 57.2 58.4 1.751 1.575 2.316 CE2255 18 20.7 42 CE2256 16 24 47.8 0.9 0.33 0.2 CE2257 30 48.3 61.4 CE2258 3.7 42.9 38.1 1.624 1.5 1.212 CE2259 3.3 43 59.6 0.597 0.846 0.502 CE2260 0.39 68.3 59.7 3.532 3.053 1.894 CE2261 0.36 CE2262 0.42 CE2263 0.67______________________________________
Example 115
Ex vivo inhibition of elastase
Sixty (60) minutes after the oral adminstration of an inhibitor with an appropriate vehicle, a blood sample (0.9 ml) is collected through the abdominal aorta by a syringe containing 0.1 ml of a 3.8% sodium citrate solution.
The blood sample is processed as follows: 60 μl of (final 0.1-1 mg/ml) a suspended solution of opsonized zymosan in Hank's buffer is added to the preincubated whole blood (540 μl) for 5 minutes at 37° C., and the resulting mixture is incubated for 30 minutes at the same temperature. The reaction is terminated by immersing the test tube into ice water. The reaction mixture is then centrifuged at 3,000 rpm for 10 minutes at 4° C. Twenty (20) μl each of the resulting supernatant (the Sample) is measured for elastase activity.
The mixture consisting of the following components is incubated for 24 hours at 37° C., and then optical density is measured at 405 nm:
______________________________________0.2 M tris-HCl buffer (pH 8.0) 100 μl 2.5 M NaCl 40 μl Distilled water 36 μl 50 mM solution of a substrate (*) 4 μl The Sample 20 μl______________________________________ *N-Methylsuccinyl-Ala-Ala-Pro-Val-p-nitroanlide (SEQ ID NO: 1)
A test sample mixed with 1-methyl-2-pyrrolidone instead of the substrate is regarded as Substrate (-). A test sample mixed with saline instead of the Sample is regarded as Blank. The remaining elastase activity in the Sample is calculated according to the following:
optical density of Substrate (+)-(optical density of Substrate (-)+optical density of Blank) as a total production of p-nitroaniline over 24 hours based on a standard curve for the amount of p-nitroaniline.
An average activity is calculated based on the test sample of 5-6 animals. An agent at 3, 10 or 30 mg/kg is orally given by a forced administration to a 24 hour fasted animal at 60 minutes before the blood sampling. Optical density is measured by SPECTRA MAX 250 (Molecular Devices).
__________________________________________________________________________# SEQUENCE LISTING - - - - <160> NUMBER OF SEQ ID NOS: 1 - - <210> SEQ ID NO 1 <211> LENGTH: 4 <212> TYPE: PRT <213> ORGANISM: Human <220> FEATURE: <221> NAME/KEY: BLOCKED <222> LOCATION: (1)...(1) <223> OTHER INFORMATION: MeOSucc <220> FEATURE: <221> NAME/KEY: BLOCKED <222> LOCATION: (4)...(4) <223> OTHER INFORMATION: p-nitroanilide - - <400> SEQUENCE: 1 - - Ala Ala Pro Val__________________________________________________________________________ | The present invention relates to certain compounds comprising substituted oxadiazole, thiadiazole and triazole structures which are useful as inhibitors of serine proteases, including human neutrophil elastase (HNE). Compounds described herein are characterized by their relatively low molecular weight, high potency and selectivity with respect to HNE, and can be used to effectively prevent, alleviate or otherwise treat disease states characterized by the degradation of connective tissue by proteases in humans. | 2 |
RELATED APPLICATIONS
[0001] This application is a divisional of U.S. application Ser. No. 11/173,103, filed Jun. 30, 2005, and is a divisional of U.S. application Ser. No. 11/459,597, filed Jul. 24, 2006, both claiming the benefit of and priority to U.S. Provisional Application Ser. No. 60/586,337, filed Jul. 7, 2004, the contents of all of which are incorporated by reference herein in their entirety.
BACKGROUND
[0002] 1. Field
[0003] The present disclosure generally relates to accurate and specific control of water oxidation reduction potentials, and more particularly to systems, methods and apparatus for safe and effective water sanitation and treatment.
[0004] 2. General Background
[0005] Various methods and apparatus have been utilized in order to treat/sanitize water. For example, the use of oxidants such as gaseous ozone for disinfection is well known. Typically, retention chambers are utilized into which ozone is introduced to water contained therein. Oxidation-reduction reactions then take place between the introduced ozone and contaminants in the water, where the oxidants are reduced and contaminants in the water are oxidized. Various oxidants are well known in the water treatment arts, such as bromine and chlorine, for example.
[0006] A common problem with such prior art systems is the reliance on less than accurate/controllable methods for monitoring and controlling the amount of residual oxidant (e.g. ozone) retained in water after introduction of the oxidant into water to be treated. Another troublesome aspect is the production of various radicals and side reactions that result in residual oxidizing species. Various methodologies have been employed to control oxidant-contaminant reactions. One prior art method utilizes multiple chambers to allow the introduction of an oxidant, ozone, to break down and oxidize contaminants, the remaining ozone then dissipating into oxygen. In such a system, a main component is time. That is, there is a passive reliance on the inherent breakdown of the oxidant introduced into the system. Additionally, when an oxidant is introduced at a consistent rate or amount into a process stream of water to be treated, fluctuations in the amount of contaminants in the water to be treated greatly affects the reaction dynamics between the introduced oxidant and the contaminant. Reductions in the amount of contaminants, or those compounds to be oxidized in a process stream, without an accurate and concordant reduction of introduced oxidant will lead to unacceptably high concentrations of residual oxidants' in the process stream.
[0007] This typically leads to introduction of an oxidant at unacceptable levels into a water system or water source. This is particularly an issue when the destination of this treated water includes/supports various life forms that will be adversely affected by the introduction of treated water having unacceptably high concentrations of residual oxidants. Inaccurate prior art chemical methods for neutralizing oxidants introduced to sanitize water typically result in unwanted chemical reactions that can be detrimental, particularly when water in which such reactions are introduced into an aquatic ecosystem.
[0008] Other prior art methodologies include technology utilizing oxidation reduction potential monitoring for controlling oxidant feed. Typically these methods regulate oxidant feed based on how the oxidant is consumed, reacting with target substances/contaminants and unwanted organisms, within a system. As an example, a typical prior art method for treating water utilizes dissolved ozone as an oxidant and hydrogen peroxide to decompose remaining ozone concentrations left after the passage of a set amount of time. The addition of peroxide merely creates a less stable and more reactive oxidant that is less likely to persist. Allowing for the natural decay of the oxidant presents some major limitations to these technologies.
[0009] One limitation of the prior art is the fact that the rate of oxidant feed is limited by the demand and ability of the target system to remove it. This often prevents one from being able to dose an oxidant at high enough rates and/or concentrations to effect complete sterilization/sanitation. For example, Cryptosporidium is a significant health hazard for humans that can cause life threatening diarrhea. This pathogen is highly resistant to all but very high oxidant concentrations, concentrations that may not be obtainable utilizing prior art methods due to the inability of such methods to effectively neutralize the high concentration of the oxidant in a useful manner. In the case of lagoons, reefs, or any sensitive ecosystem into which such treated water is introduced, the release of even the smallest amounts of oxidant is potentially life threatening to flora and fauna residing therein.
[0010] Hydrogen peroxide is a weak acid that is partially dissociated in water, based on the pH, into its hydroperoxide ion.
[0011] An equilibrium equation is, H 2 O 2 +H 2 O HO 2 − +H 3 O + , pK a =11.6
[0012] The hydrogen peroxide molecule itself reacts very slowly with ozone, conversely the hydroperoxide ion reacts very quickly. The actual reaction profile is very complex with the formation of multiple types of free radicals including the production of hydroxide radicals. It is through the production of these radicals, from the combination of ozone and hydrogen peroxide, that provides for the techniques of prior art advanced oxidation processes for a variety of water remediation challenges. The mechanism of ozone decomposition, initiation and propagation reactions are proposed as follows (Ozone in Water Treatment: Application and Engineering, 1991):
[0000] H 2 O 2 +H 2 O HO 2 − +H 3 O +
[0000] O 3 +HO 2 − →OH+O 2 − +O 2
[0000] O 2 − +H + HO 2
[0000] O 3 +O 2 − →O 3 − +O 2
[0000] HO 3 →OH+O 2
[0013] As can be seen from the equations above, the actual decomposition of ozone by hydrogen peroxide is fairly complex and includes the production of hydroxide and superoxide radicals. The products of these reactions will provide for further oxidation of oxidizable organics and/or inorganics.
[0014] As can be seen from the above equations, the use and addition of hydrogen peroxide into a process stream to control or neutralize dissolved residual ozone will decompose ozone molecules, but in the process create unwanted free radical residuals along with some remaining unreacted hydrogen peroxide that will contribute to elevated oxidation reduction potentials of water in a treated effluent stream. Such reaction remnants are highly undesirable and indeed may be detrimental to flora and fauna that reside in water into which such treated effluent streams may be introduced.
[0015] An amusement park aquarium system is an example where accurate control of a process stream of water is required and unwanted free radical residuals along with unreacted hydrogen peroxide, are not desired. Amusement park aquarium systems typically house substantially synthetic seawater. These systems can be quite large, holding and maintaining millions of gallons of seawater. These systems are typically closed in that no water is added or removed except through evaporation and slight operation losses. Seawater in aquatic displays typically supports various aquatic life forms. As such, the water contained therein receives significant waste products/contaminants from marine mammals and fish that reside therein, in addition to the various plant, color bodies and other contaminants typically found in such displays.
[0016] Excess waste products result in organic build up and color bodies that render waters in such displays uninhabitable. The buildup also limits visibility to patrons visiting the aquarium. For example, seawater in such aquariums take on a significant green/yellow cast that limits visibility and gives the aquarium an unhealthy and unnatural appearance.
[0017] Unfortunately, in prior art systems, the rate of oxidation is traditionally limited by the susceptibility of the resident aquatic species to tolerate byproducts produced by the oxidation reactions, such as hypobromous acid. Often the animals housed in these aquatic habitats are very sensitive to, and easily damaged by even slight residual amounts of ozone, chlorine, bromine, or other halogens. There are times when marginally acceptable water quality often takes precedent over increased oxidation treatments due to animal health concerns. Oxidation treatments would be effective at treating color and waste concerns, but the necessary dosing required would likely lead to harm the surrounding environment and animals residing therein.
[0018] There exist treatment systems for neutralizing oxidizing agents by delivering neutralizing and converting chemicals like sulfur dioxide, sodium thiosulphate and ascorbic acid. However, these systems are used almost exclusively with chlorine. Traditionally, the conversion chemicals are “dumped” wholesale into a process stream to completely erase any oxidative potential and there is no regulation of oxidative potential. These systems are typically used to de-chlorinate water before the water is released into surface water systems. The method of conversion is crude, largely uncontrolled, and potentially releases significant amounts of unreacted neutralizing chemicals into the environment. In a closed system such as a commercial aquarium, the unreacted neutralizing chemicals can cycle back through a process stream and deactivate oxidizing agents that are introduced and before they react with the target contaminants and harmful waste products. The uncontrolled release of the neutralizing chemicals also results in incomplete conversion of the oxidizing agents or harmful chemicals to safe compounds, which results in harm to the surrounding environment.
[0019] Water treatment systems utilized in other applications also experience similar problems. For example, watercrafts, such as cruise ships, must also disinfect discharge waters that are dumped into the ocean. Discharge waters are typically substantially made up of grey and/or black water that is generated onboard the watercraft. Grey water is typically used water from showers, sinks or basins, including used kitchen water. Black water is water contaminated with human waste, collected from shipboard toilets. Under various national and international standards, black water must be treated before being discharged from a vessel. During water treatment, undesirable by-products and unreacted oxidants discharged by these watercraft harm the environment and bodies of water in which these vehicles travel. In some cases, typically depending upon the types of water treatment system employed onboard and/or the location of the vessel, the watercraft are not allowed to discharge treated water into surrounding natural bodies of water. Often, watercraft must store the grey and/or black water generated onboard and transfer such water to a water treatment system located off board.
SUMMARY
[0020] In one aspect, the present disclosure provides for a system, apparatus and method that intensely oxidizes and treats water as it navigates through a filtration system and further neutralizes oxidant and oxidation by-products before the water exits the system.
[0021] One aspect of this system and method of process control oxidation is capable of sequestering a typical filtration stream and disinfecting the stream without impacting sensitive animals in a habitat for which water is treated. This is accomplished through precise regulation of oxidation and subsequent neutralization of unreacted oxidants and undesirable by-products. The technique utilizes precise regulation, by computers, of a process stream where oxidation values, represented by oxidation reduction potential (ORP), are manipulated.
[0022] In another aspect, the system comprises a process where high levels of oxidizing agents are delivered into a process stream to affect disinfection. The oxidizing agents are subsequently converted to harmless compounds. This process is computer controlled using oxidant dispensers, such as ozone generators, chlorine pumps, or other similar devices. The output rate of the oxidizing agent is varied to correlate with target set points as measured by oxidation state probes.
[0023] In particular embodiments, subsequent neutralization or conversion of the process stream is completed before the process stream is returned to a main water supply or water source, from which the process stream originates. This stage in the process is regulated by computer controlled injection of a neutralizing chemical. The output rate of the neutralizing chemical is varied to correlate with a target set point as measured by oxidation state probes. While there are devices that provide oxidant feed based on oxidation-reduction potential or demand, the present system has the ability to reduce oxidation-reduction potential to a specific target value, once desired disinfection is accomplished. In particular embodiments, a target value can be a value that still provides the treated water with a oxidation-reduction potential that is capable of reducing contaminants (e.g. an oxidation-reduction potential greater than zero).
[0024] In one embodiment, a water treatment apparatus is provided that comprises a conduit, from a water source, defining a flow path containing water from the water source. This conduit is in communication with the water source and a water treatment system. The system includes a first oxidation reduction potential measuring point having at least one sensor for measuring a first oxidation reduction potential of water from the water source. The at least one first sensor is in communication with a master controller. An oxidant injection controller, in communication with an oxidant dispenser, is also provided and is in communication with the master controller. An oxidant dispenser, in communication with the flow path, dispenses at least one oxidant at an oxidant injection point along the flow path and into the water, is also provided. The conduit includes a first mixing portion of the flow path for mixing injected oxidant with water from the water source in order to establish and provide a first target oxidation reduction potential. At a second point of the conduit, at least a second sensor is provided and is also in communication with the master controller. The second sensor measures a second oxidation reduction potential, and the second sensor is located downstream from the first mixing portion. A neutralizing chemical dispenser is also provided and is located downstream of the oxidant injection point. A neutralizing chemical injection controller, also in communication with the master controller and the neutralizing chemical dispenser, dispenses at least one neutralizing agent via a neutralizing chemical injection point along the flow path. A second mixing portion of the flow path is provided for mixing water emanating from the first mixing portion with the at least one neutralizing agent. This mixing establishes and provides a second target oxidation reduction potential in the water in the flow path. The flow path includes a water return portion for conducting water from the second mixing portion back to the water source.
[0025] In particular embodiments, the oxidant dispenser and the neutralizing chemical dispenser dispense their respective contents into the flow path, containing water, at computer-controlled rates that are correlated to and establish the desired first target oxidation reduction potential and the second target oxidation reduction potential, obtained and measured in real-time.
[0026] In particular embodiments, the water's first oxidation reduction potential (as it is obtained from the water source) is less than the first target oxidation reduction potential. The first target oxidation reduction potential is typically a sanitizing oxidation reduction potential that is predetermined and established in accordance with the particular application of the teachings of the present disclosure.
[0027] In some embodiments, various configurations of the conduit are contemplated to provide desired mixing characteristics of the various mixing portions. In one embodiment, mixing portions include venturi arrangement of conduits, for example.
[0028] Various useful compounds are contemplated, in accordance with the present disclosure. In particular embodiments, at least one oxidant is introduced into water of the flow path. In some embodiments, the at least one oxidant is combined with at least one additional oxidant. Exemplary oxidants include ozone, bromine, chlorine, fluorine and iodine. Various neutralizing chemicals/compounds can be utilized in various embodiments. For example, the at least one neutralizing chemical can be a thiosulfate-containing compound, such as sodium thiosulfate, for example.
[0029] Additionally and in some embodiments, a combination of neutralizing chemicals can be utilized. For example, the thiosulfate compound may be combined with at least one additional neutralizing chemical such as, but not limited to, sodium sulfite, ascorbic acid, or hydrogen sulfite or any combination thereof. In other embodiments, sodium sulfite, ascorbic acid and hydrogen sulfite can be utilized alone or in any useful combination.
[0030] Exemplary first target oxidation reduction potentials are about two to about four times higher than the first oxidation reduction potential of the water taken from the water source, but may range from about 1.1 to 10 times higher. For example, the first target oxidation reduction potential is a sanitizing oxidation reduction potential that is utilized and known to sanitize water to a desired degree. Exemplary first target oxidation reduction potentials can be about two to four times greater than the first oxidation reduction potential of the water when taken from the water source. As such, the second target oxidation reduction potential that is established upon addition of the at least one neutralizing chemical is typically less/a lower value than the first target oxidation reduction potential that is established upon addition of at least one oxidant.
[0031] The teachings of the present disclosure also provide water treatment apparatus, systems and methods wherein the second target oxidation reduction potential is reduced to about 50 to about 80 percent of the first target oxidation reduction potential established after addition of the at least one oxidant to water in the flow path. In some embodiments, the flow path includes a filter for filtering particulates out of the water obtained from the water source. In still other embodiments, at least one qualitative sensor is provided along the flow path. An exemplary qualitative sensor detects a color and/or color level/intensity and/or turbidity which correlates to a contamination level of water being analyzed by the at least one sensor, such a qualitative sensor.
[0032] Particular embodiments include a conduit portion for conducting treated/sanitized water back to the water source, where water flowing from the second mixing portion contains a desired target amount/level of residual oxidant (and hence has a particular oxidation reduction potential) that does not substantially change the overall average oxidation reduction potential of water in said water source. In still other embodiments, water emanating from the second mixing portion contains substantially no residual oxidant or other oxidative radicals resulting from injection the at least one oxidant into water in the flow path.
[0033] In one aspect, water emanating from the second mixing portion has an oxidation reduction potential between about 550 mV to about 700 mV. In other examples, the oxidation reduction potential can be between about 570 mV to about 625 mV or from between about 580 mV to about 610 mV.
[0034] In some embodiments, a portion of the injected at least one oxidant remains unreduced by contaminating reducing agents located in water from the water source. This portion of unreduced at least one oxidant is then reduced by interaction with the at least one neutralizing chemical at the second mixing portion of said flow path. The at least one neutralizing chemical is injected in a sufficient amount in order to achieve the second target oxidation reduction potential.
[0035] Particular embodiments utilize various types of controllers to dispense the at least one oxidant and at least one neutralizing chemical into the flow path of water in the conduit. For example, some embodiments utilize an oxidant injection controller that is a programmable logic controller. This can be combined with the use of a neutralizing chemical injection controller that is also a programmable logic controller. In one embodiment, such programmable logic controllers include a proportional integral derivative loop.
[0036] Some embodiments employ a second mixing portion of the flow path that contains a reaction that proceeds in accordance with the chemical formula:
[0000] 4O 3 +2S 2 O 3 2− +4OH − →4SO 4 2− +2O 2 +2H 2 O.
[0037] In another aspect, the present disclosure also provides a method for water treatment. Particular embodiments include the steps of providing a conduit for conducting water from a water source and thereby obtaining an amount of water from the water source. This amount of water, to be treated from said water source, has an oxidation reduction potential. After measuring a first oxidation reduction potential of the water, the water is conducted to at least one oxidant injection point where the step of introducing an effective amount of at least one oxidant to the water takes place. A second oxidation reduction potential is measured, wherein the second oxidation reduction potential is greater than the first oxidation reduction potential and the second oxidation reduction potential is a predetermined sanitizing target oxidation reduction potential. This predetermined sanitizing target oxidation reduction potential is achieved by introduction of the effective amount of the at least one oxidant and allowing for a first oxidation-reduction reaction to occur. This first oxidation reduction reaction proceeds between the introduced at least one oxidant and at least one contaminant in the water. A further step is provided where a measurement of a third oxidation reduction potential of the water, after allowing a predetermined amount of time to pass following commencement of the a first oxidation-reduction reaction, is taken. Afterwards, a step of introducing an effective amount of at least one neutralizing chemical into the water is executed, the effective amount being based upon the measured third oxidation reduction potential and a target effluent oxidation reduction potential and allowing for a second oxidation reduction reaction to take place in the water. The second oxidation reduction reaction proceeds substantially between remaining amounts of the at least one oxidant and the at least one neutralizing chemical. A target effluent oxidation reduction potential is then established in the water, and the resultant treated water, now having the target effluent oxidation reduction potential, is then distributed.
[0038] In accordance with the present disclosure, water to be treated by the apparatus, systems and methods disclosed herein can originate from at least one of a plethora of sources. Exemplary water sources, include a sea, a lake, a stream, an ocean, a storage tank, an aquarium, a swimming pool, a fountain, a river, a contaminated spill area, a delta, a swamp, a pond, a channel, a sewer, a canal, a food processing station, water park or an agricultural harvesting or processing location or any combination thereof.
[0039] In accordance with particular embodiments, methods disclosed herein can further comprise a step of filtering water before and/or during and/or after treatment, in addition to exposing the water to the various chemical based sanitation protocols provided herein. Where computer control is utilized, various embodiments can further include steps of entering the predetermined sanitizing target oxidation reduction potential value and/or target effluent oxidation reduction potential value into a master controller, which can be a computer or a network of computers.
[0040] Various methods disclosed herein utilize ozone as the at least one oxidant. In some embodiments, the at least one oxidant is combined with at least one additional oxidant. Exemplary additional oxidants to be added to ozone, for example, are selected from the group consisting of bromine, chlorine, hydrogen peroxide and potassium monopersulfate. In other embodiments the at least one oxidant is selected from the group consisting of ozone, bromine and chlorine. Various methods disclosed herein utilize sodium thiosulfate as the at least one neutralizing chemical. Exemplarily, the at least one neutralizing chemical can be combined with at least one additional neutralizing chemical selected from the group consisting of sodium sulfite, ascorbic acid and hydrogen sulfite. In still other embodiments, the at least one neutralizing chemical is selected from the group consisting of sodium thiosulfate, sodium sulfite, ascorbic acid and hydrogen sulfite or any combination thereof.
[0041] Particular embodiments treat water that originates from various sources. Some embodiments include grey water and/or black water. Such water is typically generated onboard a watercraft, and at least one of gray and/or black water comprises the water source from which water is to be treated. In another aspect, water to be treated may come from water collected from at least one food processing station. Such water is typically utilized to wash at least one food item at the at least one food processing station. Large volumes of water that are to be treated may originate from post-harvesting activities, for example during handling and processing of fruits and vegetables.
[0042] In some embodiments, a washing step results in water contamination with at least one natural bodily fluid or at least one bodily secretion. Such contamination can take place at meat processing centers, for example, such as slaughterhouses and/or meat packaging plants. In such cases, the at least one natural bodily fluid comprises any single or combination of blood and/or intracellular fluid and/or interstitial fluids. In some instances, the at least one bodily secretion includes at least one or a combination of urine, saliva, feces, or semen, for example.
[0043] In some embodiments, a process control oxidation water treatment system is provided that includes a water source located at a primary holding area with a main line in communication with the water source. The main line includes a main line injection point adjacent and upstream from a secondary holding area inlet. A set distance is provided between the main line injection point and the secondary holding area inlet. A process stream is provided and flows through the main line. The secondary holding area is provided with a secondary holding area inlet and a secondary holding area outlet. An oxidant dispenser, which delivers an oxidant into the process stream at the main line injection point, is also provided. The injected oxidant raises the oxidation reduction potential in the process stream and initiates a first reaction between the injected oxidant and contaminants within the process stream. Subsequently, a neutralizing chemical is injected into the secondary holding area, to which the water passes, and a second reaction between the neutralizing chemical and the oxidant and by-products of the first reaction takes place, lowering the oxidation-reduction potential of the process stream. Such lowering brings the oxidation reduction potential to a predetermined target oxidation reduction potential, such as a non-zero oxidation reduction potential.
[0044] In particular embodiments, at least one oxidation state probe is provided in or adjacent to the secondary holding area inlet to monitor oxidation-reduction potential of the water to which the at least one oxidant is added. A computer, having a target oxidation reduction potential set point and in communication with the oxidation state probe is also provided, along with a proportional-integral-derivative (PID) controller or other appropriate controller, in communication with the computer. The PID varies an injection rate of the oxidant into the process stream, based on the target oxidation-reduction potential set point.
[0045] Particular embodiments further includes another oxidation state probe, located adjacent or in the secondary holding area outlet to monitor the oxidation reduction potential, and the computer contains a second target oxidation-reduction potential set point connected to the oxidation state probe located adjacent, or in, the secondary holding area outlet. A second PID controller is connected to the computer to vary an injection rate of the neutralizing chemical into the secondary holding area.
[0046] In particular embodiments, the process stream originates from a water supply, subsequently flows through a main line/conduit, and is sanitized to form a sanitized process stream. This sanitized process stream is then returned to the water supply from which the process stream originated. In some embodiments, an oxidation state probe can be located in the water supply to monitor the process control oxidation water treatment system in an overall fashion, utilizing the oxidation reduction potential reading/level of the water supply as one indication show that the water treatment system is operating properly and within desired limits.
[0047] In some configurations, various embodiments provide a water treatment system and associated method that includes a secondary holding area outlet that further comprises an aeration tower and/or a discharge pipe.
[0048] As before, various embodiments utilize various water sources. Non-limiting examples include a sea, a lake, a stream, an ocean, a storage tank, an aquarium, a swimming pool, a fountain, a river, a contaminated spill area, a delta, a swamp, a pond, channel, canal, food processing or handling stations or any combination of water from such sources.
[0049] In particular embodiments, water to be treated that forms a process stream from a water source contains at least one contaminant or combination of contaminants. Exemplary at least one contaminant or combination of contaminants include, but are not limited to, at least one or any combination of color bodies, bacteria, viruses, fungi, natural bodily fluid of an organism or bodily secretion of an organism, for example. As an example, the at least one contaminant or combination of contaminants can originate or be introduced into the water to be treated from a food processing/handling station.
[0050] The various embodiments disclosed herein can treat water containing at least in part one of black or grey water, which can be produced onboard a watercraft, for example. In other embodiments, such black and/or grey water can originate and be generated from dwellings located on land (e.g., houses, office buildings, etc.).
[0051] In still another embodiment for treating water, a process stream of water from a water source is established and a first oxidation reduction potential is measured at a first measurement point. This measurement is conducted via at least one oxidation state probe in contact with water in the process stream of water from said water source, to which at least one oxidant is introduced at an oxidant introduction point. Subsequently, a second oxidation reduction potential is measured at a second measurement point downstream of the oxidant introduction point.
[0052] The introduction of the at least one oxidant provides for a first reaction between the at least one oxidant and contaminants within said process stream. In another step, a third oxidation reduction potential is measured at a third measuring point at or proximate to a treated process stream outlet and downstream from the first and second measurement points.
[0053] At least one neutralizing chemical is introduced into the process stream at a point downstream from the oxidant introduction point and before the treated process stream outlet, thereby providing a second reaction between the at least one neutralizing chemical and any remaining amounts of said at least one oxidant. As a result, a treated process stream target oxidation reduction potential set point of said process stream is achieved.
[0054] In one embodiment, a step of inputting information relating to a sanitizing oxidation reduction potential set point into a computer is provided. The sanitizing oxidation reduction potential set point determines, at least in part, a rate and/or amount of the at least one oxidizing agent is introduced into the process stream in order to establish the sanitizing oxidation reduction potential set point in the process stream.
[0055] A further embodiment includes the step of inputting information relating to a treated process stream oxidation reduction potential set point into a computer, said treated process stream oxidation reduction potential set point determining, at least in part, a rate at which said at least one neutralizing chemical is introduced into said process stream. If so desired, a filtering step is also provided whereby the process stream of water passes through at least one filter disposed at a position between the water source and the treated process stream outlet.
[0056] In particular embodiments, water treatment methods and apparatus are utilized in a closed circulating water system. Other embodiments utilize water drawn from a water source, such as a natural body of water, and pass it through the apparatus, system and subject the water to the method steps disclosed herein, and return it to the natural body of water. In some embodiments, the second oxidation reduction potential established via introduction of at least one oxidant is about two to about four times higher than a first oxidation reduction potential measurement of water as it is taken from the water source. In various embodiments a target oxidation reduction potential of a treated process flow is reduced from about 0.5 to 0.8 times the second oxidation reduction potential. In some embodiments, the natural body of water is a marine or freshwater body of water. In particular embodiments, the water source is an aquatic display that contains at least one aquatic life form. For example, life forms (i.e. flora and fauna) can include any one or combination of, but are not limited to, members of the Chordata, Echinodermata, Arthropoda, Mollusca, Cnidaria, Porifera, Angiospermophyta phyla.
[0057] In embodiments associated with an aquatic display having aquatic life forms contained therein, the final target oxidation reduction potential of the treated process flow returning to the aquatic display is a value (oxidation reduction potential value) that corresponds to an innocuous oxidation reduction potential, such that the at least one aquatic life form is not adversely affected as a result of introducing the treated process flow into the aquatic display. This is achieved in part by the step of introducing the at least one neutralizing chemical into the processing stream. In particular embodiments, the amount of the at least one neutralizing chemical is such that substantially no residual levels of an at least one oxidizing agent remains in the treated process flow, or oxidant levels are such that they are innocuous to the aquatic life form living in water into which the treated process flow is introduced.
[0058] In various embodiments, such precision is achieved by utilizing a computer in communication with a controller, such as, but not limited to, at least one proportional integral derivative controller that varies rates of introduction, in real-time, of the at least one oxidant and the least one neutralizing chemical into the processing stream. An exemplary second reaction proceeds in accordance with 4O 3 +2S 2 O 3 2− +4OH − →4SO 4 2− +2O 2 +2H 2 O, wherein ozone is the least one oxidant and a thiosulfate compound is the least one neutralizing chemical introduced into the process stream to give rise to the treated process flow.
[0059] The present disclosure also provides a method for treating water where a circulating water treatment system is provided. A main water source and a water treatment portion are provided. Water from the main water source is conducted to the water treatment portion, the conduction establishing a process stream and a first oxidation reduction potential of water from said main water source is measured.
[0060] A first oxidation reduction potential target set point is inputted into a computer, the first oxidation reduction potential target set point being a sanitizing oxidation reduction potential level which corresponds to an introduced effective amount of least one oxidant into the process stream. The effective amount is sufficient to raise the first oxidation reduction potential to the first oxidation reduction potential target set point. A first portion of the circulating water treatment system is provided for mixing of the introduced effective amount of at least one oxidant with water in the process stream, thereby allowing a first reaction to proceed between the effective amount of the at least one oxidant and contaminants in the process stream, in order to sanitize said process stream.
[0061] A second oxidation reduction potential is then measured, downstream of the first portion of the circulating water treatment system. The computer also has a second oxidation reduction potential target set point inputted into the computer, by which an effective amount of at least one neutralizing chemical is introduced into the process stream. The effective amount of the at least one neutralizing chemical is sufficient to establish the second oxidation reduction potential target set point in the process stream. A second portion of the circulating water treatment system is provided for mixing the process stream with the introduced effective amount of the at least one neutralizing chemical. A second reaction proceeds between the introduced effective amount of the at least one neutralizing chemical and residual amounts of the introduced effective amount of the at least one oxidant. This second reaction establishes a second target oxidation reduction potential target set point, which is less than the first oxidation reduction potential target set point.
[0062] In particular embodiments, water from the water treatment portion is introduced back into the main water source. Some main water sources contain one or a combination of flora and fauna. When this is the case, the second target oxidation reduction potential target set point is determined in consideration of an oxidation reduction potential tolerance level of the one or a combination of flora and fauna living in the main water source. The water source can be any water source from which water is drawn and treated in accordance with the teachings presented herein.
[0063] In some embodiments, the apparatus, systems, methods and associated components, reactions and method steps of the present disclosure take place upon a watercraft. In such embodiments, the main water source comprises at least one of grey or black water produced onboard the watercraft and provides water that forms a process stream to be treated. A process stream sanitized in accordance with the teachings herein and having a second target oxidation reduction set point, to which the treated stream is maintained, can be safely conducted to and released into a body of water in which the watercraft is located. The watercraft may be docked or be moving/propelled through the body of water as the various treatment steps are carried out, for example.
[0064] In some embodiments, one or a combination of grey or black water is stored in a storage tank upon the watercraft, and is then transferred to a water treatment system to be subjected to treatment in accordance with the present teachings. The water treatment system can be onboard or proximate to a watercraft docking point, in which case the grey and/or black water is transferred to a water treatment facility that employs apparatus, systems and methods disclosed herein.
[0065] In particular embodiments, the watercraft can include a circulating water treatment system. In others, where the main water source comprises at least one of grey or black water produced onboard the watercraft, the water is treated and introduced, having the predetermined and desired second target oxidation reduction set point, into a body of water in which the watercraft is located. In particular aspects, the watercraft is propelled through the body of water at the same time as the process stream having the second target oxidation reduction set point is introduced into the body of water on which the watercraft is located, that is, occurs during the propelling/movement of the watercraft. In some embodiments, storing the at least one or a combination of grey or black water is provided by and stored in a storage tank. In particular embodiments, produced grey and/or black water can be fed directly into the process stream from their points of origin and not be stored in a storage tank.
[0066] In some embodiments, the main water source onboard includes freshwater stored onboard the watercraft, from which said grey or black water is generated. In some embodiments, the watercraft also includes apparatus to proved a step of filtering the process stream of water. In still other embodiments, a step of and apparatus for aerating the process stream is also provided onboard.
[0067] Various contaminants can be included in grey and/or black water, including, but not limited to alone or in any combination of, bacteria, viruses, natural bodily fluid of an organism and bodily secretion of an organism.
[0068] Various embodiments include a step of filtering and/or aerating of water in the process stream.
[0069] In a particular embodiment, a water treatment system is disclosed having a water source and a conduit for conducting water from the water source and providing a process stream having a process stream oxidation reduction potential. A first oxidation reduction potential sensor is disposed at a first oxidation reduction potential measuring point and provides a first oxidation reduction potential which is inputted to a computer in communication with the first sensor, the computer containing a sanitizing oxidation reduction potential set point and a target effluent oxidation reduction potential set point. The system also includes at least one oxidant dispenser that introduces an oxidant, such as ozone for example, via/at a computer controlled rate, into the process stream at an oxidant introduction portion of the conduit. This raises the process stream's oxidation potential to the sanitizing oxidation reduction potential set point in the computer. The conduit also includes a first mixing portion downstream from the oxidant introduction portion for mixing the introduced oxidant into the process stream, whereby a first reaction between the oxidant, contaminants and bromide in the process stream takes place. This first reaction results in the formation of hypobromous acid, reduction of contaminants and lowers the level of oxidant. Water then travels to a second mixing portion of the conduit for mixing water, now having a first mixing portion oxidation reduction potential with a neutralizing compound. The neutralizing compound is introduced into the process stream in accordance with a computer controlled rate, the rate being based upon consideration of the first mixing portion oxidation reduction potential and the target effluent oxidation reduction potential set point. A second reaction is thereby provided and proceeds in the second mixing portion. This second reaction includes the reaction of thiosulfate ions with residual ozone or hypobromous acid or a combination of both ozone and hypobromous acid, in the process stream. This reduces ozone and hypobromous acid to oxygen and bromide, respectively, and at the same time provides and establishes, in the processing stream, an oxidation reduction potential concordant with the target effluent oxidation reduction potential set point. Water is then passed through/to a discharge portion of the conduit. In particular embodiments, the discharge portion is in communication with and conducts water to the water source, from which the now treated water first originated.
[0070] A method for controlling oxidation reduction potentials in a process stream, is also provided, where the oxidation-reduction potential of a process stream is measured with a first oxidation state probe. This first target oxidation-reduction potential set point is inputted into a computer. An effective amount of an oxidant is then injected into the process stream based on the measurement from the first probe and variations from the first set point. A second measurement is taken, measuring the oxidation-reduction potential of the process stream with a second oxidation state probe downstream from the first probe. The computer has inputted therein a second target oxidation-reduction potential set point into a computer. An effective amount of a neutralizing chemical is injected into the process stream based on measurements from the second probe and variations from the second set point.
BRIEF DESCRIPTION OF THE DRAWINGS
[0071] The foregoing aspects and many of the attendant advantages provided herein will become more readily appreciated as the same becomes better understood by reference to the following detailed description, when taken in conjunction with the accompanying drawings, wherein:
[0072] FIG. 1 illustrates an overview of an exemplary system in accordance with one aspect of the present disclosure;
[0073] FIG. 2 illustrates one exemplary process control components of the system for an oxidation injection;
[0074] FIG. 3 illustrates one exemplary of process control components of the system for neutralizing chemical addition;
[0075] FIG. 4 illustrates one embodiment as applied to a large-scale commercial aquarium;
[0076] FIG. 5 illustrates one exemplary process flow diagram of one embodiment as applied to a large-scale commercial aquarium;
[0077] FIG. 6 depicts one exemplary configuration of exemplary components of a water treatment system in accordance with the teachings of the present disclosure;
[0078] FIG. 7 depicts steps of one exemplary method for treating water;
[0079] FIG. 8 depicts one exemplary embodiment wherein water treatment occurs onboard a watercraft; and
[0080] FIG. 9 is an exemplary chart depicting performance of one embodiment of the water treatment system disclosed herein.
DETAILED DESCRIPTION
[0081] Particular embodiments of the invention are described below for the purpose of illustrating its principles and operation. However, various modifications may be made, and the scope of the invention is not limited to the exemplary embodiments described below.
[0082] One general embodiment of the system and method of the present disclosure is illustrated by FIG. 1 . Here, a process stream 14 containing water from a water source, such a main reservoir 22 , for example, is obtained. In one example, main reservoir 22 is an aquatic tank or aquarium, such as those typically found at aquatic water parks and that contain aquatic life forms that excrete bodily fluids into the water of the tanks. However, any body of water, such as a lake or ocean, may have water taken from, treated and returned in accordance with the teachings provided herein. The process stream 14 flows through a main line 24 . At a main line injection point 26 , at least one oxidant is added to the process stream 14 from at least one oxidant dispenser 10 . The oxidizing agent cleans and sanitizes the process stream 14 as it flows through the main line 24 . That is, oxidation-reduction reactions take place between the introduced at least one oxidant and contaminants in water of process stream 14 .
[0083] In this embodiment, downstream from main line injection point 26 , process stream 14 enters an aeration tower 18 at an aeration tower inlet 20 . In this particular embodiment, aeration tower 18 is a rectangular concrete structure approximately a height of 40 ft, a width of 15 ft, and a length of 15 ft, for example. The volume/capacity of an exemplary tower is about 67,000 gallons. As water in process stream 14 is flowing through aeration tower 18 , a neutralizing chemical 12 is added to the top of aeration tower 18 . While the process stream 14 is passed through aeration tower 18 and neutralizing chemical 12 is added, neutralizing chemical 12 neutralizes surplus oxidants that were added at a main line injection point 26 into process stream 14 . Addition of neutralizing chemical 12 also converts harmful by-products produced as a result of the oxidation-reduction reaction to safe compounds. Process stream 14 then flows into the main reservoir 22 through an aeration tower outlet 16 .
[0084] While aeration tower 18 is included and is used in the exemplary embodiment schematically depicted in FIG. 1 , there exist several variations to this component, that is, a portion of the system where water from a water source mixes with at least one oxidant that is introduced into process stream 14 . Other secondary holding areas such as discharge pipes or storage tanks could also be utilized. Generally, at least one oxidizing agent is injected into a process stream. Downstream from this injection point, a conversion or neutralizing chemical is injected into the process. Further downstream, the amount of chemicals in the process are measured to determine what adjustments need to be made to the injection rates of both the at least one oxidant and at least one neutralizing chemical.
[0085] One embodiment of useful control apparatus for injecting at least one oxidizing agent is depicted in FIG. 2 . An aeration tower inlet probe 42 measures the oxidation reduction potential (ORP) 40 of process stream 14 as it flows through aeration tower inlet 20 . A target ORP set point 30 is pre-selected and entered into a master controller, such as a computer 34 . These sensors (sensors/probes that measure the ORP of water at various stages) serve as data inputs to a microprocessor or analog based computer. The computer employs some mode of control utilizing Time Based Proportional (TBP), Proportional (P), Proportional Integral (PI), Proportional Integral Differential (PID) and/or on/off control for controlling chemical(s) feed, that is, feed of the at least one oxidant and/or the at least one neutralizing chemical into process stream 14 . Computer 34 can be programmed utilizing either Fuzzy logic or Boolean logic protocols to provide the system with the ability to make changes to various settings or feed adjustments based on evaluation of input data obtained in real-time.
[0086] For example, in one embodiment, a supervisory control and data acquisition (SCADA) distributed intelligence system is utilized. In this embodiment, numerous devices are linked together and monitored and controlled by a master computer. In a smaller system, one would use as few as one computer to control the water treatment system. Based on a difference between target set point 30 and measured ORP reading 40 , an injection Proportional-Integral-Derivative (PID) controller 36 , for example, will vary the output of the at least one oxidant 32 dispensed into process stream 14 .
[0087] Examples of other controllers that could be used include simple “pumps” that deliver set rates of material until told to turn off by the computer. A PID controller, for example, is an algorithm embedded within the control program that looks at rate of change and formulates a “look ahead” delivery rate to dose to target. The PID controller looks at the curve slope and varies output based on rate of change (slope dy/dx) and distance to target. Such an approach is less critical with high impedance systems, those that respond vary slowly to input, than with those systems that are less stable and can change dramatically with small input (in this case oxidant delivery) changes.
[0088] An exemplary embodiment of control apparatus utilized to inject at least one neutralizing chemical into process stream 14 is illustrated in FIG. 3 . An aeration tower effluent probe 62 measures the ORP 60 of the process stream 14 as it flows through the aeration tower outlet 16 . A second target ORP set point 50 , which is an ORP value that is pre-selected, is entered into a computer 34 . Based on the difference between second target set point 50 and the measured ORP reading 60 , taken by aeration tower effluent probe 62 , an injection Proportional-Integral-Derivative (PID) controller 56 will vary the output/rate of the at least one neutralizing chemical 52 dispensed into the process stream 14 by at least one neutralizing chemical dispenser. In one aspect, the least one neutralizing chemical is introduced in order to interact with any residual amounts of the at least one oxidant 32 dispensed into process stream 14 that is still present and provides an ORP value that is too high to safely pass aeration tower outlet 16 and be introduced into a body of water. This second oxidation-reduction reaction typically takes place between the at least one neutralizing chemical 52 and residual amounts of oxidants that were added at a main line injection point 26 and as well as between the at least one neutralizing chemical 52 and other oxidizing species, such as, but not limited to hypobromous acid and hypochlorous acid, that form as a result of introduction of the at least one oxidant into process stream 14 .
[0089] There exist other possible ways to control this sensitive process for accurately balancing and varying the amount/rate of introduced oxidizing agents from at least one oxidant dispenser 10 to raise the ORP of process stream 14 to a desired predetermined sanitizing ORP level, allow a first reaction to proceed between the introduced at least one oxidant and contaminants in the process stream and then neutralizing residual oxidizing species such that a second target ORP is achieved.
[0090] For example, instead of utilizing oxidation-reduction probes/sensors which measure the presence of an oxidant, but cannot differentiate between the types of oxidants in the process stream, direct readings of specific oxidants such as chlorine or ozone using the appropriate respective meters could be used to detect the amount of chemicals. For example, a probe that measures chlorine or ozone is specifically designed to directly measure that oxidant only and produce a quantifiable value, i.e. ppm or mg/L of the measured oxidant. A calorimetric sensor, for example an in-line spectrophotometer, which measures the color changes of a process stream as a result of addition of the reactants, could also be utilized.
[0091] FIG. 4 shows one example of an embodiment of a water treatment system used in a large-scale commercial aquarium containing seawater. In this example, process stream 14 flows from water source such as, a main reservoir 22 , into a water treatment system comprising a main line 24 and an aeration tower 18 , before flowing back into main reservoir 22 . In another exemplary embodiment, the process stream separates from the water supply at tank skimmers (not shown). In one example, the water treatment system can utilize a filter or filtering arrangements as part of the water treatment process/apparatus. In one embodiment, water enters a 48″ pipe and travels to ten 30 ft by 10 ft high pressurized sand filters which remove particulate matter to 5 microns. The water then reenters main line 24 where at least one oxidant, such as ozone, is injected at main line injection point 26 . Aeration tower 18 contains both an inlet 20 and an outlet 16 for the process stream 14 to traverse. While process stream 14 travels through the system it is sanitized.
[0092] To sanitize the process stream 14 in this implementation, at least one oxidants is added to the main line 24 at the main line injection point 26 . In this particular embodiment, main line 24 pipe diameter is 48″ and the flow rate of the process stream 14 is approximately 30,000 gallons per minute. Exemplary oxidants include, but are not limited to ozone, bromine and chlorine.
[0093] In one embodiment, ozone 104 is added to process stream 14 from at least one ozone generator 90 , such as a liquid-oxygen-based ozone generator, for example. An exemplary ozone generator that can be utilized is identified under the trade name MEGOS, manufactured by Schmidding, Inc. of Germany. In this particular embodiment, approximately 15 to 22 lbs of ozone 104 is added each day at a rate of 0.061 mg/L.
[0094] This is one exemplary concentration based on the ozone production rate in mass per unit time and flow rate (volume per unit time) and employing particular calculations for the mass transfer of the ozone into solution. Because of the highly variable nature of the process stream, the amount of ozone required to produce a sanitizing ORP will vary depending on the oxidation demand of the contaminants (e.g. contaminant level and/or type or types) in the process stream. Accordingly a PID computer control system is advantageously disclosed and taught herein, since such system can accommodate the changes in oxidant demand to reach or maintain a desired ORP that will sanitize the process stream.
[0095] An exemplary oxidation reaction where ozone 104 is the oxidant and which occurs in process stream 14 is shown below.
[0000] O 3 +Br − →O 2 +BrO −
[0000] BrO − +H 3 O + HBrO+H 2 O
[0096] The injected ozone 104 will react with a number of organic compounds, lyse bacterial cell walls, decolorize chromophores, and react with bromide ions present in the water that makes up process stream 14 . The ozone 104 will oxidize bromide into hypobromite ions. The hypobromite ion is a weak acid and so will exist in its protonated and unprotonated form, the respective ratios being based on the acidity of the system's seawater.
[0097] With the appropriate reaction time, in this exemplary implementation of the teachings provided herein, measured from the point of ozone injection 26 to a top of the aeration tower 84 , for example, about 3 minutes, the predominant residual oxidants that are responsible for driving the ORP at the location of the aeration tower inlet probe 42 are dissolved ozone and hypobromous acid.
[0098] This is just one example of possible oxidation reactions that occur in an exemplary filtration and water treatment method. Due to the nature of this system and in accordance with the teachings provided herein, that is, the consistent computer controlled introduction of chemicals that exhibit a high oxidation state, such as ozone and exhibit toxicity on oxidative power, such as thiosulfate containing compounds, can be employed. For example, other oxidizing agents, such as, but not limited to, chlorine, bromine, and other halogens, could also be used in addition to ozone.
[0099] In the embodiment shown in FIG. 4 , at the top of aeration tower 84 , dissolved sodium thiosulfate 106 from a supply tank 82 is injected at a rate specified by the Proportional-Integral-Derivative controller, based on the second target ORP set point for the aeration tower effluent probe 62 . The probe 62 measures the amount of oxidizing agents in the system, and an amount of sodium thiosulfate 106 is added to neutralize the oxidizing agents. The neutralizing chemical, in this case a sodium thiosulfate solution, is prepared at a specific concentration. A typical concentration of sodium thiosulfate solution is approximately 45 mg/L as sodium thiosulfate. Too high a concentration of thiosulfate could lead to an overly aggressive response from the injection of the neutralizing chemical which could lead to an excessive dampening of the second target ORP. Conversely, a too weak of a thiosulfate solution could lead an insufficient response (damping) of the ORP levels and may require amounts of solution that exceed the pumping capacity of the injection pumps. Thiosulfate ions immediately react with residual ozone and hypobromous acid, reducing them into oxygen and bromide, respectively. This in turn reduces the first target ORP to the second targeted ORP level, which is a desired, safe level. Exemplary reactions for this embodiment is shown below.
[0000] 4O 3 +2S 2 O 3 2− +4OH − →4SO 4 2− +2O 2 +2H 2 O
[0000] Br 2 +2S 2 O 3 2− →2Br − +S 4 O 6 2−
[0100] This is just one example of the possible conversion reaction that could occur in this filtration method. Other neutralizing chemicals, such as sulfur dioxide, ascorbic acid or sodium sulfite, could also be used in addition to or in place of sodium thiosulfate. Alternative embodiments would be obvious to one skilled in the art, in light of the teachings disclosed herein.
[0101] In the example utilizing the exemplary configuration in FIG. 4 , seawater traverses through the filtration and water treatment system and back to the main reservoir 22 . A high level of ozone 104 is injected by venturi into the main line injection point 26 . An exemplary level of ozone could be considered where the residual concentration after reacting with contaminates is greater than 0.02 mg/L. This level is relative, since for an aquarium system it could be considered a high level. For other potential disinfection applications a high level could be a residual ozone concentration of about 0.1 to 0.5 mg/L or greater, such as 0.5 to 1.0 mg/L, for example. Ultimately, it is the targeted ORP level that would be dictating as to the level of disinfection in a first mixing chamber or portion, such as ORP levels above 700 mV to as high as 900 mV, for example.
[0102] The ozone can be introduced via a gas bubble diffuser to produce the fine gas bubbles required for mass transfer. An inline static mixer could be used also to shear the gas bubbles into the process stream and thereby achieve mass transfer. In one example, the injection rate is digitally controlled to maintain an ORP level at an exemplary target set point of 850 mV, measured at the aeration tower inlet 20 . This is one example of a sanitizing oxidation reduction potential. In theory, such a sanitizing oxidation reduction level can be between about 700 mV and about 900 mV. The injected ozone 104 reacts with the seawater, destroying contaminants and disinfects the process stream 14 during its traverse to the aeration tower inlet 20 . A set distance based on pipe diameter, length and flow rates is needed to provide enough time for this first reaction, that includes the introduced at least one oxidant and contaminants, to occur. Exemplary reaction times for most oxidizers are in the order of about three to five minutes. Of course longer or shorter first reaction times may be utilized or necessary in accordance with, for example and not limited to, contamination levels of the water, the amount and/or type of oxidant introduced to the process stream, pipe size and length, among other factors. The optimal reaction times can depend on a number of factors, usually related to the species or target contaminant that is intended to be oxidized. For disinfection of most bacterial, viral and parasitic containing waters, a reaction time of up to five minutes with ozone residual concentrations in the 1 mg/L range is considered to be adequate. Conversely, in some process streams, the reaction time can be significantly shorter, for example 2 to 3 minutes, if the target contaminants have a fast reaction rate with ozone, such as nitrite, iron, hydrogen sulfide, most chromophores, etc.
[0103] While inside aeration tower 18 , sodium thiosulfate 106 is injected into process stream 14 to reduce the first target ORP to a second target oxidation reduction set point, which can be about 600 mV, for example. Other exemplary second target oxidation reduction set points may be achieved in accordance with variables such as water profiles into which effluent water is to be released and/or the presence of flora and/or fauna in areas into which treated water may be released. If, for example, the release point contains aquatic animals that are very sensitive to oxidants, as represented by ORP, and the amount of discharged water is fractionally a high percentage of the overall system volume, the discharge set point could be as low as 220 mV. Exemplary life forms (i.e. flora and fauna) include, but are not limited to, Chordata, Echinodermata, Arthropoda, Mollusca, Cnidaria, Porifera and Angiospermophyta organisms. The discharge stream from an ocean going vessel, such as a cruise ship, is typically highly regulated in accordance with various laws to reduce possible degradation of sensitive aquatic life such as coral reefs. In such instance, it is desirable to be able to control/regulate the effluent discharge stream such that it effectively matches the water conditions around the reef, in terms of oxidant potential, and thus does not cause harm. The injection rate of the at least one neutralizing chemical, here sodium thiosulfate, is controlled and varied, by computer, to achieve the desired second target oxidation reduction set point. At this point in this exemplary embodiment, treated water enters the aquarium and after mixing leaves a residual ORP of 250 mV in the display. Oxidation state sensors/probes in the main reservoir 22 monitor ORP and provide checks that the system is functioning properly.
[0104] Turning to FIG. 6 , an exemplary configuration of exemplary components of a water treatment system in accordance with the teachings of the present disclosure is provided. A water source 110 from which water in process stream 14 in a flow path originates is provided. In this embodiment, the water treatment system is a closed system, that is, water that is taken from water source 110 is taken, treated and then returned back to water source 110 .
[0105] As water in process stream 14 is conducted though the exemplary water treatment system, a first sensor point 112 is reached. Here, a starting oxidation reduction potential is measured and relayed to a master controller 120 . Master controller 120 can be an analog or digital computer. Master controller then compares this starting oxidation reduction potential to a first target oxidation reduction potential set point. Based upon this difference master controller 120 , which is in communication with an oxidant injection controller 118 , communicates this difference to the oxidation injection controller 118 which in turn injects, via at least one oxidant supply/dispenser 116 , at least one oxidant into process stream 14 , at least one oxidant injection point 27 . The at least one oxidant and water then proceed to mix at a first mixing portion 114 of the flow path to raise the starting oxidation reduction potential to a first target oxidation reduction potential set point in order to sanitize process stream 14 of contaminants in the water. The first mixing portion 114 may be a tank or a length of pipe or a section of the flow path having appropriate dimensions to facilitate thorough mixing of water at the at least one introduced oxidant. For example, pipes, for example, greater than 24 in. in diameter, retention basins, or contact chambers configured similarly to storage tanks located in the flow path can be utilized for the first mixing/dosing portion 114 . The target first target oxidation reduction potential set point, in one example, is anywhere from about 700 to 900 mV ORP or any range or ranges therebetween, and can be achieved in any of these vessels whose function is to retain water while the oxidant is introduced until a desired set point is achieved, here a first target oxidation reduction potential set point. Once the target dosing level is achieved the water should remain in the vessel long enough for the desired sanitizing oxidation reactions to occur. In one example, when utilizing ozone, a vessel large enough to retain the water in a dynamic process for two minutes or thereabouts, can be utilized after the target dose, that is, a first target oxidation reduction potential set point, typically 800 mV or thereabouts, is achieved. Of course, this time can be varied in accordance with the final ORP levels desired.
[0106] The water in the flow path then comes upon a second sensor/probe point 122 at which a second oxidation reduction potential is measured. The second sensor/probe point 122 is also in communication with master controller 120 . Master controller then compares this new oxidation reduction potential value, established after introduction and mixing of the at least one oxidant with the water in process stream 14 , with a desired second target oxidation reduction set point. Accordingly, master controller 120 communicates to neutralizing chemical injection controller 128 to introduce an effective amount of at least one neutralizing chemical from at least one neutralizing chemical supply/dispenser 130 . The at least one neutralizing chemical supply/dispenser 130 is in communication with process stream 14 via at least one neutralizing chemical injection point 133 along the flow path. The at least one neutralizing chemical injection point 133 can be located before or in a second mixing portion 132 of the flow path. During the passage of water through second mixing portion 132 , the introduced effective amount of at least one neutralizing chemical reacts with remaining portions of oxidant and other oxidizing species in order to lower the oxidation reduction potential of the water from about the first target oxidation reduction potential set point to the second target oxidation reduction set point. As various useful configurations are contemplated for first mixing portion 114 , various useful configurations of second mixing portion 132 of the flow path are also contemplated, including but not limited to venturi configurations, use of at least one inline static mixer, or gaseous diffusers such as, but not limited to, ceramic “air stones”, bubblers, or specially designed counter current labyrinthal contact chambers, or any combination thereof. A third sensor point 126 , in communication with master controller and downstream of second mixing portion 132 , can be provided so as to monitor effluent oxidation reduction potentials of water emanating from second mixing portion 132 . This would prevent the routing of water back to water source 110 that does not have the proper oxidation reduction potential profile, that is, an oxidation reduction potential that is too high or too low in relation to a desired oxidation reduction potential level or range of oxidation reduction potentials.
[0107] Various effective and accurate water treatment methods are also provide by the teachings of the present disclosure. An exemplary methodology is depicted in FIG. 7 . Some exemplary methods provided herein include a step of obtaining water to be treated 136 from a water source. Such water can originate from various water sources. Water to be treated can originate from a lake, a sea, a stream, an ocean, a storage tank, an aquarium, a swimming pool, a fountain, a river, a contaminated spill area, a delta, a swamp, a pond, a channel, a sewer or a canal. Water to be treated may also come from storage tanks and/or at least one receptacle that are located onboard watercraft and that contain grey and/or black water for example. Grey water is typically used water from showers, sinks or basins, including used kitchen water. Black water is water contaminated with human waste, collected from shipboard toilets. Water to be treated can also originate from food processing stations/areas. Such stations can be food processing stations typically found at meat handling/processing centers, where large volumes of water are utilized during food production and handling, and which, as a result, contain various contaminants such as, but not limited to, intracellular fluid and/or interstitial fluids, blood, fat, bacteria, bodily secretion such as feces, urine, saliva, semen, mucus and the like. In some embodiments, washing of at least one food item takes place at a food processing station.
[0108] Another application to which the water treatment methods and apparatus of the present disclosure may be applied are post harvesting and handling activities of fruits and vegetables, which typically require large volumes of water. Economic considerations and wastewater discharge regulations make water recirculation a common practice in the agriculture industry. Disinfection of water is a critical step to minimize the potential transmission of pathogens from a water source to produce, among produce within a lot, and between lots over time. Water-borne microorganisms, whether postharvest plant pathogens or other pathogens that can cause illness, can be rapidly acquired and taken up on plant surfaces. Natural plant surface contours, natural openings, harvest-and trimming wounds, and handling injuries are known points of entry for microbes. Within these protected sites, microbes are unaffected by common postharvest water treatments. It is essential, therefore, that water used for washing, cooling, transporting, postharvest drenches, or procedures be maintained in a condition suitable for the application, that is, have a controllable and desired oxidation reduction potential. By utilizing and in accordance with the teachings provided herein, water utilized in such operations can be recycled, and money saved, due to the accurate establishment and control of sanitizing oxidation reduction potentials provided by the teachings provided herein.
[0109] Water to be treated 136 has a first oxidation reduction potential measured 138 . A difference between the first oxidation reduction potential measured 138 and a predetermined sanitizing target oxidation reduction potential is determined 140 . Based upon these differences, wherein the predetermined sanitizing target oxidation reduction potential is an ORP higher than the first oxidation reduction potential measured 138 , at least one oxidant is introduced 142 into the water to be treated in order to raise the ORP to the predetermined sanitizing target oxidation reduction potential. Upon introduction of said at least one oxidant to the water to be treated, a first reaction takes place reaction between the at least one oxidant and contaminants in the water, where at least a portion of introduced oxidant is reduced and contaminants in the water are oxidized. A second ORP 146 is measured to check to determine that the predetermined sanitizing target oxidation reduction potential has been reached. This second ORP is then compared to a target effluent oxidation reduction potential and, if existing, the difference between the two is determined 147 , and based upon this comparison, at least one neutralizing chemical is introduced to the water 148 in order to initiate a second oxidation reduction reaction 150 that proceeds between the at least one neutralizing chemical and remaining levels of the at least one oxidant that was introduced into the water and/or other oxidizing species that are in the water. This second oxidation reduction reaction 150 proceeds to a point at which a third ORP is measured 152 and the water attains the target effluent oxidation reduction potential, after which the water is released 160 . The release can be back to the water source from which it came or to storage tanks or other receptacles for transport and/or storage and/or further use.
[0110] In particular embodiments, the water treatment apparatus, systems and methods disclosed herein can be utilized onboard watercraft or with water to be treated that originates from onboard activities. An exemplary depiction of one embodiment of such a water treatment system is shown in FIG. 8 . Water is utilized at various locations onboard a watercraft and collected. Exemplary locations include kitchens 162 , basins 164 , and bathrooms 166 . While only three exemplary locations are depicted, the number of points from which either black and/or grey water can be generated can be as few as one location or many hundreds or even thousand of locations onboard a watercraft, depending on its size. Exemplary watercraft include, but are not limited to, personal boats and house boats, naval vessels, including clippers, destroyers, frigates, battleships, aircraft carriers, support vessels, surface combatants in general, submarines, and patrol boats. Other vessels which can employ the water treatment methods, system and apparatus disclosed herein include cruise ships and other pleasure craft. Water discharge and water pollution by such watercraft are of great concern, particularly when such watercraft are proximate to bodies of water/areas that support ecosystems that can be harmed by water discharged from such watercraft. Such areas include, but are not limited to, coral reefs, lagoons, marshes, stream and river mouths.
[0111] Bathrooms 166 typically include a shower, which can form a portion of the grey water generated onboard, and a toilet, which will contribute to black water generated onboard. From these exemplary locations, water is collected at a central water collection point 110 . From this water source, a process stream is established (arrows in FIG. 8 ) from which a first oxidation potential is measured at a first point by a first sensor probe 168 . First sensor probe 168 , is in communication with a computer 120 and relays this information to computer 120 . Computer 120 then compares this first oxidation potential with a first target oxidation reduction potential set point, which is a sanitizing oxidation reduction potential. Computer 120 is in communication with a first controller 128 that controls introduction (rate/amount) of at least one oxidant from an oxidant supply/dispenser 116 into the process stream of water. Water, now including the introduced at least one oxidant, transverses a first mixing portion 114 of a treatment conduit, where the introduced at least one oxidant and contaminants in the grey and/or black water interact and where the first target oxidation reduction potential set point is established, to disinfect/sanitize the water of process stream. Water in the process stream then contacts a second sensor probe 170 , which is also in communication with computer 120 , which measures a second oxidation reduction potential and transmits the data to computer to computer 120 . Computer 120 then compares this second oxidation reduction potential to a second oxidation reduction potential set point that is an effluent target oxidation reduction potential set point. Based on the comparison of this second oxidation reduction potential to a second oxidation reduction potential set point, computer 120 communicates with a second controller 118 that controls introduction of (rate/amount) of at least one neutralizing chemical into the process stream. Introduction of at least one neutralizing chemical can be before the process steam reaches a second mixing portion 132 of the treatment conduit or directly into the second mixing portion 132 . Water is then mixed with the at least one neutralizing chemical in order to lower the oxidation reduction potential of the water to the second oxidation reduction potential set point. During this reaction, the at least on chemical reacts with any residual amounts of the least one oxidant and other oxidizing species that are in the water, such as hypochlorous acid, hypobromous acid, of the process stream. Exemplary oxidants and neutralizing chemicals include ozone and sodium thiosulfate. A third sensor probe 172 can be placed in the conduit, in communication with computer 120 in order to check and verify that water leaving second mixing portion 132 has an oxidation reduction potential concordant with the second oxidation reduction potential set point. Water is then passed to a final destination 174 . Final destination can be, but is not limited to, a holding tank, a sea, a lake, a stream, an ocean, a storage tank, a river, a delta, a swamp, a pond, a channel, or a canal or any combination thereof.
[0112] In accordance with one aspect of the teachings presented herein, an exemplary process flow diagram for one embodiment is illustrated in FIG. 5 , which depicts an exemplary schematic of an ozone system process flow for water treatment for an aquarium system. Computer 34 (not shown) first determines if the system is being run in a manual or automatic mode at block 510 . In manual mode the system does not function, and thus there is no regulation of ORP potentials. In automatic mode, software is used to control the process as illustrated in FIG. 5 . In one exemplary embodiment, software such as the FactoryFloor product suite including, for example, OptoControl, a graphical flowchart-based development environment with optional scripting, OptoDisplay, a full-featured HMI with advanced trending, OptoServer, an OPC/DDE server, and OptoConnect, a bidirectional interface between databases and control systems as manufactured by Opto 22 (Temecula, Calif., USA) is used to automate the system.
[0113] When running in automatic mode, and as depicted in FIG. 5 ,
[0114] Action Blocks—(Rectangles) contain commands like turning things on and off and setting variables;
[0115] Condition Blocks—(Diamonds) contain commands that decide whether or not a variable is true or not;
[0116] Continue Blocks—(Ovals) contain no commands but route the process to the top of the chart, such as a start routine.
[0117] As indicated at block 500 the program is initiated and starts processing. As indicated at Block 510 , Computer 34 determines if the ozone system has been selected to process the control routine based on a “TRUE” (automatic) or “FALSE” (manual) selection from a human interface. If the operator has not selected to operated the ozone system in automatic mode, the process proceeds with manual operations 515 until an automatic selection has been made.
[0118] Selection of automatic mode prompts at least one ozone injection pump and at least one ozone generator to turn on, as shown at block 520 . Block 530 verifies that all sensors, here ORP sensors, are operating within system tolerances. Subsequent to turning on ozone generators and reading process inputs from an aeration tower inlet ORP sensor, the system will regulate the concentration of ozone based on readings from aeration tower inlet ORP and the pre-determined first target oxidation reduction potential set point, which is a sanitizing level of oxidation reduction potential. This is indicated at block 540 . In this embodiment, at least one thiosulfate pumps are then turned on at block 550 . Block 560 regulates injection of at least one neutralizing chemical, here thiosulfate in solution, based on readings from a second ORP probe/sensor at the aeration tower outlet, as compared to a predetermined effluent set point. The system then processes the readings from the water source, here a main aquarium tank, and determines if the readings are within safe limits, as indicated at block 570 . If the readings are within the safe limits (block 580 ), the process is repeated again. If levels are not found to be safe, then, at block 590 , a safety routine, including a set of instructions which will set oxidant generators/oxidant dispensers, such as ozone generators, output to zero until input readings from the main tank return to a safe level, is run. The process is then repeated over again from the start, as indicated at block 595 .
[0119] The chart shown in FIG. 9 exemplifies performance of one embodiment of the water treatment system disclosed herein, as utilized as part of an aquarium tank/exhibit. The rate that ozone and thiosulfate are injected into the system varies based on the need for oxidizing agents or neutralizing chemicals. By allowing controllers to vary the respective injection rates, the proper oxidation-reduction potential for certain points along the process stream is maintained to coincide with pre-determined set points, as discussed above. This maintains safe levels of oxidizing agents in the water source, from which the process stream originates, and high enough levels in the process stream to achieve desired disinfection. The symbols (closed circle, circle with a cross, open circle, open triangle and closed square) are for illustrative purposes to clearly indicate the various lines in the chart. ORP in milli-volts (mV) is provided on the left hand vertical axis and pump frequency and percent ozone generator output is provided on the right hand vertical axis.
[0120] Pump frequency is generally measured as strokes per minute with a maximum rate of 100 strokes per minute. The volume flow rate of thiosulfate is generally dependent on the initial concentration of the sodium thiosulfate solution and the amount required to reduce the ORP to the ATO set point. This flow rate dynamically changes as the ozone demand in the process water fluctuates. For the current system that is described the thiosulfate flow rate could range from 0 to 350 mL/min. The “percent ozone generator output” is the actual percentage of the total watts that the ozone generator is producing to create the ozone gas. Therefore, the generator at its maximum wattage is at 100% of its ozone generating capability. For the current system that is described the maximum output of ozone is approximately 34 lbs/day or 644 grams/hour. The “percent ozone generator output” is remotely controlled by the computer controller and the PID loop. The right hand axis serves as two different axes. When looking at the “percent ozone generator output” line, the numbers on the right axis represent that percentage, “% Output”, maximum is 100%. When one is looking at the “Thio Freq” data, the frequency of the thiosulfate pump(s), the axis is to be read in strokes per minute, with 100 strokes per minute as the maximum.
[0121] In this one example, the straight line in the graph of FIG. 9 represents the setpoint for the target ORP of the aeration tower inlet 20 . The circle with a cross represents the actual ORP values for the Aeration Tower Inlet (ATI), 20 . The solid circle represents the ORP values for the Aeration Tower Outlet (ATO). This is the controlled target ORP value resulting from the injection of the neutralizing agent. In this example, the ATO setpoint was 600 mV (not shown on the graph of FIG. 9 ) The ATI set point is set at 750 to 800 mV on the graph. The open circle represents the ORP values measured in the main aquarium (main tank) of the exhibit which can be considered in this instance an exemplary main reservoir 22 . The open triangles represent the recorded output, in percentage, of the ozone generator, 104 , as controlled by the PID loop based on the ATI setpoint and actual value. The closed square represents the recorded output of the neutralizing chemical dosage pump. The output of the pump is from 0 to 100 strokes per minute.
[0122] The uses for this technology are numerous. Cruise ships and or large ocean going vessels could use this technology to clean-up waste streams without affecting sensitive coastal environments like coral reefs. Zoos and Aquaria could treat animal environments, cleaning the water and removing harmful bacteria and viruses without causing health problems, e.g. irritated fish gills, corneal damage to sea lions and crocodiles, caused by the oxidizing chemicals.
[0123] While the above description contains many particulars, these should not be consider limitations on the scope of the invention, but rather a demonstration of embodiments thereof. The system, method and apparatus disclosed herein include any combination of the different species or embodiments disclosed. One skilled in the art would recognize that these elements should be interpreted in light of the following claims and any equivalents thereto and/or useful combinations thereof. Accordingly, it is not intended that the scope of the invention in any way be limited by the above description. | The present disclosure provides for a system and method that intensely oxidizes water as it navigates through a system and accurately, controllably neutralizes the oxidation by-products before the water exits the system. | 2 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to subsea production of hydrocarbons. More specifically, the invention relates to a system and method to provide flow/pressure boosting in a subsea environment.
2. Description of the Related Art
Petroleum development and production must be sufficiently profitable over the long term to withstand a variety of economic uncertainties. Booster pumping is increasingly being used to aid in the production of wellhead fluids. Subsea installations of these pumps are particularly helpful in producing remote fields and many companies are considering their use for producing remote pockets of oil and for producing deep water reservoirs from remote facilities located in shallower water. Such booster pumps allow producers to transport multiphase fluids (oil, water, and gas) from the wellheads to remote processing facilities (instead of building new processing facilities near the wellheads and often in deep water). These booster pumps also allow fluid recovery at lower final reservoir pressures before abandoning production. Consequently, there is a greater total recovery from the reservoir.
For deep water reservoirs, booster pumps are used to transport wellhead fluids from deep water wellheads to remote processing facilities located in shallower water. While there are a number of technical difficulties in this type of production, the cost savings are very large. Consequently, producers would like to transport wellhead fluids from the seafloor in deep waters through pipelines to remote processing facilities in moderate water depths. Transport distances of tens of kilometers are not uncommon with longer distances currently in the planning stages.
Commonly available booster pumping systems commonly include a submersible pump installed in the producing well or a pumping system connected to a subsea Christmas tree manifold attached to the wellheads from which fluids flow as a result of indigenous reservoir energy. The other end of the pumps are connected to a pipeline which transports the fluids from the wellhead to the remote processing site. Submersible pumps and their operation, including their installation, are well known and understood in the art. A problem, however, is that should a failure occur, valuable production flow can be interrupted while the pump is repaired. Subsea pumping systems connected externally to the producing well are typically unique to each application and require modifications and adaptations of surface pumps to the subsea environment. Such systems are typically more expensive and more difficult to install than submersible pumps.
Wellhead fluids can exhibit a wide range of chemical and physical properties. These wellhead fluid properties can differ from zone to zone within a given field and can change with time over the course of the life of a well. Furthermore, well bore flow exhibits a well-known array of flow regimes, including slug flow, bubble flow, stratified flow, and annular mist, depending on flow velocity, geometry, and the aforementioned fluid properties. Consequently, the ideal pumping system should allow for a broad range of input and output parameters without unduly compromising pumping efficiency and service life. Submersible pumps typically operate at conditions of lower gas fractions than seafloor mounted systems and thus exhibit fewer problems from such multi-phase flows.
The methods and apparatus of the present invention overcome the foregoing disadvantages of the prior art by providing a submersible pump system that provides flow/pressure boosting and does not jeapordize production flow during downtime.
SUMMARY OF THE INVENTION
The present invention contemplates a subsea pumping system for boosting the flow energy of a production flow.
In one aspect, the present invention is a system for producing hydrocarbon fluids from a subsea formation, comprising at least one producing well penetrating the formation for producing hydrocarbon fluids. At least one dummy well is hydraulically connected to the at least one producing well for routing the hydrocarbon fluids from the producing well to the dummy well. At least one pump is disposed in the at least one dummy well. The pump takes suction flow from the dummy well and boosts the flow energy of the discharge flow of hydrocarbon fluids.
In another aspect, the present invention describes a method for producing hydrocarbon fluids from a subsea formation, comprising installing at least one pump in at least one dummy well where the dummy well is hydraulically connected to at least one producing well. The at least one dummy well acts as a suction reservoir for the pump. Production flow is routed from the producing well to the dummy well where the pump is used for imparting flow energy to the production flow.
Examples of the more important features of the invention thus have been summarized rather broadly in order that the detailed description thereof that follows may be better understood, and in order that the contributions to the art may be appreciated. There are, of course, additional features of the invention that will be described hereinafter and which will form the subject of the claims appended hereto.
BRIEF DESCRIPTION OF THE DRAWINGS
For detailed understanding of the present invention, references should be made to the following detailed description of the preferred embodiment, taken in conjunction with the accompanying drawings, in which like elements have been given like numerals, wherein:
FIG. 1 is a schematic drawing of a subsea flow system according to one preferred embodiment of the present invention;
FIG. 2 is a schematic drawing of a booster pumping system according to one preferred embodiment of the present invention;
FIG. 3 is a flow diagram according to one preferred embodiment of the present invention; and
FIG. 4 is a flow diagram according to another preferred embodiment of the present invention.
DESCRIPTION OF PREFERRED EMBODIMENTS
FIG. 1 shows a production system according to one embodiment of the present invention. Producing well 1 is shown penetrating a hydrocarbon bearing formation 2 at some depth below the seafloor 18 . Well 1 is completed using any of the myriad of common techniques known in the art. Well 1 may be a vertical well as shown or, alternatively, may be highly inclined including horizontal. Formation fluid 3 flows up the wellbore 19 to a wellhead 4 . The fluid 3 may be single phase or multiphase. Multiphase as used herein means (i) oil, water, and gas; (ii) oil and water; (iii) oil and gas; and (iv) water and gas. Well 1 is located at some distance from subsea processing station 12 where the distance may be on the order of tens of kilometers. As previously indicated, in many such cases, the pressure of the formation driving the flow of fluid, such as fluid 3 , is insufficient to force adequate flow to reach processing station 12 . Booster pumping system 40 is installed to provide sufficient flow energy to force adequate flow to reach the processing station 12 .
Booster pumping system 40 (see FIG. 1 and FIG. 2 ), in one preferred embodiment, comprises a dummy well 7 extending to a predetermined depth below the seafloor 18 . Dummy well 7 is drilled and cased with casing 44 using techniques known in the art. Dummy well 7 may be drilled and cased at the time that producing well 1 is drilled using the same rig (not shown) used to drill well 1 . Alternatively, dummy well 7 may be drilled at any time using coiled tubing supported by a surface vessel equipped with coiled tubing equipment and using techniques known in the art. Wellhead 6 is attached to the top of dummy well 7 and flow conduit 5 connects producing wellhead 4 to dummy wellhead 6 . Conduit 5 enables flow of fluid 3 from producing well 1 to dummy well 7 . Liner 10 is hung off from wellhead 6 and extends to near the bottom of dummy well 7 . A pump string 60 comprising submersible pump 8 , motor 9 , and tubing 17 is run into liner 10 on tubing 17 and hung off from wellhead cap 41 . Tubing 17 may be a length of coiled tubing. Alternatively, tubing 17 may be lengths of threaded tubing joined together. In a preferred embodiment, electrical conductors 43 are run inside tubing 17 and connect motor 9 to power source 21 through a wet-mateable connector 49 . Such connectors are known in the art and are not described here. Alternatively, electrical conductors 43 may be attached to the outside of tubing 17 using techniques known in the art.
The inlet to pump 8 is sealed to the liner 10 by seal 42 directing fluid 3 in the annulus 45 between casing 44 and liner 10 to enter pump 8 . Well 7 depth is selected to provide sufficient suction pressure to allow pump 8 to operate at a desired efficiency. For example, for cases where a substantial portion of fluid 3 is liquid, the dummy well 7 may be just deep enough to fit a submersible pump string, on the order of 100 to 200 feet. In cases where there is a substantial gas fraction in fluid 3 , the depth of dummy well 7 may be significantly deeper, on the order of 1000 feet. The increased depth reduces the gas-oil ration (GOR) due to increased pressure, and may also act to drive the gas back into solution in the liquid, both such conditions resulting in significantly increased pump efficiency. Such determinations are specific to each application. For cases where there is substantial gas entrained in the flow, vanes 47 may be attached to the outside of liner 10 to break up any large bubbles and mix the gas in the liquid phase as the flow passes the vanes 47 . Vanes 47 may be spirally attached to the liner 10 .
Flow 50 exits pump 8 with increased flow energy as compared to the inlet flow 3 . Flow 50 travels up in annulus 46 and exits through pipeline 11 and travels to subsea processing station 12 (see FIG. 1) for further processing and distribution. Sensors 50 , 51 , 30 , 31 , 32 , and 33 may be placed in the flow lines at multiple locations to characterize the flow conditions. Such sensors may be adapted to measure parameters of interest including, but not limited to (i) wellhead pressure at the producing well; (ii) hydrocarbon flow rate at the producing well; (iii) gas fraction at the wellhead; (iv) pressure in the dummy well; (v) pump discharge pressure; and (vi) pump discharge flow rate. Additional sensors may be connected to motor 9 for performance monitoring.
As shown in FIG. 1 and FIG. 2, the submersible pump 8 and motor 9 are insertable and extractable using a coiled tubing reel 14 and coiled tubing 15 operated from a surface vessel 16 which may be a light intervention type vessel of a type known in the art.
In one preferred embodiment, shown in FIG. 3, three booster pumping systems 40 a-c are connected with producing well 1 through manifold system 50 . Manifold system 50 comprises valves 22 and 23 for directing flow from producing well 1 to any combination of booster pumping systems 40 a-c. Typically each booster pumping system will be sized such that two of pumping systems 40 a-c are always used, thereby providing a spare pump for high reliability. It should also be noted that multiple pumps may be installed in a pump string to increase reliability and/or flow output.
In operation, for example, if one of pumps 40 a-c fails, the failed pump system may be isolated using the appropriate valves 22 and 23 . Coiled tubing 15 is lowered from vessel 16 . A suitable connector (not shown) on coiled tubing 15 is attaches to connector 48 on cap 41 and extracts pump string 60 from dummy well 7 . The pump string 60 is repaired or replaced and reinserted back in dummy well 7 and put back in service as needed.
A subsea controller 65 (see FIG. 2) controls the pumping systems 40 a-c. The controller may contain circuits for interfacing with various sensors and controlling the motor 9 and the valves 23 and 22 according to sensor data and programmed instructions. The subsea controller also contains communication circuits and communicates with other subsea systems such as processing station 12 and/or surface controllers (not shown).
In another preferred embodiment, see FIG. 4, three producing wells 1 a-c are connected to flow control manifold 70 . Manifold 70 directs the flow to pumping systems 140 a-c as required. While three producing wells 1 a - 1 c are shown, any number of producing wells may be connected to such a booster pumping system. In any such system, the pumps will be sized for the appropriate flows.
In all of the previously disclosed booster pump systems, a flow bypass system such as bypass 67 (see FIG. 3) may be incorporated to bypass the booster pump and allow natural (unboosted) production flow should such a need arise, for example with a failure of pump power. Such a bypass may have a remotely operated valve 66 for enabling such a bypass flow.
A system has been disclosed wherein a number of industry proven devices and techniques are combined in a novel arrangement to provide pressure/flow boosting to a production flow in a subsea environment. A dummy well is used to act as a suction reservoir for a submersible pump disposed in the dummy well. The dummy well has a case dependent depth to provide increased suction pressure resulting in improved pump efficiency, especially for flows with high gas content. The submersible pump is insertable and retrievable from a surface vessel using coiled tubing techniques. Multiple pumps may be inserted in one dummy well. In addition, multiple dummy wells with pumps may be manifolded to one or more producing wells.
The foregoing description is directed to particular embodiments of the present invention for the purpose of illustration and explanation. It will be apparent, however, to one skilled in the art that many modifications and changes to the embodiment set forth above are possible without departing from the scope of the invention. It is intended that the following claims be interpreted to embrace all such modifications and changes. | A system for producing hydrocarbon fluids from a subsea formation includes at least one producing well penetrating the formation for producing hydrocarbon fluids. At least one dummy well is hydraulically connected to the at least one producing well for routing the hydrocarbon fluids from the producing well to the dummy well. At least one pump is disposed in the at least one dummy well. The pump takes suction flow from the dummy well and boosts the flow energy of the discharge flow of hydrocarbon fluids. | 4 |
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